 | MAEKAWA MasahikoScience and Technology Research Institute Professor | ||
Last Updated :2024/04/25
Researcher Information
Degree
URL
Research funding number
- 70229293
ORCID ID
J-Global ID
Research Interests
- 有機金属化学 錯体化学 配位高分子 Orgamometallic Chemistry Coordination Chemistry Coordination polymers
Research Areas
Academic & Professional Experience
- 2010/04 - Today Kinki UniversityResearch Institute for Science and TechnologyProfessor
- 2003/04 - 2010/03 Kinki UniversityResearch Institute for Science and TechnologyAssociate Professor
- 1999/04 - 2003/03 Kinki UniversityResearch Institute for Science and TechnologyAssistant Professor
- 1990/04 - 1999/03 Kinki UniversityResearch Institute for Science and Technologyresearch associate
- 1995/08 - 1996/08 The University of LiverpoolDepartment of ChemistryPostdoctoral Research Fellow
Education
- 1987/04 - 1990/03 Kinki University Graduate School of Chemistry Department of Chemistry (Doctor Course)
- 1985/04 - 1987/03 Kinki University Graduate School of Chemistry Department of Chemistry (Master Course)
- 1981/04 - 1985/03 Kinki University Faculty of Science and Engineering Department of Chemistry
Association Memberships
Published Papers
- Tomoki Nishiyama; Hirotaka Kitoh-Nishioka; Senku Tanaka; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Masaki Yoshida; Masako Kato; Takashi OkuboDalton Transactions Royal Society of Chemistry (RSC) 53 (4) 1445 - 1448 1477-9226 2024/02 [Refereed]
A photoconductive luminescence coordination polymer having an infinite two-dimensional (2D) structure containing copper(I) thiocyanate and a nitrogen-containing π-conjugated ligand. - Masahiko Maekawa; Terumasa Hayashi; Kunihisa Sugimoto; Takashi Okubo; T. Kuroda-SowaDalton Transactions Royal Society of Chemistry (RSC) 52 (41) 14941 - 14948 1477-9226 2023/11 [Refereed]
Novel four di-, tetranuclear and polymeric Cu(I)–bpprd/C2H4 complexes were anion-dependently prepared by the reactions of [Cu(C2H4)n]X (X = ClO4–, NO3–, BF4–) with 2,4-bis(2-pyridyl)pyrimidine (bpprd) in Me2CO under C2H4 and they... - Masahiko Maekawa; Shoki Oda; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-SowaRESULTS IN CHEMISTRY ELSEVIER 4 100550 2211-7156 2022/10 [Refereed]
The reactions of [Ir(H)(2)(PPh3)(2)(tptz)]PF6 (1) (tptz = 2,4,6-tris(2-pyridyl)-s-triazine) with {Cu(I), Ag(I)} salts under Ar afforded heterometallic trinuclear {Cu(I), Ag(I)}-Ir(III)-tptz hydride complexes [CuIr2(H)(4)(PPh3)(4)(tptz)(2)](PF6)(3)center dot 2Me(2)CO (2), [AgIr2(H)(4)(PPh3)(4)(tptz)(2)](PF6)(3)center dot 4Me(2)CO center dot H2O (3a) and [AgIr2(H)(4)(PPh3)(4)(tptz)(2)] (CF3SO3)(2)(PF6)center dot 4Me(2)CO (3b). We have demonstrated that Ir(III)-tptz complex 1 can serve as a potentially bridgeable Ir metalloligand. X-ray analyses showed that meaningful intramolecular pi-pi stacking interactions exist in {Cu(I), Ag(I)}-Ir(III)-tptz hydride complexes 2, 3a and 3b. These intramolecular pi-pi stacking interactions could be contributed to the structural stabilization of the distorted boat-shaped structure. H-1 and P-31 NMR analyses showed that the structures of {Cu(I), Ag(I)}-Ir(III)-tptz hydride complexes 2 and 3a are kept in solution. The significant H-1 NMR upfield shifts could be induced by the ring current effect from the phenyl groups of adjacent PPh(3 )ligands. - Naohiro Takahashi; Tomoki Nishiyama; Takuto Mibu; Yusaku Suenaga; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaInorganica Chimica Acta Elsevier BV 541 121095 - 121095 0020-1693 2022/10 [Refereed]
- Tomoki Nishiyama; Naohiro Takahashi; Takuto Mibu; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Yusaku Suenaga; Takashi OkuboResults in Chemistry Elsevier BV 4 100470 - 100470 2211-7156 2022/08 [Refereed]
- Masahiko Maekawa; Mafuyu Yabuta; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-SowaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 528 120628 0020-1693 2021/12 [Refereed]
The reactions of [Cu(MeCN)(4)]PF6 or [Cu(C2H4)(n)]ClO4 with 2,2' :6',4 ''-terpyridine (2,2' :6',4 ''-terpy) in MeOH under C2H4 afforded dinuclear Cu(I) complexes [Cu2(2,2' :6',4 ''-terpy)(2)](PF6)(2) (1) and [Cu-2(2,2':6',4 ''-terpy)(2)(ClO4)(2)] (2), respectively. In complex 1, the Cu(I) atom is coordinated by one N atom in the terminal site of 2,2' :6',4 ''-terpy and two N atoms in the chelate site of another 2,2':6',4 ''-terpy in the distorted trigonal-planar geometry. In complex 2, the Cu(I) atom is coordinated by one N atom in the terminal site of 2,2' :6',4 ''-terpy, two N atoms in the chelate site of another 2,2' :6',4 ''-terpy and one O atom of ClO4 anion in the distorted trigonal-pyramidal geometry. In both of complexes 1 and 2, two Cu(I) atoms are bridged by two 2,2' :6',4 ''-terpy in the head-to-tail fashion to form dinuclear Cu(I) complexes with a rectangular [Cu-2(2,2' :6',4 ''-terpy)(2)](2+) framework. In contrast, the reaction of [Cu(MeCN)(4)]PF6 with 2,2':6',4 ''-terpy in MeOH/CHCl3 under C2H4 afforded 1D Cu(I) coordination polymer {[Cu-2(2,2' :6',4 ''-terpy)(2)(C2H4)](PF6)(2)center dot CHCl3 center dot MeOH}(n) (3). One Cu(I) atom is coordinated by four N toms in the chelate sites of two 2,2':6',4 ''-terpy in the head-to-head fashion to form a distorted tetrahedral geometry. The other Cu(I) atom is coordinated by two N toms in the terminal sites of two 2,2' :6',4 ''-terpy in the tail-to-tail fashion and the C=C bond of C2H4 to form a trigonal-planar structure. These Cu (I) atoms are in turns bridged by 2,2' :6',4 ''-terpy in the two kinds of head-to-head and tail-to-tail fashions to form a unique 1D helical chain structure. When the complex 2 was dissolved in MeCN and the resultant red-brown solution was diffused with diethyl ether, Cu(I) coordination polymer {[Cu-2(2,2' :6',4 ''-terpy)(2)(MeCN)(2)] (ClO4)(2)}(n) (4) was collected. The Cu(I) atom is coordinated by two N atoms in the chelate site of 2,2' :6',4 ''-terpy, one N atom in the terminal site of another 2,2' :6',4 ''-terpy and one N atom of MeCN in the distorted tetrahedral geometry. The Cu(I) atoms are in turns bridged by 2,2' :6',4 ''-terpy in the head-to-tail fashion to form a unique 1D helical chain structure. - Takuto Mibu; Atsushi Iba; Yusaku Suenaga; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Kunihisa SugimotoInorganica Chimica Acta Elsevier BV 527 120538 - 120538 0020-1693 2021/11 [Refereed]
- Kouichi Matsumoto; Kazuhiro Yamashita; Yuuki Sakoda; Hinata Ezoe; Yuki Tanaka; Tatsuya Okazaki; Misaki Ohkita; Senku Tanaka; Yuki Aoki; Daisuke Kiriya; Shigenori Kashimura; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Takashi OkuboEUROPEAN JOURNAL OF ORGANIC CHEMISTRY WILEY-V C H VERLAG GMBH 2021 (33) 4620 - 4629 1434-193X 2021/09 [Refereed]
New star-shaped non-fullerene acceptors (5Z,5 ' Z,5 '' Z)-5,5 ',5 ''-((benzo[1,2-b : 3,4-b ' : 5,6-b '']trithiophene-2,5,8-triyltris(4-octylthiophene-5,2-diyl))tris(methaneylylidene))tris(3-octyl-2-thioxothiazolidin-4-one) (1: BTT-OT-ORD) and 2,2 ',2 ''-((5Z,5 ' Z,5 '' Z)-((benzo[1,2-b : 3,4-b ' : 5,6-b '']trithiophene-2,5,8-triyltris(4-octylthiophene-5,2-diyl))tris(methaneylylidene))tris(3-octyl-4-oxothiazolidine-5,2-diylidene))trimalononitrile (2: BTT-OT-OTZDM) with a benzotrithiophene core, alkyl-thiophen units, and acceptor units were designed and synthesized. The HOMO-LUMO levels of 1 and 2 were determined by photoemission spectroscopy and UV-Vis absorption spectroscopy. Binary blend and ternary blend bulk heterojunction (BHJ) organic solar cells with non-fullerene acceptors 1 and 2 were fabricated with the inverted device structures of glass/ITO/ZnO/active_layer/MoO3/Ag. Both binary blend BHJ solar cells with 1 and 2 show lower J(SC) and larger V-OC values than P3HT : PCBM solar cells. On the other hand, ternary blend BHJ organic solar cells, including 10 % of 1, exhibited a larger power conversion efficiency than P3HT : PCBM solar cells because the J(SC) value was largely improved. - Yusaku Suenaga; Takuto Mibu; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Kunihisa SugimotoDalton transactions (Cambridge, England : 2003) 50 (31) 10983 - 10983 2021/08 [Refereed]
Correction for 'Dinuclear cobalt complexes with a redox active biphenyl bridging ligand [Co2(BP)(tqa)2](PF6)2 (H4BP = 4,4'-bis(3-tert-butyl-1,2-catechol), tqa = tris(2-quinolylmethyl)amine): structure and magnetic properties' by Yusaku Suenaga et al., Dalton Trans., 2021, DOI: . - Yusaku Suenaga; Takuto Mibu; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Kunihisa SugimotoDALTON TRANSACTIONS ROYAL SOC CHEMISTRY 50 (28) 9833 - 9841 1477-9226 2021/07 [Refereed]
The biscatechol, H4BP (4,4’-bis(3-tert-butyl-1,2-catechol)) that connects two redox active catechol moieties directly was synthesized. Also, tpa (tris(2-pyridylmethyl)amine), bpqa (bis(2-pyridylmethyl)(2-quinolylmethyl)amine), pbqa ((2-pyridylmethyl)bis(2-quinolyl methyl)amine), and tqa (tris(2-quinolylmethyl)amine) were synthesized as terminal ligands...
- Kunihisa Sugimoto; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaCRYSTAL GROWTH & DESIGN AMER CHEMICAL SOC 21 (7) 4178 - 4183 1528-7483 2021/07 [Refereed]
Single crystals of an iron(II) spin crossover (SCO) complex containing an N2O Schiff base ligand, [Fe-II(qsal-COOH)(2)], were successfully prepared. The crystal structures from a single-crystal X-ray diffraction study were obtained at 100 and 170 K and yielded information regarding both the low-spin and high-spin states, without any crystal breakage being observed after the phase transition. Structural analysis was performed to visualize the origin of the SCO phenomenon in the [Fe-II(qsal-COOH)(2)] complex. We report that the fundamental requirements for an abrupt SCO, particularly in Fe-qsal complexes, are not only a combination of weak interaction effects, such as pi-pi, P4AE (parallel four-fold aryl embrace), and hydrogen bonding, but also the presence of solvents in the crystalline structure, since the solvent molecules can influence the interactions between the [Fe-II(qsal-X)(2)] molecules. - Misaki OHKITA; Aya FUJIWARA; Tomoki NISHIYAMA; Masahiko MAEKAWA; Takayoshi KURODA-SOWA; Takashi OKUBOX-ray Structure Analysis Online Japan Society for Analytical Chemistry 37 (6) 29 - 31 2021/06 [Refereed]
- Masahiko Maekawa; Kota Terada; Shoki Oda; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-SowaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 514 119962 0020-1693 2021/01 [Refereed]
The reactions of [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]X (X = PF6, BF4) with terpy in CHCl3, Me2CO and CH2Cl2 under Ar afforded three novel Ir(III)-hydride complexes 1-3 by the choices of solvents and anions. Ir(III)-terpy hydride complexes [Ir(H)(2)(PPh3)(2)(terpy-kappa(2)/N,N')]PF6 center dot CHCl3 (1) and [Ir(H)(2)(PPh3)(2)(terpy-kappa N-2,N')]BF4 center dot Me2CO (2) with two cis hydride atoms, two PPh3 and terpy-kappa N-2,N' possess a octahedral N2P2H2 coordination mode, while pincerlike Ir(III)-terpy hydride complex {[Ir(H)(PPh3)(2)(terpy-kappa(3)/N,N',N '')](BF4)(2)center dot 2CH(2)Cl(2)}(2) (3) with one hydride atom, two PPh3 and terpy-kappa N-3,N',N '' possess a octahedral N3P2H coordination mode. H-1 NMR analyses showed that the asymmetric and symmetric structures of three Ir(III)-terpy hydride complexes 1-3 are kept in solution. It was found that the significant H-1 NMR upfield shifts could be induced by the ring current effect from the phenyl groups of adjacent PPh3 ligands. - K. Matsumoto; M. Matsumoto; T. Hayashi; M. Maekawa; K. Nishiwaki; S. KashimuraElectrochemitry The Electrochemical Society of Japan 88 (4) 314 - 320 1344-3542 2020/08 [Refereed]
The electrochemical reduction of anthracenes in the presence of esters and chlorotrimethylsilane in LiClO4/THF in the undivided cell equipped with magnesium electrodes affords the corresponding cyclized products at low to moderate yields. Herein, the chemical structure of the product is determined by X-ray analysis, as well as 1H NMR, 13C NMR, and HRMS. The in situ generation of magnesium anthracenes is indicated. The scope and limitations of the current reactions using anthracene and its derivatives with various esters are investigated.
- Takuto Mibu; Yusaku Suenaga; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaINORGANIC CHEMISTRY COMMUNICATIONS ELSEVIER 114 107826 1387-7003 2020/04 [Refereed]
Co-dioxolene complex [Co(DBCat)(pbqa))(PF6) (DBCat = 3,5-di-tert-butylcatechol, pbqa = (2-pyridylmethyl)bis (2-quinolylmethyl)amine), was prepared from methanol solution. Single crystal X-ray structural analysis revealed that the valence of the cobalt ion to be + III, as DBCat is formally a catecholate dianion, whereas the acetonitrile solution exhibits an MLCT absorption near 575 nm, suggesting it is present as hs-Co-II (SQ). Of note, this MLCT band disappears with decreasing temperature. This behavior suggests that [Co(DBCat)(pbqa)1(PF6) undergoes a temperature-dependent change from hs-Co-II(SQ) to ls-Co-III(Cat). Magnetic susceptibility vs. temperature data for the compound displayed a gradual variation over 250 K, due to intramolecular electron transfer in the solid-state as well. (Co(DBCat)(pbqa)](PF6) demonstrates valence tautomerism due to a strong pi-pi interaction between the quinoline rings of the ancillary ligand. Comparison of this pbqa compound to similar Co compounds provides further evidence for these conclusions. - Masahiko Maekawa; Terumasa Hayashi; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-SowaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 497 119088 0020-1693 2019/11 [Refereed]
The reaction of [Cu(MeCN)(4)]X (X = BF4, PF6) with 2,2': 5', 4 ''-terpyridine (2,2': 5', 4 ''-terpy) in MeOH/MeCN under Ar/C2H4 afforded 1-D Cu(I) coordination polymers {[Cu(2,2': 5', 4 ''-terpy)(MeCN)]BF4}(n) (1) and { { [Cu (2,2': 5', 4 ''-terpy)(MeCN)]PF6}(2)center dot H2O}(n) (2). In complex 1, the tetrahedral Cu(I) atoms are bridged by 2,2': 5', 4 ''-terpy in the head-to-tail fashion to form an infinite 1-D zigzag chain structure. In complex 2, there are two independent infinite 1-D zigzag chain structures along the b- and c-axises in the unit cell. The weak intermolecular pi center dot center dot center dot pi stacking interactions exist between opposite 2,2':5', 4 ''-terpy ligands. The PF6- anions are surrounded by four opposite MeCN molecules in two crossed zigzag chains. In contrast, the reaction of [ Cu( MeCN) 4] PF6 with 2,2':5', 4 ''-terpy in Me2CO/MeCN under Ar/C2H4 afforded Cu(I) metallomacrocycle [Cu-4(2,2':5', 4 ''-terpy) 4](PF6)(4)center dot 5Me(2)CO (3). Four Cu(I) atoms are bridged by the four 2,2':5', 4 ''-terpy in a head-to-tail fashion to afford a rhombic Cu(I) metallomacrocycle. One distorted Me2CO molecule is encapsulated in the central vacant space of [Cu-4(2,2':5', 4 ''-terpy)(4)](4+) core and two PF6- anions are sandwiched between the rhombic Cu(I) metallomacrocyclic layers. The reactions of Cu(NO3)(2)center dot 3H(2)O and Cu turnings with 2,2':5',4 ''-terpy in MeOH/MeCN under Ar afforded 1-D Cu(I) coordination polymer {[Cu(2,2':5', 4 ''-terpy)(MeCN)]NO3}(n) (4). It has been proved that complex 4 could be induced by the autoreduction of Cu(II) species to Cu(I) species. - Takuto Mibu; Yusaku Suenaga; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaX-RAY STRUCTURE ANALYSIS ONLINE JAPAN SOC ANALYTICAL CHEMISTRY 35 (10) 61 - 62 1883-3578 2019/10 [Refereed]
The reaction of a methanol solution containing Co(BF4)(2)center dot 6H(2)O and (2-pyridylmethyl)bis(2-quinolylmethyl)amine (pbqa) afforded a dinuclear cobalt(II) complex, [Co-2(mu-F)(2)(pbqa)(2)](BF4)(2), where the two metal centers are doubly bridged by two fluoride ions. BF4- is a fluoride source. A temperature-dependent magnetic susceptibility measurement reveal that a strong spin orbit contribution with a zero-field splitting effect of two high-spin Co(II) ions. It crystallizes in the monoclinic space group C2/c with a = 24.9600(9)angstrom, b = 11.1533(3)angstrom, c = 20.0575(6)angstrom, alpha = 90 degrees, beta = 109.439(4)degrees, gamma = 90 degrees, V = 5265.4(3)angstrom(3), D-calc = 1.535 g/cm(3), and Z = 4. The R1 [I > 2 sigma(I)] and wR2 (all data) values are 0.0403 and 0.1018, respectively, for all 7897 independent reflections. - Yusaku Suenaga; Takuto Mibu; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 171 480 - 485 0277-5387 2019/10 [Refereed]
Two types of biscatechol, namely H(4)L1 (5,5'-(buta-1,3-diyne-1,4-diyl)bis(3-t-butylcatechol)) and H(4)L2 (5,5'-(ethyne-1,2-diyl)bis(3-t-butylcatechol)) were synthesized. In these ligands, two redox active catechol moieties are connected by one or two triple bonds. Also, tpa (tris(2-pyridylmethyl) amine), bpqa (bis(2-pyridylmethyl)(2-quinolylmethyl)amine) and pbqa ((2-pyridylmethyl)bis(2-quinolylmethyl)amine) were synthesized as terminal ligands of the tetracoordinated tripod type. In total, six dinuclear Co complexes were synthesized from these biscatechol and terminal ligands as follows: [Co-2(L1)(tpa)(2)](BF4)(2) (1), [Co-2(L1)(bpqa)(2)](PF6)(2) (2), [Co-2(L1)(pbqa)(2)](PF6)(2) (3), [Co-2(L2)(tpa)(2)](BF4)(2) (4), [Co-2(L2)(bpqa)(2)](PF6)(2) (5), [Co-2(L2)(pbqa)(2)](PF6)(2) (6). Of the six dinuclear Co complexes, complex 6, which was isolated as a mixed valent state Co-II(HS)-[SQ-Cat]-Co-III(LS) compound, showed an absorption intensity at around 703 nm (MLCT bands) that increased with increasing temperature in acetonitrile solution. In addition, an investigation of the magnetic properties of the complex 6 with SQUID showed that the chi T-M value gradually increased as the temperature increased from 150 to 380 K. This suggests that a transition from Co-III(LS) (S = 0) to Co-II(HS) (S = 3/2) accompanies the temperature rise. This means the steric hindrance and electronic effect of the quinolyl groups around the Co ion produce a coordination atmosphere weaker than that of pyridyl groups, with the result that the Co-III ions easily convert to Co-II ions. (C) 2019 Elsevier Ltd. All rights reserved. - Takashi Okubo; Kento Himoto; Koki Tanishima; Sanshiro Fukuda; Yusuke Noda; Masanobu Nakayama; Kunihisa Sugimoto; Masahiko Maekawa; Takayoshi Kuroda-SowaInorganic Chemistry American Chemical Society 57 (5) 2373 - 2376 0020-1669 2018/03 [Refereed]
A new semiconducting 3D coordination polymer, [Cu2Br2(ttz)]n (1), with an acceptor bridging ligand, 1,2,4,5-tetrazine (ttz), was synthesized. The complex shows large absorption bands extending to the near-IR region, indicating a small band gap in the coordination polymer. This complex shows higher conductivity than those of [CuBr(pyz)]n (2), including pyrazine (pyz) with a higher lowest unoccupied molecular orbital level. We performed density functional theory band calculations using the VASP program to understand the electronic states and conducting paths of the coordination polymer. - Kento Himoto; Toshiya Horii; Takumi Syoji; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaInorganic Chemistry Communications Elsevier B.V. 88 34 - 37 1387-7003 2018/02 [Refereed]
A new one-dimensional coordination polymer, [CuII(3-Py-CHO)]n (3-Py-CHO = 3-pyridinecarboxaldehyde), consisting of an infinite copper(I)-iodide ladder chain and a pendant ligand, 3-Py-CHO, was prepared and structurally characterized using X-ray diffraction analysis. This material shows semiconducting properties with a relatively small activation energy, as shown by impedance measurements. We also estimated the electrical conductivity from a current-voltage (I-V) curve measured from a single crystal of the coordination polymer. - Kento Himoto; Toshiya Horii; Shoki Oda; Shimpei Suzuki; Kunihisa Sugimoto; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaActa Crystallographica Section E: Crystallographic Communications International Union of Crystallography 74 233 - 236 2056-9890 2018/02 [Refereed]
A new heterometallic CuI-NiII coordination polymer, poly[[tetra-3-iodido-2-iodido-bis(3-piperidine-1-dithiocarbamato)propionitrilepentacopper(I)nickel(II)] chloroform monosolvate], {[CuI 5NiIII5(C6H10NS2)2(C3H5N)]CHCl3}n, has been synthesized and structurally characterized. This coordination polymer consists of an NiII mononuclear unit of NiII(Pip-dtc)2 (Pip-dtc is piperidine-1-dithiocarbamate) and a pentanuclear copper(I) cluster unit of Cu5I5(CH3CH2CN). The NiII ion, which lies on an inversion centre, is surrounded by four S atoms in a square-planar coordination geometry while all CuI ions have distorted tetrahedral coordination geometries. In the pentanuclear copper(I) cluster unit, a mirror plane passes through one CuI ion and three I ions. All the S atoms in NiII(Pip-dtc) are also coordinated by the CuI ions, forming an infinite zigzag chain structure along the b-axis direction. The chains are weakly connected by solvent CHCl3 molecules via Cl I [3.653 (1) Å] and Cl S [3.4370 (1) Å] short-contact interactions. - Kunihisa Sugimoto; Hikaru Takaya; Masahiko Maekawa; Takayoshi Kuroda-SowaCrystal Growth and Design American Chemical Society 18 (2) 571 - 575 1528-7505 2018 [Refereed]
The reaction of Ni(mnt)2 (mnt = 1,2-dicyano-1,2-ethylenedithiolate) with CuI in THF results in the formation of a Ni(mnt)2Cu4I4 unit with an eight-membered Cu4I4 crown motif. Coordination polymers with Ni(mnt)2Cu4I4 building units, having doubly bridged 1-D chains, were formed with bulky NBu4 counterions. To pack the bulky NBu4 cations into the crystal structure, no direct interactions between the 1-D chain structures are observed. When the bulky NBu4 cations are exchanged for small sodium cations, direct interactions between the 1-D chain structures dominate. A doubly bridged 2-D sheet structure is formed through the bridging of the cyano groups of the Ni(mnt)2Cu4I4 units of neighboring 1-D chain structures by sodium atoms. The monomeric [Na2(18-crown-16)]2[Ni(mnt)2Cu4I4] complex is formed when the sodium cations of the 2-D sheet structure are captured by 18-crown-6. The configuration of the coordination polymer or the monomer is controlled through the selection of the appropriate countercation to the Ni(mnt)2Cu4I4 building unit. Furthermore, the eight-membered Cu4I4 crown motifs in the 2-D sheet structure captures sodium cations. In this regard, we propose that the flexible Cu4I4 crown motif is capable of capturing atoms or molecules of various sizes such a material may act as a useful molecular adsorbent through electrostatic interactions. - K. Himoto; S. Suzuki; T. Okubo; M. Maekawa; T. Kuroda-SowaNew Journal of Chemistry Royal Society of Chemistry 42 (6) 3995 - 3998 1369-9261 2018 [Refereed]
A novel mixed-valence coordination polymer [CuI4CuIIBr4(dmpip-dtc)2(CH3CN)]n (dmpip-dtc = dimethylpiperidine-dithiocarbamate) with an infinite one-dimensional structure was synthesized and structurally characterized using X-ray diffraction. The electronic properties of the coordination polymer were investigated by UV-vis-NIR spectroscopy. Impedance measurement results demonstrated that this complex has a narrow bandgap, inducing semiconducting behavior. - Takayoshi Kuroda-Sowa; Rina Isobe; Norifumi Yamao; Tomohiro Fukumasu; Takashi Okubo; Masahiko MaekawaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 136 74 - 78 0277-5387 2017/11 [Refereed]
The preparation and magnetic properties of four Fe(11) Schiff-base complexes, [Fe(qsal(x))(2)] (Hqsal(x) = N-(8'-quinoly1)-2-hydroxy-5-halogeno-l-salicylaldimine; X = F(1), C1(2), Br(3), 1(4)) are reported. X-ray single crystal structure analyses of 1 and 2 reveal that Fe(II) ions in both complexes are coordinated by two qsalx ligands in meridional fashion. Molecular packing of 1 shows that a non-planar qsal(F) ligand interacts with neighboring two qsal(F) ligand's through pi-pi interactions, while that of 2 shows that two planar qsal(cl) ligands interact each other through pi-pi interaction. Although the magnetic property of 1 shows a high spin state at all the temperature range measured, the chi T-T plots of 2, 3, and 4 show gradual spin crossover behaviors with T1/2 of 308 K, 341 K, and 340 K, respectively. (C) 2017 Elsevier Ltd. All rights reserved. - Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 467 204 - 211 0020-1693 2017/10 [Refereed]
The reactions of CuX2 center dot nH(2)O (X = ClO4, BF4), Cu turnings and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) with excess 1,5-cyclooctadiene (cod) in Me2CO under C2H4 afforded dinuclear Cu(I)-bptz/eta(2), eta(2)-cod-X complexes {(1) and (4)} and dinuclear Cu(I)-2,5-H(2)bptz/eta(2), eta(2)-cod-X complexes {(2) and (5)}. In complexes 1 and 4, each Cu(I) atom is coordinated by two chelate N atoms of bptz and two C=C bonds of eta(2), eta(2)-cod in the distorted tetrahedral geometry to produce a transoid dinuclear structure. It should be noted that the redox state of the central tetrazine ring is electrochemically neutral. In complexes 2 and 5, each Cu(I) atom is coordinated by two chelate N atoms of 2,5-H(2)bptz and two C=C bonds of eta(2), eta(2)-cod in the distorted tetrahedral geometry to afford a transoid dinuclear structure in the 2,5-dihydro form. In contrast, the reactions of Cu(BF4)(2)center dot nH(2)O, Cu turnings and bptz with excess 2,5-norbornadiene (nbd) in MeEtCO under C2H4 afforded Cu(I)-2,5-H(2)bptz/eta(2)-nbd-BF4 complex (6). Each Cu(I) atom is coordinated by two chelate N atoms in bptz and one C=C bond in eta(2)-nbd to form a transoid dinuclear structure in the 2,5-dihydro form. These facts show that the flexible cod can preferentially produce a Cu(I)cyclodiene complex in the eta(2), eta(2)-mode (complexes 1, 2, 4 and 5) while the rigid nbd can produce a Cu (I)-cyclodiene complex in the eta(2)-mode (complex 6). Furthermore, the reaction of Cu(NO3) center dot 3H(2)O, Cu turnings and bptz with excess nbd in Me2CO under C2H4 afforded tetranuclear Cu(I)-4,5-H(2)bptz-NO3 complex (7) containing a unique anionic [Cu-2(nbd)(NO3)(4)](2) moiety. In the cationic [Cu-4(4,5H(2)bptz) 4] 4+ moiety, four Cu(I) atoms are bridged by four 4,5-H(2)bptz ligands to form a [4 x 4] grid-like tetranuclear structure with two 4,5-H(2)bptz ligands lying above the Cu4 mean plane and two lying below. In the anionic [Cu-2(nbd)(NO3)(4)](2) moiety, the two Cu atoms are bridged by one nbd ligand in the mu(2)-eta(2), eta(2)-mode. (C) 2017 Elsevier B. V. All rights reserved. - Kunihisa Sugimoto; Masahiko Maekawa; Takayoshi Kuroda-SowaACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES INT UNION CRYSTALLOGRAPHY 73 C181 - C181 2053-2733 2017 [Refereed]
- Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataCHEMISTRYSELECT WILEY-V C H VERLAG GMBH 1 (13) 3812 - 3822 2365-6549 2016/08 [Refereed]
The reactions of [Cu(MeCN)(4)]BF4 or [Cu(C2H4)(n)]ClO4 complexes with 4,6-bis(2-pyridyl)pyrimidine (bppym) in Me2CO under C2H4 afforded dinuclear Cu(I)-bppym/C2H4 adducts [Cu-2-(bppym)(C2H4)2](BF4)(2)center dot Me2CO (1) and [Cu-2(bppym)(2)(C2H4)(2)](ClO4)(2)center dot Me2CO (2), respectively. One Cu(I) atom is coordinated by bppym and C2H4 in a distorted trigonal-planar geometry. The other Cu(I) atom is coordinated by bppym, Me2CO, and C2H4 toward a distorted tetrahedral geometry. The reaction of [Cu(MeCN)(4)]BF4 with 2,3-bis(2-pyridyl)pyrazine (bppz) in MeOH under C2H4 afforded a Cu(I)-bppz coordination polymer {[Cu-2(bppz)(2)](BF4)(2)center dot MeOH} n (3). Two Cu(I) atoms are alternately bridged by two bppz to form a 1-D zigzag-chain structure. Each Cu(I) coordination sphere is largely distorted from a normal tetrahedral structure toward a square planar structure. The reaction of [Cu(MeCN)(4)]PF6 with 2,4,6-tris(2-pyridyl)-s-triazine (tptz) in MeEtCO under C2H4 afforded a tetranuclear Cu(I)-tptz/C2H4 adduct [Cu-4(tptz)(2)(C2H4)(2)(MeCN)(2)](PF6)(4)center dot MeEtCO (4b). Two Cu(I) atoms are bridged by the central triazine ring, the 2-pyridyl group, the central triazine ring, and the 2-pyridyl group in a different tptz to form a double helical structure. The other Cu(I) atom is coordinated by the central triazine ring, the 2-pyridyl group, MeCN, and C2H4 in a distorted tetrahedral geometry. The reaction of [Cu(MeCN)(4)]PF6 with tetra-2-pyridylpyrazine (tppz) in MeOH under C2H4 afforded a tetranuclear Cu(I)-tppz complex [Cu-4(tppz)(2)(MeCN)(4)](PF6)(4)center dot MeOH (5a). Each Cu(I) atom is coordinated by the central pyrazine ring, the 2-pyridyl group, the 2-pyridyl group in a different tppz, and MeCN in a distorted tetrahedral geometry. These four Cu(I) atoms are bridged by the two opposite tppz ligands to form a unique tetranuclear Cu(I) cage structure. - Masahiko Maekawa; Yukimi Kubo; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataEUROPEAN JOURNAL OF INORGANIC CHEMISTRY WILEY-V C H VERLAG GMBH (1) 78 - 91 1434-1948 2016/01 [Refereed]
A new type of Ir-III metalloligands containing an unsaturated nitrogen coordination site, [Ir(H)(2)(PPh3)(2)(pprd)]BF(4)2CHCl(3) (1), [Ir(H)(2)(PPh3)(2)(Me(2)bpm)]BF4CHCl3 (2), {[Ir(H)(2)(PPh3)(2)(Me(2)bpm)]PF6CHCl3}(4) (3), [Ir(H)(2)(PPh3)(2)(biqz)]BF(4)2CHCl(3) (4), and [Ir(H)(2)(PPh3)(2)(biqz)]PF6 (5), have been prepared by reaction of [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]X (X = BF4 or PF6) with 4-(2-pyridyl)pyrimidine (pprd), 6,6-dimethyl-4,4-bipyrimidine (Me(2)bpm), or 4,4-biquinazoline (biqz). Subsequently, three novel heterometallic Ag-I-Ir-III hydride coordination polymers, {[Ir(H)(2)(-pprd)(PPh3)(2)Ag(-CF3COO)]BF4Me2CO}(n) (6), {[Ir(H)(2)(-biqz)(PPh3)(2)Ag-2(-CF3COO)(3)]Me2CO}(n) (7), and {[Ir(H)(2)(-Me(2)bpm)(PPh3)(2)Ag-2(-CF3COO)(2)]PF(6)2Me(2)CO}(n) (8) have been constructed by reaction of the Ir-III metalloligands 1, 3, and 5 with AgCF3COO. In coordination polymer 6, the [Ir(H)(2)(PPh3)(2)(pprd)](3+) units are linked through the Ag-I atoms to form a 1D zigzag chain structure. In coordination polymer 7, the dinuclear [Ag-2(-CF3COO)(3)](-) units are linked through the terminal N atoms of biqz in two different [Ir(H)(2)(PPh3)(2)(biqz)](3+) units to form a 1D zigzag chain structure. In coordination polymer 8, the [Ag-2(-CF3COO)(2)] frameworks are linked through the terminal N atoms of Me(2)bpm and the Ir-III atom in two different [Ir(H)(2)(PPh3)(2)(Me(2)bpm)](3+) units to form a waved rectangular cavity. These waved rectangular cavities are connected to each other to afford a unique 2D sheet structure. - Kenji Nakatani; Kento Himoto; Yuki Kono; Yuuki Nakahashi; Haruho Anma; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaCRYSTALS MDPI AG 5 (2) 215 - 225 2073-4352 2015/06 [Refereed]
- Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 426 64 - 70 0020-1693 2015/02 [Refereed]
The reaction of [Cu(MeCN)(4)]PF6 with 3,5-bis(2-pyridyl)-1H-1,2,4-triazole (Hbptrz) in MeOH under C2H4 afforded the colorless needle crystals of [Cu-2(bptrz)(C2H4)(2)]PF6 center dot MeOH (1). The X-ray crystallographic study showed that there are two [Cu-2(bptrz)(C2H4)(2)](+) cation moieties, two PF6 anions and two solvated MeOH molecules in the unit cell. This result indicates that the central triazole ring was deprotonated to produce the anionic bptrz ligand. Each Cu(I) atom is coordinated by two chelate N atoms of bptrz and the C=C bond of C2H4 in the trigonal-planar geometry to produce a notable dinuclear Cu(I)-bptrz/C2H4 adduct bearing the anionic bptrz in the transoid conformation. In contrast, the reaction of Cu(NO3)(2)center dot H2O, Cu turnings and 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine (4-bptz) in Me2CO under C2H4 gave black brick crystals of {[Cu-4(4,5-H-2-4-bptz)(2)(C2H4)(2)(NO3)(4)]center dot Me2CO center dot 0.5H(2)O}(n) (2). This result indicates that 3,6-bis(4-pyridyl)-4,5-dihydro-1,2,4,5-tetrazine (4,5-H-2-4-bptz) was produced by the two-electron reduction of 4-bptz. Four Cu(I) atoms are bridged by two 4,5-H-2-4-bptz and four NO3 anions to form two distinct rectangular [Cu-4(4,5-H-2-4-bptz)(2)(NO3) 4] frameworks. Furthermore, these rectangular [Cu-4(4,5-H-2-4-bptz)(2)(NO3)(4)] subunits are linked via the N atom in the central 4,5-dihydrotetrazine ring each other to generate a unique 2-D Cu(I)-4,5-H-2-4-bptz/C2H4-NO3 coordination polymer with a channel structure along the a-axis. Thermogravimetric analysis (TG-DTA) showed that complexes 1 and 2 were thermochemically stable to a relatively high temperature. (C) 2014 Elsevier B.V. All rights reserved. - Masahiko Maekawa; Ai Minamino; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 414 257 - 263 0020-1693 2014/04 [Refereed]
The reactions of [Cu(MeCN)(4)](X) (X = BF4 or PF6) with 4,4'-biquinazoline (biqz) in MeOH under C2H4 afforded brown plate crystals of {[Cu-4(biqz)(2)(MeCN)(4)(MeOH)(4)](BF4)(4)}(n) (1) and orange prismatic crystals of {[Cu-4(biqz)(2)(MeCN)(8)](PF6)(4)}(n) (2), respectively. In both of complexes 1 and 2, two Cu(I) atoms are bridged by two biqz ligands to form a 14-membered Cu4C6N4 framework. Furthermore, the Cu4C6N4 frameworks are linked by the two chelate and bridging sites of biqz to generate a 1-D double-chain Cu(I) coordination polymer. It should be noted that two N atoms in the chelate site of the biqz ligand does not act as a normal bidentate chelate mode but form a bridge between two Cu atoms in an unidentate bridging mode. In contrast, the reaction of [Cu(C2H4)(n)]ClO4 with biqz in Me2CO under C2H4 afforded orange plate crystals of polymeric Cu(I)-biqz/C2H4 adduct {[Cu-2(biqz)(C2H4)(2)](ClO4)(2)center dot Me2CO}(n) (3). The Cu atom is coordinated by two N atoms of biqz in the chelate site and the C=C bond of C2H4 in a rather distorted trigonal-planar geometry. The other Cu atom is coordinated by two N atom of two biqz ligands in the exo bridging site and the C=C bond of C2H4 in a trigonal-planar geometry to form a 1-D zigzag-chain structure. It was proved that the Cu(I) coordination polymers bridged by the biqz ligand in the different coordination modes can be preferentially produced by the choices of the precursor Cu(I) complexes. The thermogravimetric analysis (TG-DTA) measurements showed that Cu(I)-biqz-{BF4, PF6} complexes 1 and 2 were thermochemically stable to a relatively high temperature (330-340 degrees C). (C) 2014 Elsevier B. V. All rights reserved. - Yusaku Suenaga; Honami Inada; Masataka Inomata; Ryotaro Yamaguchi; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaCHEMISTRY LETTERS CHEMICAL SOC JAPAN 43 (4) 562 - 564 0366-7022 2014/04 [Refereed]
Trinuclear Co(III) complex [Co-3(III)(tpa)(3)(L)](BF4)(4) (tpa: tris-(2-pyridylmethyl)amine, H6L: 2,3,6,7,10,11-hexahydroxytriphenylene) is prepared from methanol solution. Single-crystal structure analysis revealed that the valency of the three cobalt ions is +3 and that the tris(dioxolene) bridging ligand is formally in the -5 [cat,cat,sq] oxidation state. This complex is stable in the entire temperature range investigated. Various-temperature magnetic susceptibility data for the compound displayed little variation in the range 2-300K, and the reason caused the distinct charge distribution on Co-L (L: bridging ligand) by the natural rigidity of the tripodal ligands. Also, its CH3CN solution exhibits a very strong NIR absorption arising from an internal ligand transition within the triphenylene ligand. Cyclic voltammetry (CV) measurements in CH3CN solution show three reversible cat sq redox waves for the triphenylene ligand. - Takashi Okubo; Haruho Anma; Yuuki Nakahashi; Masahiko Maekawa; Takayoshi Kuroda-SowaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 69 103 - 109 0277-5387 2014/02 [Refereed]
New mixed-valence coordination polymers {[(Cu5CuI5L2)-Cu-I-I-II(C2H5CN)(2)]center dot CHCl3)(n) (L = piperidinedithiocarbamate and hexamethyl-dithiocarbamate) with isomorphous infinite one-dimensional (1D) structures were prepared and structurally characterized via X-ray diffraction. These complexes comprised a mononuclear Cu(II) unit, (CuL2)-L-II, and a pentanuclear Cu(I) cluster unit, (Cu5I5)-I-I(C2H5CN)(2). Impedance measurements demonstrated that these Cu(I)-Cu(II) mixed-valence 1D coordination polymers displayed semiconducting behavior with low conductivities. (C) 2013 Elsevier Ltd. All rights reserved. - 杉本邦久; 藤原明比古; 上町裕史; 前川雅彦日本結晶学会誌, 日本結晶学会 56 (1) 49 - 53 0369-4585 2014/02 [Refereed]
- Masahiko Maekawa; Takeshi Miyazaki; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 410 46 - 53 0020-1693 2014/01 [Refereed]
The reaction of [Cu(C2H4)n]NO3, Cu turnings, 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz), and ferrocene in Me2CO under C2H4 afforded black crystals of [Cu-4(4,5-H(2)bptz)(4)][Cu(C2H4)(NO3)(2)](2)(NO3)(2)center dot 2Me(2)CO (7). In the [Cu-4(4,5-H(2)bptz)(4)](4+) cation moiety, four Cu(I) atoms are bridged by four 4,5-H(2)bptz ligands to form a [4 x 4] grid-like tetranuclear structure. In the [Cu(C2H4)(NO3)(2)] anion moiety, the Cu atom is coordinated by two NO3 anions in the unidentate coordination mode and by the C=C bond of C2H4 to form a mononuclear Cu(I)-C2H4 adduct in the trigonal-planar geometry. It should be noted that two anionic Cu(I)-C2H4 adducts [Cu(C2H4)(NO3)(2)] are present as a co-crystal. The similar reaction of Cu(BF4)(2)center dot H2O, Cu turnings, bptz, and ferrocene in MeEtCO under C2H4 afforded colorless crystals of [Cu-2(bpdpyz)(C2H4) (2)](BF4)(2) (9). In the [Cu-2(bpdpyz)(C2H4)(2)](2+) cation moiety, each Cu(I) atom is coordinated by two chelate N atoms of bpdpyz and the C=C bond of C2H4 to afford an unusual cisoid dinuclear structure. This result shows that 3,6-bis(2-pyridyl)-4,5-dihydropyridazine (bpdpyz) can be produced by the cycloaddition of bptz with C2H4 via a Diels-Alder addition and retro-Diels-Alder elimination of dinitrogen to form complex 9. In contrast, the reaction of Cu(BF4)(2)center dot H2O, Cu turnings, and bptz in Me2CO in the absence of ferrocene afforded black crystals of [Cu-4(4,5-H(2)bptz)(4)](BF4)(4)center dot Me2CO (12). Although the apparent structure of the [Cu-4(4,5-H(2)bptz)(4)](4+) cation moiety is similar to that of the [Cu-4(4,5-H(2)bptz)(4)](4+) cation moiety in complex 7, the shape of the Cu-4 framework is closer to a square structure, resulting in the adjacency of the two opposite tetrazine rings. The preparations and structural diversity of Cu(I)-C2H4 adducts with the related bptz ligands are described in addition to related previous results. (C) 2013 Elsevier B.V. All rights reserved. - SUENAGA Yusaku; INOMATA Masataka; UWAI Kazuya; OKUDA Koji; OKUBO Takashi; MAEKAWA Masahiko; KURODA-SOWA TakayoshiX-ray Structure Analysis Online The Japan Society for Analytical Chemistry 30 57 - 58 1883-3578 2014 [Refereed]
The reaction of a methanol solution containing Co(BF4)2·6H2O and tris(2-pyridylmethyl)amine (tpa) afforded the unexpected dinuclear cobalt(III)-peroxo complex [Co2(μ-F)(μ-O2)(tpa)2](BF4)3, where the two metal centers are simultaneously doubly bridged by one fluoride ion such that BF4- is a fluoride source. It crystallizes in the triclinic space group P1 with a = 10.452(3)Å, b = 12.529(3)Å, c = 16.708(5)Å, α = 106.410(4)°, β = 106.916(4)°, γ = 90.2807(13)°, V = 1999.0(9)Å3, Dcalc = 1.678 g/cm3, and Z = 2. The R1 [I > 2σ(I)] and wR2 (all data) values are 0.0450 and 0.1679, respectively, for all 9093 independent reflections. - Sugimoto Kunihisa; Maekawa Masahiko; Kuroda-Sowa TakayoshiACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 70 C181 2053-2733 2014 [Refereed]
- Naoya Tanaka; Takashi Okubo; Haruho Anma; Kyung Ho Kim; Yoshie Inuzuka; Masahiko Maekawa; Takayoshi Kuroda-SowaEuropean Journal of Inorganic Chemistry (19) 3384 - 3391 1434-1948 2013/07 [Refereed]
New mixed-valence CuI-CuII 1D coordination polymers of the structure [CuI 2CuIIX2(Pip- dtc)2(CH3CN)2]n [Pip-dtc = piperidine-1-carbodithioate X = Br (1a), I (1b)] containing a dithiocarbamate derivative have been synthesized and structurally characterized by X-ray diffraction. The 1D infinite chains were formed from mononuclear copper units [Cu(Pip-dtc)2] connected by bromido- or iodido-bridged copper dinuclear units that include acetonitrile ligands {i.e., [Cu2X 2(CH3CN)2]}. Evaluation of the magnetic properties of 1a and 1b revealed that these complexes displayed relatively strong antiferromagnetic interactions [J = -20.4 cm-1 (1a) and J = -18.8 cm-1 (1b)] between unpaired electrons of the copper(II) ions through the dinuclear halido-copper(I) units. Impedance spectroscopy revealed that complexes 1a and 1b exhibit intriguing semiconducting properties at activation energies of Ea = 0.78 eV (1a) and Ea = 0.62 eV (1b). Coordination polymers 1a and 1b were then adopted as the sensitizing material in dye-sensitized solar cells (DSSCs). New halido-bridged mixed-valence CuI-CuII coordination polymers with 1D infinite chain structures have been synthesized and structurally characterized The complexes show a relatively strong antiferromagnetic interaction and interesting semiconducting behavior. These coordination polymers were applied as sensitizing materials for DSSCs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. - Takashi Okubo; Haruho Anma; Masahiko Maekawa; Takayoshi Kuroda-SowaActa Crystallographica Section E: Structure Reports Online 69 (5) m275 - m276 1600-5368 2013/05 [Refereed]
The reaction of Cu(Hm-dtc)2 (H2m-dtc is azepane-1-carbodithioic acid), CuBr2 and methyl isothiocyanate yielded the title mixed-valence nonanuclear CuI/CuII compound, [Cu 9Br5(C7H12NS2) 5] or [CuI 8CuIIBr5(Hm-dtc)5], encapsulating a bromide anion in the center of the Cu9Br 4S10 cluster cage. The cage consists of a mononuclear CuII unit [Cu(Hm-dtc)2], three μ4-bridging Hm-dtc- ligands, eight CuI ions with distorted tetrahedral or trigonal pyramidal coordination geometries and four μ2-bridging bromide anions. The incorporated central bromide anion interacts with nine Cu ions with shorter Cu - Br separations than the sum of the van der Waals radii for Cu and Br. - Kunihisa Sugimoto; Hiroshi Uemachi; Masahiko Maekawa; Akihiko FujiwaraCrystal Growth and Design 13 (2) 433 - 436 1528-7483 2013/02 [Refereed]
A new stable cyclohexasulfur (cyclo-S6) was discovered in the crystal of 3,5-diphenyl-1,2,4-dithiazol-1-ium (dpdti) dpdti was synthesized via an oxidation reaction of thiobenzamide with iodine in benzene, under reflux. Two kinds of crystal habits - brick-shaped (crystal-A) and needle-shaped (crystal-B) - were obtained following recrystallization from acetonitrile solvent. Single-crystal structure analysis using synchrotron X-ray radiation showed that both crystal-A and -B consist of a dpdti cation and an iodine anion. Furthermore, neutral cyclo-S6 molecules are present in crystal-A as cocrystals, enclosed by the dpdti cation and the iodide anion. This is akin to cyclosulfur of Sn in zeolites and sodalities, suggesting a contribution to the stabilization of cyclo-S6 molecules. The results show that crystal engineering of cocrystals may be used as a method to control the stability and activity of sulfur, for improved utilization. © 2012 American Chemical Society. - Masahiko Maekawa; Takeshi Miyazaki; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaDALTON TRANSACTIONS ROYAL SOC CHEMISTRY 42 (12) 4258 - 4266 1477-9226 2013 [Refereed]
The reaction of Cu(ClO4)center dot 6H(2)O, Cu turnings, and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) in Me2CO under C2H4 afforded brownish-red needle crystals of {[Cu-2(bptz(center dot-))(C2H4)(2)](ClO4)}(2) (1) as a minor product and brown plate crystals of [Cu-2(2,5-H(2)bptz)(C2H4)(2)](ClO4)(2)center dot 2Me(2)CO (2). The X-ray crystallographic study showed that complex 1 is composed of two independent [Cu-2(bptz(center dot-))(C2H4)(2)](+) cation moieties and two ClO4- anions. In both of the cation moieties, each Cu(I) atom is coordinated by two chelate N atoms of bptz(center dot-) and the C=C bond of C2H4 in the trigonal-planar geometry to form a unique transoid dinuclear Cu(I)-bptz(center dot-)/C2H4 adduct bearing a metal-stabilized tetrazine anion radical, bptz(center dot-), which was produced by the one-electron reduction of bptz. In contrast, complex 2 consists of one [Cu-2(2,5-H(2)bptz)(C2H4)(2)](2+) cation moiety, two ClO4- anions, and two solvated Me2CO molecules. Each Cu(I) atom is coordinated by two chelate N atoms of 2,5-H(2)bptz and the C=C bond of C2H4 in the trigonal-planar geometry to afford a transoid dinuclear Cu(I)-C2H4 adduct with 2,5-H(2)bptz, which was produced by the two-electron reduction of bptz. Additionally, the similar reaction of Cu(ClO4)center dot 6H(2)O, Cu turnings, and bptz in Me2CO or MeEtCO under C2H4 in the presence of ferrocene afforded orange brick crystals of [Cu-2(bpdpyz)(C2H4)(2)]- (ClO4)(2)center dot Me2CO (3) and [Cu-2(bpdpyz)(C2H4)(2)](ClO4)(2) (4), respectively, together with complex 1 in higher yield. This result shows that 3,6-bis(2-pyridyl)-4,5-dihydropyridazine (bpdpyz) was produced by the cyclo-addition of bptz with C2H4 via a Diels-Alder addition and retro-Diels-Alder elimination of dinitrogen. In complexes 3 and 4, each Cu(I) atom is coordinated by two chelate N atoms of bpdpyz and the C=C bond of C2H4 to afford an unusual cisoid dinuclear Cu(I)-C2H4 adduct. Further attempts to react excess [Cu(C2H4)(n)]ClO4 with bptz in Me2CO under C2H4 afforded black brick crystals of [Cu-4(4,5-H(2)bptz)(4)](ClO4)(4)center dot 2Me(2)CO (5) together with complex 1. Complex 5 is the first [4 x 4] grid-like tetranuclear Cu(I) complex constructed by the combination of Cu(I) ion and 4,5-H(2)bptz. The four Cu(I) atoms are spanned by four 4,5-H(2)bptz ligands, with two lying above the Cu-4 mean plane and two lying below. In contrast, the similar reaction of excess [Cu(C2H4)(n)]ClO4 with bptz in Me2CO under C2H4 in the presence of ferrocene afforded reddish-brown brick crystals of {[Cu-2(2,5-H(2)bptz)(C2H4)(2)](ClO4)(2)}(2)center dot Me2CO (6) together with complexes 1 and 5. Complex 6 is composed of two independent [Cu-2(2,5-H(2)bptz)(C2H4)(2)](2+) cation moieties, four ClO4- anions, and a solvated Me2CO molecule. It is interesting that the structures of the two [Cu-2(2,5-H(2)bptz)(C2H4)(2)](2+) cation moieties are different: one has a nearly planar structure and the other possesses a boat conformation owing to the bent central dihydrotetrazine ring. - Takashi Okubo; Haruho Anma; Naoya Tanaka; Kento Himoto; Shu Seki; Akinori Saeki; Masahiko Maekawa; Takayoshi Kuroda-SowaCHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY 49 (39) 4316 - 4318 1359-7345 2013 [Refereed]
A novel mixed-valence Cu(I)-Cu(II) coordination polymer with an infinite two-dimensional structure, [(Cu3CuBr3)-Cu-I-Br-II(3,5-Dmpip-dtc)(2)](n) (3,5-Dmpip-dtc(-) = 3,5-dimethylpiperidine dithiocarbamate), was prepared, and its structure was characterized by X-ray diffraction. It shows semiconducting behavior with a relatively small activation energy and high carrier mobility, which were investigated using impedance spectroscopy and flash photolysis time-resolved microwave conductivity measurements, respectively. - Kunihisa Sugimoto; Hiroshi Uemachi; Masahiko Maekawa; Akihiko FujiwaraACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES INT UNION CRYSTALLOGRAPHY 69 S542 - S543 2053-2733 2013 [Refereed]
- Takashi Okubo; Naoya Tanaka; Haruho Anma; Kyung Ho Kim; Masahiko Maekawa; Takayoshi Kuroda-SowaPOLYMERS MDPI AG 4 (3) 1613 - 1626 2073-4360 2012/09 [Refereed]
One-dimensional (1D) halide-bridged Cu(I)-Ni(II) heterometal coordination polymers containing a hexamethylene dithiocarbamate (Hm-dtc) ligand have been synthesized and crystallographically characterized. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of the coordination polymers were estimated using UV-Vis-NIR and photoelectron spectroscopies, and it was revealed that these coordination polymers have appropriate HOMO levels for use as dye sensitizers. Direct-current electrical conductivity measurements and impedance measurements indicated that these 1D Cu(I)-Ni(II) heterometal coordination polymers were insulators (sigma(300K) < 10(-12) S cm(-1)). In addition, the coordination polymers were used as sensitizing materials in dye-sensitized solar cells (DSSCs). DSSCs with 1D Cu(I)-Ni(II) heterometal coordination polymers showed lower performances than those with 1D halide-bridged Cu(I)-Cu(II) mixed-valence coordination polymers. - Masahiko Maekawa; Yukimi Kubo; Kunihisa Sugimoto; Toshie Minematsu; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 40 (1) 145 - 152 0277-5387 2012/06 [Refereed]
The reaction of [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]BF4 with 2,2'-bipyimidine (bpym) in CHCl3 afforded the yellow needle crystals of mononuclear Ir(III)-bpym/hydride complex [Ir(H)(2)(PPh3)(2)(bpym)]BF4 center dot 4CHCl(3) (1). In contrast, when CH2Cl2 or CHCl3 solution of [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]BF4 were layered by the THF solution of bpym, red brick crystals of dinuclear Ir(III)-bpym/hydride complex [Ir-2(H)(4)(PPh3)(4)(bpym)](BF4)(2)center dot 2CH(2)Cl(2)center dot 2THF (2) and orange brick crystals of [Ir-2(H)(4)(PPh3)(4)(bpyrn))(BF4)(2)center dot 2CHCl(3) (3) were solvent-selectively formed. The UV-Vis spectra of complexes 1-3 in the solid state demonstrated that the absorptions of complexes 2 (495 nm) and 3 (510 nm) exhibited a significant red-shift relative to that (420 nm) of complex 1. Complexes 1-3 redissolved in CD2Cl2 gave several well-resolved H-1 NMR signals at 23 degrees C. It is noteworthy that all H-1 NMR signals of the coordinated pyrimidine rings in complexes 1-3 were shifted to the upfield region relative to those of the metal-free bpym ligand, in which the coordination shifts (Delta delta = delta(complex) - delta(metal-free)) are {-0.12 (H-6.6'), -0.73 (H-4.4') and -0.55 (H-5.5') ppm} for complex 1, {-0.81 (H-4.4') and -0.67 (H-5.5') ppm} for complex 2, and {-0.72 (H-4.4') and -0.58 (H-5.5') ppm} for complex 3. It was proved that unusual upheld shifts can be caused by the diamagnetic anisotropic ring current effect between the adjacent bpym and phenyl groups of PPh3. Thermogravimetric analysis (TG-DTA) showed that Ir(III)-bpym/hydride complexes 1-3 were thermochemically stable to a relatively high temperature near 330 degrees C. (C) 2012 Elsevier Ltd. All rights reserved. - Masahiko Maekawa; Toshi Tominaga; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaCRYSTENGCOMM ROYAL SOC CHEMISTRY 14 (4) 1345 - 1353 1466-8033 2012 [Refereed]
The reaction of [Cu(C2H4)(n)]NO3 with 4,4'-bipyrimidine (bpm) in Me2CO under C2H4 afforded a polymeric Cu(I)-bpm/C2H4 adduct [Cu-2(bpm)(C2H4)(NO3)(2)](n) (1) with an infinite 1-D zigzag chain structure. Similar reactions of [Cu(C2H4)(n)]ClO4 or [Cu(MeCN)(4)]BF4 with bpm in Me2CO under C2H4 afforded Cu(I)-bpm/C2H4 adducts {[Cu-3(bpm) (2)(C2H4) (2)](ClO4)(3)}(n) (2) and {[Cu-3(bpm)(2)(C2H4)(2)](BF4)(3)}(n) (3), respectively, which have an infinite 1-D zigzag ladder structure. It is interesting that two disordered ClO4- or BF4- anions are accommodated in the inside cavity of the ladder chains. In contrast, the reaction of [Cu(MeCN)(4)]BF4 with bpm in MeOH under C2H4 afforded a Cu(I)-bpm/C2H4 adduct {[Cu-4(bpm) (3)(C2H4) (3)(MeOH)](BF4)(4)center dot 2H(2)O center dot 3MeOH}(n) (4). Three Cu atoms are bridged by three bpm ligands to form a metallacalix[3] arene structure with three legs of C2H4. Furthermore, these metallacalix[3] arenes are linked through another Cu atom in the terminal N atom of bpm to produce a chiral 2-D sheet structure with space group P6(3). One BF4- anion is accommodated in the small triangular Cu-3 cavities, whereas three disordered BF4- anions are encapsulated in the large triangular Cu-3 cavities. In contrast to complex 4, [Cu(MeCN)(4)]BF4 was reacted with bpm in MeOH under Ar, and C2H4 gas was then bubbled into the resultant brown suspensions. The reaction solution was allowed to come to room temperature, and Cu(I)-bpm complex {[Cu-3(bpm)(3)](SiF6)(1.5)}(n) (5) was collected. The tetrahedral Cu atom is coordinated by two N atoms in the chelate site of bpm and two N atoms in the terminal sites of two other bpm ligands to form two racemic metallacalix[3] arene structures. It is noteworthy that these metallacalix[3] arenes are joined through the bpm ligands to afford a 3-D cage structure consisting of two right-handed and left-handed helix networks. One disordered SiF62- anion is accommodated in the inside cavity between two opposite metallacalix[3] arene structures. On the basis of these results, it has been concluded that BF4-, PF6-, ClO4- and SiF62- anions can serve as anion templates to self-assemble polymeric Cu(I) C2H4 adducts and a cage compound in complexes 2-5. The NO3- anion is ineffective as an anion template, as indicated by the higher coordination ability of the NO3- anion in complex 1. Additionally, solvent-dependent effects have been observed in the formation process: Me2CO can preferentially induce polymeric 1-D chain and 1-D ladder structures in complexes 1-3, whereas MeOH can produce 2-D sheet and 3-D cage structures by the linage of metallacalix[3]arene structures in complexes 4 and 5. - Masahiko Maekawa; Toshi Tominaga; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaCRYSTENGCOMM ROYAL SOC CHEMISTRY 14 (18) 5955 - 5962 1466-8033 2012 [Refereed]
The reactions of Cu(I) ion with {BF4-, ClO4-, or PF6-} anions and 6,6'-dimethyl-4,4'-bipyrimidine (Me(2)bpm) under C2H4 or CO in MeOH preferentially afforded three 2D sheet Cu(I)-Me(2)bpm/{C2H4, CO} adducts [Cu-4(Me(2)bpm)(3)(C2H4)(3)(MeCN)](BF4)(4)center dot 0.33MeOH}(n) (2), {[Cu-4(Me(2)bpm)(3)(C2H4)(3)(MeOH)(0.33)](ClO4)(4)}(n) (3), and {[Cu-4(Me(2)bpm)(3)(CO)(3)(MeCN)](PF6)(4)center dot 0.33MeCN}(n) (4), whereas the similar reaction of Cu(I) ion with a BF4- anion and Me(2)bpm under CO in MeOH gave the metallamacrocyclic tetranuclear Cu(I)-Me(2)bpm/CO adduct [Cu-4(Me(2)bpm)(4)(CO)(4)](BF4)(4)center dot 4MeOH (5). In Cu(I)-Me(2)bpm/{C2H4, CO} adducts 2-4, it should be noted that the metallacalix[3]arene structures of the [Cu-3(Me(2)bpm)(3)](3+) framework are linked through another Cu atom with MeCN (2 and 4) or MeOH (3) to produce a chiral 2D sheet structure with small Cu-3 and large Cu-9 cavities. In the small triangular Cu-3 cavities, one MeOH (2) or MeCN (4) molecule is encapsulated in complexes 2 and 4, whereas these Cu-3 cavities are empty in complex 3. In the large Cu-9 cavities, one anion (X = BF4- (2), ClO4- (3) or PF6- (4)) is surrounding by six Me groups of three Me(2)bpm on the upside and three anions (X) are functionally accommodated on the downside for complexes 2-4, respectively. In the Cu(I)-Me(2)bpm/CO adduct 5, two of the four BF4- anions are accommodated in the upper and lower cavities of the [Cu-4(Me(2)bpm)(4)] framework. We demonstrated that the metallamacrocyclic and polymeric 2D sheet Cu(I)-Me(2)bpm/{C2H4, CO} adducts can be reasonably self-assembled under the direction of anions and solvents. - Takayoshi Kuroda-Sowa; Kana Kimura; Jun Kawasaki; Takashi Okubo; Masahiko MaekawaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 30 (18) 3189 - 3192 0277-5387 2011/11 [Refereed]
The preparation and magnetic properties of two Fe(II) Schiff-base complexes, [Fe(qnal-12)(2)]center dot 2C(6)H(6) (1) and [Fe(Hqsalc)(2)] (2), (Hqnal-12 = N-(8'-quinolyl)-1-hydroxy-2-naphthaldimine, H(2)qsalc = 4-hydroxy-3-[(8-quinolinylimino)methyl][benzoic acid) are reported. X-ray single crystal structure analysis of 1 reveals that an Fe(II) ion is coordinated by two qnal-12 ligands in a meridional fashion. Molecular packing of 1 shows that a qnal-12 interacts with neighboring two qnal-12's through it-it interactions, which results in the formation of one-dimensional chain. Although the magnetic property of 1 shows a high-spin state at all the temperature range measured, the chi T-T plot of 2 shows abrupt spin crossover behavior with a wide hysteresis of 21 K, probably due to the hydrogen-bond network originated by carboxyl groups. (C) 2011 Elsevier Ltd. All rights reserved. - Kyung Ho Kim; Takashi Ueta; Takashi Okubo; Shinya Hayami; Haruho Anma; Kazuya Kato; Tetsuya Shimizu; Jyunji Fujimori; Masahiko Maekawa; Takayoshi Kuroda-SowaCHEMISTRY LETTERS CHEMICAL SOC JAPAN 40 (10) 1184 - 1186 0366-7022 2011/10 [Refereed]
A novel mixed-valence Cu(I)-Cu(II) coordination polymer with an infinite one-dimensional (1-D) structure, [(Cu4CuI4)-Cu-I-I-II(Mor-dtc)(2)(CH3CN)(2)](n) (Mor-dtc(-): morpholine dithiocarbamate), was prepared and structurally characterized by X-ray diffraction. This complex consists of a mononuclear copper(II) unit of [Cu-II(Mor-dtc)(2)] and a tetranuclear Cu(I) unit of [Cu4I4(CH3CN)(2)]. It also shows semiconductive behaviors with a relatively small activation energy, which was revealed by impedance analysis. - Takashi Okubo; Hiroyasu Kuwamoto; Kyung Ho Kim; Shinya Hayami; Akihito Yamano; Motoo Shiro; Masahiko Maekawa; Takayoshi Kuroda-SowaINORGANIC CHEMISTRY AMER CHEMICAL SOC 50 (7) 2708 - 2710 0020-1669 2011/04 [Refereed]
The reaction of Cu(Hm-dtc)(2), Br-2, and CuBr2 yielded a new mixed-valence octanuclear Cu-I/Cu-II/Cu-III cluster, encapsulating a Br anion in the center of the cluster cage. The octanuclear cluster units form a 1D assemblage, which induces intervalence charge-transfer transitions from Cu-II ions to Cu-III ions between the clusters. - Takashi Okubo; Naoya Tanaka; Kyung Ho Kim; Haruho Anma; Shu Seki; Akinori Saeki; Masahiko Maekawa; Takayoshi Kuroda-SowaDALTON TRANSACTIONS ROYAL SOC CHEMISTRY 40 (10) 2218 - 2224 1477-9226 2011 [Refereed]
A novel mixed-valence Cu(I)-Cu(II) coordination polymer having an infinite three-dimensional (3D) structure, {[(Cu4Cu2Br4)-Cu-I-Br-II(Pyr-dtc)(4)]center dot CHCl3}(n) (1) (Pyr-dtc(-) = pyrrolidine dithiocarbamate), has been prepared and structurally characterized via X-ray diffraction. This complex consists of 1D Cu(I)-Br chains and bridging mononuclear copper(II) units of Cu-II(Pyr-dtc)(2), which form an infinite 3D network. A magnetic study indicates that this complex includes copper(II) ions exhibiting a weak antiferromagnetic interaction (theta = -0.086 K) between the unpaired electrons of the copper(II) ions present in the diamagnetic Cu(I)-Br chains. The carrier transport properties of 1 are investigated using an impedance spectroscopy technique and flash-photolysis time-resolved microwave conductivity measurement (FP-TRMC). The impedance spectroscopy reveals that this complex exhibits intriguing semiconducting properties at a small activation energy (E-a = 0.29 eV (bulk)). The sum of the mobilities of the negative and positive carriers estimated via FP-TRMC is Sigma mu similar to 0.4 cm(2) V-1 s(-1). - Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 29 (14) 2807 - 2813 0277-5387 2010/09 [Refereed]
Three novel 1D Cu(I) coordination polymers [Cu4X4(pprd)(2)](n) (X = Cl(1), Br(2) and I(3): pprd = 4-(2-pyridyl)pyrimidine) were systematically synthesized by Cu(I) halides and the pprd ligand, and they have been characterized by X-ray, IR, and TG-DTA analyses. The molecular structure of complex 1 essentially resembles to that of complex 2. In complexes 1 and 2, four Cu(I) atoms are bridged by four Cl or Br anions to form an eight-membered Cu4X4 framework in the twist-chair form. Furthermore, the Cu4X4 frameworks are coordinated by the chelate and bridging sites of two pprd ligands to form a unique 1D two-stepped Cu(I) coordination polymer, in which two stairs are formed by the Cu4X4 core and two heteroaromatic planes of pprd. In the crystal packing structures, it is interesting that two heteroaromatic planes of pprd are stacking along the b-axis for complex 1 and the a-axis for complex 2. In contrast, four Cu(I) atoms in complex 3 are bridged by four I atoms to form a Cu4I4 stepped cubane tetramer. Additionally, the Cu4I4 stepped cubane cores are linked by the chelate and bridging sites of two pprd ligands to form an infinite 1D zigzag-chain Cu(l) coordination polymer. The thermal decomposition behaviors for Cu(I)-X/pprd complexes 1, 2 and 3 were determined by thermogravimetric analysis (TG-DTA). Although the thermal decomposition behaviors of complex 1 were unidentified, those of complexes 2 and 3 were assigned. The mass loss at the first stage of thermal decomposition for polymeric [Cu4X4(pprd)(2)](n) was identical to the formation of oligomeric [Cu4X4(pprd)] by the elimination of one pprd molecule. The mass loss at the next stage was decided to the formation of Cu4X4 by the elimination of another pprd molecule. (C) 2010 Elsevier Ltd. All rights reserved. - Kyung Ho Kim; Takashi Okubo; Naoya Tanaka; Naoto Mimura; Masahiko Maekawa; Takayoshi Kuroda-SowaCHEMISTRY LETTERS CHEMICAL SOC JAPAN 39 (7) 792 - 793 0366-7022 2010/07 [Refereed]
The application of halide-bridged mixed-valence Cu(I)Cu(II) coordination polymers with hexamethylenedithiocarbamate (Hm-dtc) ligand as sensitizing materials for dye-sensitized solar cells (DSSCs) with poly(3,4-ethylenedioxythiophene) tetramethacrylate (PEDOT-TMA) counter electrode is novel. DSSCs having coordination polymers in comparison with a mononuclear Cu(Hm-dtc)(2) complex exhibited better power conversion efficiency because of the high photocurrent density. - Takashi Okubo; Naoya Tanaka; Kyung Ho Kim; Hironobu Yone; Masahiko Maekawa; Takayoshi Kuroda-SowaINORGANIC CHEMISTRY AMER CHEMICAL SOC 49 (8) 3700 - 3702 0020-1669 2010/04 [Refereed]
New mixed-valence Cu-I-Cu-II coordination polymers with one-dimensional, infinite-chain structures, [(Cu2CuX2)-Cu-I-X-II(Hm-dtc)(2)(CH3-CN)(2)](n) [Hm-dtc(-) = hexamethylene dithiocarbamate, X = Br- (1), I- (2)], have been prepared and structurally characterized by X-ray diffraction. These complexes consist of a mononuclear copper(II) unit Cu-II(Hm-dtc)(2) and dinuclear copper(I) units Cu-2(I)(CH3CN)(2)X-2. Magnetic studies have revealed that these complexes have a relatively strong antiferromagnetic interaction [J = -26.9 cm(-1) (1) and J = -22.2 cm(-1) (2)] between the unpaired electrons of the Cu-II ions through the dinuclear copper(I) halide unit of (Cu2X2)-X-I in the chain. The electrical properties of 1 and 2 are investigated using an impedance spectroscopy technique, and it is revealed that these complexes exhibit intriguing semiconducting properties with small activation energies [E-a = 0.562 eV (1) and E-a = 0.479 eV (2)]. - Zhong Yu; Toshiyuki Shimizu; Toshi Tominaga; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 82 (10) 1274 - 1276 0009-2673 2009/10 [Refereed]
Columnar assembly of dimeric Fell Schiff base complex based on twisted-overlap orientation of salophen platfonns exhibits ferromagnetic interactions at low temperature, which is ascribable to mu-phenoxy-bridged Fe ... Fe interactions and pi-pi interactions. - Masahiko Maekawa; Toshi Tominaga; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataEUROPEAN JOURNAL OF INORGANIC CHEMISTRY WILEY-V C H VERLAG GMBH (28) 4225 - 4231 1434-1948 2009/10 [Refereed]
Four novel Cu-I-Ph(2)bpm/C2H4 adducts [Cu(Ph(2)bpm)(C2H4)]X [X = BF4 (1a, 1b), ClO4 (2) and PF6 (3); Ph(2)bpm = 6,6'-diphenyl-4,4'-bipyrimidine] were prepared and they have been characterized by X-ray, H-1 NMR, IR and TG-DTA analyses. The molecular structures of Cu-I-Ph(2)bpm/C2H4 complexes la, 1b, 2 and 3 are essentially similar: the Cu atom is coordinated by two N atoms in the chelate site of Ph(2)bpm and the C=C bond of C2H4 in the trigonal-planar geometry. Interestingly, their crystal packing structures are much different from the connection manners of an intermolecular pi-pi stacking interaction and a C-H center dot center dot center dot N contact, resulting in the self-assembly of Cu-I-C2H4 adducts with a unique three-dimensional network structure. The X-ray, H-1 NMR, IR data support the assumption that the contribution of the larger Cu-I -> C2H4 pi back-donation bonding is induced by the electron-releasing phenyl group. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) - Atsuhiro Nabei; Takayoshi Kuroda-Sowa; Toshiyuki Shimizu; Takashi Okubo; Masahiko Maekawa; Megumu MunakataPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 28 (9-10) 1734 - 1739 0277-5387 2009/06 [Refereed]
The preparation and magnetic properties of three Fe(II)-bis-Schiff base complexes, [Fe(2)(L1)2(4,4'-bpy)]center dot MeOH (1), [Fe(L2)(EtOH)] (2) and [Fe(L3)(MeOH)] (3) (L1 =N,N'-bis(2-hydroxy-1-naphthaldehyde)-1,2-phenylenediimine; L2 = N,N'-bis(salicylidene)-1,2-phenylenediamine; L3 = N,N'-bis(5-Cl-salicylidene)-1,2-phenylenediamine; 4,4'-bpy = 4,4'-bipyridine) are reported. X-ray single crystal structure analyses for 1-3 reveal that 1 shows a dinuclear Fe(II)-bis-Schiff base complex bridged by 4,4'-bpy, while 2 and 3 show mononuclear structures. Molecular packing of 2 shows a uniform one-dimensional chain structure through hydrogen bonds and Fe center dot center dot center dot pi interaction and that of 3 indicates significant pi-pi interaction to form a dimmer structure. The chi T-T plots of 1-3 show all ferromagnetic interaction at low temperature. The origin of the ferromagnetic interaction observed in 2 is tentatively ascribed to the dimer formation through Fe center dot center dot center dot pi interaction at low temperature. (C) 2008 Elsevier Ltd. All rights reserved. - Zhong Yu; Takayoshi Kuroda-Sowa; Hiroaki Kume; Takashi Okubo; Masahiko Maekawa; Megumu MunakataBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 82 (3) 333 - 337 0009-2673 2009/03 [Refereed]
The spin-crossover (SCO) complex [Fe(qnal)(2)]center dot CH2Cl2 (1), (Hqnal: N-(8'-quinolyl)-2-hydroxy-1-naphthaldimine) with an N4O2 donor set, has been synthesized and characterized. Investigation of magnetic properties shows that the complex exhibits an abrupt and complete spin transition with a 5 K wide thermal hysteresis loop. The X-ray diffraction analysis of complex 1 reveals that the molecules are connected into a quasi one-dimensional chain through extended pi-pi interactions between aromatic rings of ligands. The effects of metal doping on SCO properties have been investigated in the mixed-metal system [Fe1-xMx(qnal)(2)]center dot CH2Cl2 (M = zinc(II) and nickel(II)). The results reveal that metal doping increases the gradual character of spin transition, and no marked differences found between zinc and nickel doping, which suggest the dominant effect of the doping-degree (concentration) rather than metal species on cooperativity. However, the metal doping shows different effects on critical temperature (T-1/2), where a more pronounced descending of T-1/2 is observed in response to increased Zn-doping than in Ni-doping, indicating the noticeable consequence of internal pressure due to the different radii of doping metal ions. - Zhong Yu; Takayoshi Kuroda-Sowa; Atsuhiro Nabei; Masahiko Maekawa; Takashi OkuboACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE WILEY-BLACKWELL PUBLISHING, INC 65 (3) M257 - U298 1600-5368 2009/03 [Refereed]
In the title complex, [Co(C(26)H(20)N(2)O(4))(NCS)]center dot C(4)H(10)O center dot CH(2)Cl(2), the pentacoordinated Co(III) atom exhibits a distorted square-pyramidal geometry with an N,N',O,O' tetradentate Schiff base ligand in the basal plane and one thiocyanate ligand at the apical site. The diethyl ether molecule is located in a cavity provided by four O atoms of the ligand with weak C-H center dot center dot center dot O interactions, generating two short O center dot center dot center dot O contact distances [2.766 (3) and 2.745 (3) angstrom] between the diethyl ether molecule and the ligand. The crystal structure is stabilized by the weak C-H center dot center dot center dot O and C-H center dot center dot center dot N interactions and pi-pi interactions between the naphthyl ring system and the benzene ring [centroid-centroid distance = 3.657 (5) angstrom] and between the two naphthyl ring systems [centroid-centroid distance = 4.305 (2) angstrom]. - Atsuhiro Nabei; Takayoshi Kuroda-Sowa; Takashi Okubo; Masahiko Maekawa; Megumu MunakataACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE WILEY-BLACKWELL 65 (2) M188 - U669 1600-5368 2009/02 [Refereed]
The title compound, [Co(C(22)H(18)N(2)O(4))]center dot 2CH(2)Cl(2), was isolated from the reaction of N,N '(o-phenylene)bis(vanillalimine) (H(2)L) with Co(SCN)(2). The crystal structure contains a Co(II) ion surrounded by the L(2-) ligand in a slightly distorted square-planar fashion. Intermolecular C-H center dot center dot center dot O hydrogen-bonding contacts between the dichloromethane solvent molecules and the methoxy or carboxylate O atoms are observed in the crystal structure. The planar complex molecules stack through inversion related pi-pi interactions between the six-membered rings of the vanillalimine half ligands. The distance between centroids is 3.498 (2) angstrom and the perpendicular distance is 3.345 angstrom. A partial stacking is observed with a centroid-centroid distance of 3.830 (2) angstrom, a perpendicular distance of 3.350 angstrom and a slippage of 1.856 angstrom. - Masahiko Maekawa; Atsuhiro Nabei; Toshi Tominaga; Kunihisa Sugimoto; Toshie Minematsu; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaDALTON TRANSACTIONS ROYAL SOC CHEMISTRY (3) 415 - 417 1477-9226 2009 [Refereed]
Three novel Cu(I)-C2H4 adducts bearing 4-(2-pyridyl)-pyrimidine were self-assembled, and the roles of anion and solvent were proved in the formation process. - Takayoshi Kuroda-Sowa; Zhong Yu; Yuka Senzaki; Kunihisa Sugimoto; Masahiko Maekawa; Megumu Munakata; Shinya Hayami; Yonezo MaedaCHEMISTRY LETTERS CHEMICAL SOC JAPAN 37 (12) 1216 - 1217 0366-7022 2008/12 [Refereed]
Novel Fe-II complexes with N4O2 donor sets having, extended pi-conjugated aromatic rings, [Fe(qnal)(2)]center dot CH2Cl2 and [Fe(qnal)21, show abrupt spin transitions at 220 and 265 K, respectively. Both complexes show LIESST effects below 80 K. - Atsuhiro Nabei; Takayoshi Kuroda-Sowa; Takashi Okubo; Masahiko Maekawa; Megumu MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 361 (12-13) 3489 - 3493 0020-1693 2008/09 [Refereed]
Two new one-dimensional Fe(II)-bis-Schiff base complexes, [Fe(L1)(pyz)] center dot CH(2)Cl(2) (1) and [Fe(L2)(pyz)] center dot 2CH(2)Cl(2) (2) (H(2)L1 = bis(O-vanillin)-O-phenylenediimine, H(2)L2 = bis(O-vanillin)-2,3-naphthalenediimine, pyz = pyrazine) are reported with their crystal structures and magnetic property. Compound 1 shows a two-step SCO behavior while 2 shows HS at all the temperature range measured. Although the extension of aromatic moiety from benzene (L1) to naphthalene (L2) was introduced for the purpose of strengthening the cooperativity, it leads to the absence of SCO, due to the unanticipated pi-pi interaction, which leads to the longer Fe-N bond lengths and a weak ligand field around Fe(II) ion. (c) 2008 Elsevier B. V. All rights reserved. - Ming Wen; Megumu Munakata; Yi-Zhi Li; Yusaku Suenaga; Takayoshi Kuroda-Sowa; Masahiko Maekawa; Manabu AnahataPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 26 (12) 2455 - 2460 0277-5387 2007/07 [Refereed]
For the purpose of investigating the coordination behavior of sterically congested alkenes and exploring the possibility of non-planar complexation in the polycyclic aromatic system for formation of extended polymeric networks, triptycene (tpty) has been studied with regard to its complexation with the silver(I) ion. The crystal structures of [Ag(tpty)(THF)(2)](ClO4) (1) and [Ag-6(tPtY)(4)(CF3SO3)(2-)(H2O)(6)](CF3SO3)(4) (2) have been determined by single-crystal X-ray diffraction. The polycyclic aromatic hydrocarbon triptycene is found to offer a potential site for complexation, which can be utilized to generate an interesting array of organo-metallic polymers with one-dimensional (1D) chain and three-dimensional (3D) porous frameworks. (c) 2007 Elsevier Ltd. All rights reserved. - Megumu Munakata; Jing Han; Masahiko Maekawa; Yusaku Suenaga; Takayoshi Kuroda-Sowa; Atsuhiro Nabei; Hideaki EnsuINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 360 (8) 2792 - 2796 0020-1693 2007/05 [Refereed]
A novel Cu(II) coordination polymer with photochromic 1,2-bis(2'-methyl-5'-(4 ''-pyridyl)-3'-thienyl)perfluorocyclopentene (BM-4-PTP) was prepared and crystallographically characterized. Its photochromic behavior as well as magnetic property was investigated in crystalline phase. In complex [Cu(BM-4-PTP)Br-2(DMF)(2)] (1), each copper atom is bridged by two N atoms of BM-4-PTP, two Br atoms from anions and two O atoms of DMF in an slightly distorted octahedral geometry. The basal planar center is in turn linked by bidentate ligand forming a 1-D polymeric chain. Free ligand showed typical spectral changes upon appropriate optical excitation, indicating the reversible photochromism in crystalline phase. Complex 1 occurred reversible photoisomerization not only through the pi-pi* transition but also the MLCT transition in crystalline phase. On the other hand, the magnetic property of complex 1 has been investigated by means of ESR. The spectra slightly and reversibly changed in response to UV and visible light supporting the normal photoreactivity in crystalline phase. (C) 2006 Elsevier B.V. All rights reserved. - Jing Han; Masahiko Maekawa; Yusaku Suenaga; Hideaki Ebisu; Atsuhiro Nabei; Takayoshi Kuroda-Sowa; Megumu MunakataINORGANIC CHEMISTRY AMER CHEMICAL SOC 46 (8) 3313 - 3321 0020-1669 2007/04 [Refereed]
Three new metal complexes with 1,2-bis(2'-methyl-5'-(carboxylic acid)-3'-thienyl)perfluorocyclopentene (BM-5-CATP) were synthesized and characterized by X-ray diffraction analysis. BM-5-CATP serves as a bis-monodentate ligand that bridges metal centers to generate three 1D polymers. The two thienyl rings in the three complexes adopt antiparallel fashions, and the distances of 3.39, 3.53, and 3.57 angstrom between the two reactive carbons are short enough to allow photocyclizations to occur in the crystalline phase. [Co(BM-5-CATP)(py)(2)(MeOH)(2)] (1) displayed effective photoisomerization in the crystalline phase. Interestingly, solvated 1 underwent a solid-state conversion upon heating to generate, through the release of the coordinated MeOH and rearrangement of the coordination geometry, the desolvated form (1a), while maintaining reversible photochromism. The removal of the solvent led to obvious changes in physical properties such as color and magnetic properties. The ESR spectra of 1 and 1a changed reversibly upon photoexcitation, indicating changes in coordination geometry accompanied by photoreaction. The magnetic susceptibilities of 1 and 1a showed no obvious changes, suggesting that the cobalt-cobalt interaction through the long bridging BM-5-CATP is less effective. Both [Cu(BM-5-CATP)(py)(3)](EtOH)(py)(1.8) (2) and [Zn(BM-5-CATP)(phen)(H2O)] (3) exhibited reversible photoreactions in the crystalline phase. However, 3 did not show remarkable spectral changes because of steric hindrance from the coordinated bulky phenanthroline and the intramolecular H bonds. - Masahiko Maekawa; Hisashi Konaka; Toshie Minematsu; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaCHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY (48) 5179 - 5181 1359-7345 2007 [Refereed]
Three novel Cu(I) metallacalixarenes with C2H4 and CO legs, in which an anion is accommodated in the inside cavity, were self-assembled by anion templation and have been structurally characterized. - Megurnu Munakata; Jing Han; Atsuhiro Nabei; Takayoshi Kuroda-Sowa; Masahiko Maekawa; Yusaku Suenaga; Nozomu GunjimaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 25 (18) 3519 - 3525 0277-5387 2006/12 [Refereed]
Two novel Cu(II) complexes with 1,2-bis(2'-methyl-5'-(2"-pyridyl)-3'-thienyl)perfluorocyclopentene (BM-2-PTP) or its closed-form (closed-BM-2-PTP) were synthesized and characterized by X-ray crystallographic analysis. Both complexes are tetra-coordinated to two N atoms from distinct ligands and two Cl atoms from anions, forming 1-D polymeric structures. [Cu(BM-2-PTP)Cl-2] (1) showed typical spectral changes as analogous Ag(I) complexes with the same ligand upon appropriate light stimulus. However, closed-BM-2PTP displayed different photocyclization from its open-ring form upon irradiation with UV light, indicating the photogenerated closed form turned into two kinds of closed-ring isomers. Furthermore, [Cu(closed-BM-2-PTP)Cl-2] (2) was revealed to contain two conformers by X-ray crystallographic analysis and displayed similarities in photocyclization to its free ligand. The distinct absorptions of the UV spectrum were attributed to the coexistence of two conformers in complex 2, both of which showed effective photo reactivities in the crystalline phase. The photochromic mechanism of complex 2 is tentatively concluded as two conformers displaying independent photoreactions. (c) 2006 Published by Elsevier Ltd. - Megumu Munakata; Jing Han; Atsuhiro Nabei; Takayoshi Kuroda-Sowa; Masahiko Maekawa; Yusaku Suenaga; Nozomu GunjimaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 359 (13) 4281 - 4288 0020-1693 2006/10 [Refereed]
Three novel silver(l) complexes with 1,2-bis(2-methyl-5'-(2"-pyridyl)-3'-thienyl)perfluorocyclopentene (BM-2-PTP) were synthesized by the reaction of Ag(CF3SO3) or Ag(CF3COO) with BM-2-PTP in benzene at different temperatures. The structures of these metal complexes were revealed by X-ray crystallographic analyses and the correlation between crystal structures and photochromic performance was discussed. In complexes 1 and 2, silver(I) is three-coordinated to two nitrogens from distinct ligand molecules as well as one oxygen from anions to form a I-D polymeric structure. On the other hand, complex 3 contains two crystallographic independent Ag(I) with different coordination environments, and the adjacent BM-2-PTP molecules are connected by Ag-CF3CO2-Ag chains to afford a I-D double chain structure. The difference in structures of three complexes shows the interesting anionic effect on coordination and the subtleness of crystal engineering. It is noted that complex 3 underwent reversible photochromic reaction in crystalline state despite the unfavorable framework to the rotation of thiophene groups. (c) 2006 Elsevier B.V. All rights reserved. - Jing Han; Atsuhiro Nabei; Yusaku Suenaga; Masahiko Maekawa; Hiromichi Isihara; Takayoshi Kuroda-Sowa; Megumu MunakataPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 25 (13) 2483 - 2490 0277-5387 2006/09 [Refereed]
Reaction of [Rh-2(O2CC(CH3)(3))(4)] with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene (cis-dbe) or closed-dbe in benzene and dichloromethane yielded three novel Rh(II) complexes. Their structures were characterized and photochromic properties were studied. X-ray crystallographic analyses revealed that the coordination environments of the three metal complexes are quite different. Complex 2 exhibits a 1-D infinite chain structure with two cyano groups of the ligand bridging two metal ions while in complexes 1 and 3 the metal ions have a direct interaction with at least one of the sulfur atoms of the two bisthienylethene molecules. Closed-dbe of complex 3 was transferred to the ring-open form in the crystalline phase upon photoexcitation with 529 nm light. It underwent a photocycloreversion reaction although the metal atom is coordinated to the thienyl group. The irreversible cyclization reaction was presumably attributed to the fixed rotation of thienyl rings, short Rh-S distance and steric hindrance of anions. (C) 2006 Elsevier Ltd. All rights reserved. - M Maekawa; S Kitagawa; T Kuroda-Sowa; M MunakataCHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY (20) 2161 - 2163 1359-7345 2006/05 [Refereed]
A series of sandwich-shaped complexes based on two square tetranuclear Ag(I) metallomacrocycles, {[Ag-4(pprd)(4)](2)(XF6)}(BF4)(6)center dot 8MeNO(2) (pprd = 4-(2-pyridyl)pydmidine; X = Si, Ge and Sri), in which a XF62- anion is encapsulated, were prepared and their structures were characterized both in the solid state and solution. - Ming Wen; E. Kejia; Megumu Munakata; Yusaku Suenaga; Takayoshi Kuroda-Sowa; Masahiko Maekawa; Sheng Gang YanMOLECULAR CRYSTALS AND LIQUID CRYSTALS TAYLOR & FRANCIS LTD 457 203 - 213 1542-1406 2006 [Refereed]
Two silver( I) coordination complexes of 1,10-phenanthroline-5,6-dione (pdon), [Ag-2(pdon)(2)(ClO4)(2)] (1) and [Ag( pdon)(2)](CF3SO3) (2), have been synthesized and characterized by elemental analysis, IR, and X-ray diffraction analysis. Using AgClO4 with pdon, the central silver(I) is bridged by ligand pdon with two N and one O atoms and lead to the one-dimensional (1D) chain structure in 1. When triflate anion is used as a counter ion in 2, the silver(I) is chelated by two ligands with four N atoms, and then the molecular unit is linked by intermolecular hydrogen bond to afford a novel two-dimensional (2D) network architecture. - J Han; H Konaka; T Kuroda-Sowa; M Maekawa; Y Suenaga; H Isihara; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 359 (1) 99 - 108 0020-1693 2006/01 [Refereed]
Four novel Mo(II) and Rh(II) complexes with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene (cis-dbe) or closed-dbe were synthesized and characterized. Employing [M(O2CCF3)(4)] (M = Mo, Rh) with cis-dbe or closed-dbe afforded complex [MO2(O2CCF3)(4)(cis-dbe)](benzene) (1), [Rh-2(O2CCF3)(4)(cis-dbe)](benzene) (2), [{MO2(O2CCF3)(4)}(2)(closed-dbe)] (3), and (Rh-2(O2CCF3)(4)(closed-dbe)](p-xylene) (4). The structures of four metal complexes were revealed by X-ray crystallographic analyses and the correlation between the crystal structures and the photochromic performance was discussed. In all complexes, two cyano groups of the ligand bridged two dimetal carboxylates to give a 1-D zigzag infinite chain structure. Upon irradiation with 405 nm light, complex 1 turned into reddish purple from yellow, and the color reverted to initial yellow on exposure to 563 nm light, indicating the reversible cyclization/ring-opening reaction in the crystalline phase. However, the Rh(II) complex 2 did not display similarities in reaction induced by light, which is attributable to the lower ratio of photoactive anti-parallel conformers compared with complex 1 and coordination effect of metal ions on photochromism of diarylethenes. The complexes of Rh(II) ions did not exhibit the expected reversible photoinduced behavior. (c) 2005 Elsevier B.V. All rights reserved. - M Maekawa; T Minematsu; A Nabei; H Konaka; T Kuroda-Sowa; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 359 (1) 168 - 182 0020-1693 2006/01 [Refereed]
Four novel mononuclear Rh-Cp* and Ir-Cp* complexes with polycyclic aromatic hydrocarbons (PAHs), [M(Cp*)(eta(6-)PAHs)](BF4)(2)(M= Rh and Ir; Cp* = eta(5)-C5Me5; PAHs = phenanthrene (phn), pyrene (pyr) and triphenylene (triph)), were prepared by the reactions of the intermediate [M(Cp*)(Me2CO)(3)](2+) with appreciable PAHs. Their structures were characterized by a single crystal X-ray analysis, H-1, C-13 {H-1} NMR and 2D NMR techniques. The X-ray crystallographic studies showed that the [M(Cp*)](2+) fragment is eta(6-)coordinated to one terminal benzene ring in each PAH. In particular, it is interesting to note that the partial pi/pi/pi/pi interaction was formed in the Ir-pyr complex [Ir(Cp*)(eta(6)-pyr)](BF4)(2). The 1D and 2D NMR studies described that the Rh-Cp* and Ir-Cp* complexes with PAHs gave unique H-1 and 13C [ 1 H I NMR spectra with positive coordination shifts (Delta delta(H-1, C-13) in (CD3)(2)CO at 23 degrees C, which are likely induced by the local effect and the non-local effect on the coordination of the [M(Cp*)]2+ fragment to PAHs. The decreasing of the coupling constants ((3)J(H-H)) in the eta(6)-Coordinated benzene ring is also induced, with no changes in the uncoordinated benzene rings. The time-course of 1H NMR spectra showed that Rh-Cp* and Ir-Cp* complexes with PAHs are partially dissociated to [M(Cp*)(Me2CO)(3)](2+) and metal-free PAHs in (CD3)2CO at 23 degrees C. It was demonstrated that their stabilities are in the order of Ir-triph, Ir-phn, Ir-pyr and Rh-triph complexes in (CD3)(2)CO. (c) 2005 Elsevier B.V. All rights reserved. - T Kuroda-Sowa; GQ Bian; M Hatano; H Konaka; S Fukuda; S Miyoshi; M Maekawa; M Munakata; H Miyasaka; M YamashitaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 24 (16-17) 2680 - 2690 0277-5387 2005/11 [Refereed]
The preparation and physical characterization are reported for a family of novel Mn-12 single-molecule magnets having diphenyl-phosphate (labeled dppH) bridges, [Mn12O12(O2CR)(16-x)(dpp)(x)(H2O)(y)] (R = CH3: x = 4, y = 0 (1); x = 8, y = 2 (2), R = Ph: x = 4, y = 4 (5); x = 8, = 4 (6), and R = Et: x = 4, y 4 (9)) and their tetraphenyl phosphate salts [Ph4P][Mn12O12(O2CR)(16-x)(dpp)(x)(H2O)(4)] (R = CH3: x = 4 (3); x 8 (4) and R = Ph: x = 4 (7); x = 8 (8)). The crystal structures of I and 5 were characterized by X-ray. The X-ray structure analysis of I reveals that there are four five-coordinate Mn-III ions with (MnH)-H-... approaches and without coordinating water molecules. The H-1 NMR measurements show H2O can coordinate to a vacant site of 1 in CD2Cl2 solution. Ac magnetic susceptibility measurements indicate that nine complexes are single-molecule magnets. The increase of the number of dpp(-) ligands resulted in a decrease of the U-eff values of neutral Mn-12 SMMs estimated from ac measurements. Complexes 1 and 5 show a quantum tunneling behavior, whose ground states were tentatively assigned to S = 10 with g = 1.78, and D = -0.60 K; S = 10 with g = 1.92, and D = -0.63 K, respectively. (c) 2005 Elsevier Ltd. All rights reserved. - GQ Bian; T Kuroda-Sowa; T Nogami; K Sugimoto; M Maekawa; M Munakata; H Miyasaka; M YamashitaBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 78 (6) 1032 - 1039 0009-2673 2005/06 [Refereed]
The preparation and physical characterization are reported for three Mn-12 single-molecule magnets (SMMs) having naphthalenecarboxylate bridges, [Mn12O12(2-nc)(16)(H2O)(4)] (1, 2-ncH = 2-naphthalenecarboxylic acid), its Ph4P+ salt (2) and [Mn12O12(1-nc)(16)(H2O)(4)] (3, 1-ncH = 1-naphthalenecarboxylic acid). Complex 1 center dot 2CH(2)Cl(2)center dot 4.5H(2)O crystallizes in the monoclinic space group C2/c, with cell dimensions at -160 degrees C of a = 28.524 angstrom, b = 17.819 angstrom, c = 36.058 angstrom, beta = 92.399 degrees, and Z = 4. The X-ray structure analysis of 1 center dot 2CH(2)Cl(2)center dot 4.5H(2)O reveals that each [Mn-12] molecule is connected to the neighboring molecules through eight pi... pi interactions to form a two-dimensional structure within the bc-plane. This is the first SMM that self-assembles two-dimensionally via pi... pi interaction. From Arrhenius plots of the frequency dependence of the temperatures of the X"(M) peaks, the effective energy barriers U-eff for the reversal of the magnetization spin were estimated to be 61 K, 53 K, and 61 K for high-temperature phases of 1-3, respectively, and 31 K and 33 K for the low-temperature (UT) phases of 1 and 3, respectively. The analysis of the reduced magnetization data suggests that the LT phase of I has an S = 9 ground state with g = 1.998 and D = -0.61 K. - GL Ning; XC Li; WT Gong; M Munakata; M MaekawaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 358 (7) 2355 - 2362 0020-1693 2005/04 [Refereed]
Reactions of silver(1) perchlorate with tetraphenyl-cyclopentadiene (Ph4H2-C-5) have isolated two novel silver(1) bridged tetraphenyl-pyrylium complexes: [Ag(ClO4)(Ph4HC5O+)](ClO4)(-) (1) and [Ag(ClO4)(H2O)(Ph4HC5O+)](ClO4-) (2), depending on moisture-content of the reactants. Structure studies using single-crystal X-ray diffraction have showed that complex 1contains a distorted tetrahedral metal center bridging two neighboring peripheral phenyl rings of one pyrylium cation and two perchlorate anions, whereas 2 involves a three-coordinate metal ion interacting with a pair of phenyl rings and one water molecule, leaving two perchlorate anions free from coordination. For both complexes, the precursor ligand Ph4H2C5 undergoes a ring-enlargement reaction, forming a six-membered pyrylium cation. The fundamentals of the synthesis, structure characterization and some properties are discussed. (c) 2005 Elsevier B.V. All rights reserved. - T Kuroda-Sowa; SO Liu; Y Yamazaki; M Munakata; M Maekawa; Y Suenaga; H Konaka; H NakagawaINORGANIC CHEMISTRY AMER CHEMICAL SOC 44 (6) 1686 - 1692 0020-1669 2005/03 [Refereed]
Reaction of [2.2]paracyclophane with silver(l) heptafluorobutyrate (AgC3F7CO2) has isolated three novel networks: [Ag-4(PCP)(C3F7CO2)(4)](.)pyrene (1), [Ag-4(PCP)(C3F7CO2)(4)](.)phen (phen = phenanthrene) (2), and [Ag-4(PCP)(C3F7CO2)(4)](.) fluorene (3), and an intercalation compound [Ag-4(PCP)(C3F7CO2)(4)](.)2benzene (4). All the four complexes exhibit two-dimensional (2D) sheet structures in which AgC3F7CO2 form an infinite chain and pcp acts as linkage. 1, 2, and 3 show 2D flat sheets with cavities in which guest molecules are situated, whereas 4 exhibits 2D zigzag layers between which guest benzene molecules are intercalated. Pcp shows mu-di-eta(1)-eta(2) coordination mode in 1, mu-tetra-eta(1) coordination mode in 2 and 3, and mu-tetra-eta(2) coordination mode in 4. The reversible guest exchanges were observed between complex 1, 2, or 3 and intercalation compound 4. It is unprecedented for metal-organic inclusion complexes that the guest exchange occurs where the guest is the solute molecule. Furthermore, 4 can release the guest, and the original framework was completely recovered after reincorporation of benzene. It should be noted that 4 can incorporate pyrene, phen, and fluorene to give 1, 2, and 3, respectively, after desorption. - M Maekawa; H Konaka; T Minematsu; T Kurorda-Sowa; Y Suenaga; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 358 (4) 1317 - 1321 0020-1693 2005/03 [Refereed]
Reaction of the precursor Ir complex [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]PF6 with 3,6-bis(2-pyridyl)tetrazine (bptz) in CH2Cl2 gave a novel dinuclear Ir hydrido complex [Ir-2(H)(4)(PPh3)(4)(bptz)](PF6)(2) center dot 4CH(2)Cl(2). Crystallographic study described an interesting coordination environment having a pi-pi interaction and H-1 NMR study showed unique uptield shifts of pyridyl rings that are likely induced by the ring current effect of neighboring PPh3 ligands. (c) 2004 Elsevier B.V. All rights reserved. - M Maekawa; Y Kayanuma; A Nabei; T Kuroda-Sowa; Y Suenaga; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 358 (4) 1313 - 1316 0020-1693 2005/03 [Refereed]
The single crystals 5 of dichloro-bridged dinuclear Rh-Cp* complex with neutral Me2CO molecules, [Rh-2(CP*)(2)(mu-Cl)(2)(Me-2-CO)(2)](BF4)(2) (CP* = eta(5)-C5Me5), was isolated and the structure was in first determined crystallographically. (c) 2004 Elsevier B.V. All rights reserved. - SQ Liu; H Konaka; T Kuroda-Sowa; M Maekawa; Y Suenaga; GL Ning; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 358 (4) 919 - 926 0020-1693 2005/03 [Refereed]
Coordination polymers of [2.2]paracyclophane (pep) with in situ silver(l) perfluoro-dicarboxylates characterized by single crystal X-ray analysis are described. Structures are found to strongly depend on the dicarboxylate spacer (n). With disilver(l) tetrafluorosuccinate ((CF2)(n)(COOAg)(2), n = 2), 3D network with composition of [Ag-4(PCP)(C2F4(CO2)(2))(2)] (1) forms in which silver salts afford infinite double chains and pep act as linkages between chains. Changing the silver salt to disilver hexafluoroglutarate ((CF2)(n)(COOAg)(2), n = 3) produces 3D pillared-layer structure of composition of [Ag-4(pcp)(C3F6(CO2)(2))(2)] (.) THF (2) (THF = tetrahydrofuran), in which silver salts form 2D sheets and pep act as pillars between the sheets. With silver octafluoroadipate (HO2C(CF2),CO2Ag, n = 4), 2-fold interpenetrated diamond structure, [Ag-2(pcp)(2)(HO2CC4F8CO2)(2)](2) (.) 2toluene (3), is obtained in which silver-anion chains and silver-pcp chains are connected with each other in the perpendicular manner. The three complexes represent unprecedented metal-organic networks of silver(I) multicarboxylates and polycyclic aromatic compounds. Additionally, the effects of the dicarboxylate conformations as well as the solvents on the resulting structures were discussed. (c) 2004 Elsevier B.V. All rights reserved. - GQ Bian; T Kuroda-Sowa; S Sugimoto; M Maekawa; M MunakataACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS BLACKWELL MUNKSGAARD 61 M144 - M146 0108-2701 2005/03 [Refereed]
The title one-dimensional chain polymer complex, [Mn(C6H4NO3)Cl(C6H5N)(2)](n), was isolated from the reaction of MnCl2 with 6-oxo-1,6-dihydropyridine-2-carboxylic acid (HpicOH) in pyridine. The asymmetric unit contains one [Mn(HPicO)Cl(py)(2)] moiety (py is pyridine), with the (HpicO)(-) ligand acting in a tridentate manner via the two carboxylate O atoms and the pyridone O atom. The operation of inversion centres generates eight- and 14-membered rings and, in conjunction with an a-axis translation, leads to an infinite chain extending along [100]. The Mn...Mn separations in this chain are 5.1069 (6) and 7.1869 (6) Angstrom. The Mn-II atom has a distorted octahedral coordination, with trans-axial pyridine ligands and with three O atoms and the Cl atom in the equatorial plane. The conformation of the 14-membered ring is stabilized by pairs of inversion-related N-H...O hydrogen bonds. - SQ Liu; T Kuroda-Sowa; H Konaka; Y Suenaga; M Maekawa; T Mizutani; GL Ning; M MunakataINORGANIC CHEMISTRY AMER CHEMICAL SOC 44 (4) 1031 - 1036 0020-1669 2005/02 [Refereed]
Three luminescent silver(I)-oligo(phenylenevinylene) complexes, [Ag-2(bmsb)(ClO4)(2)] (1), [Ag-2(bmsb)(H2O)(4)](BF4)(2) (2), and [Ag-2(bdb)(CF3SO3)(2)] (3) (bmsb = 1, 4-bis(methylstyryl)benzene, bdb = 4,4'-bis(2, 5-dimethylstryryl)biphenyl), have been synthesized and structurally characterized. Complexes 1 and 2 are 2D networks with unique metallocyclophane motifs. Complex 3 affords a 2D zigzag sheet, in which silver triflates form tubelike double chains and bdb molecules act as linkages. Complex 2 exhibits high electric conductivity because of columnar aromatic stackings formed through intra- and intermolecular pi-pi interactions. Complexes 1-3 in the solid state exhibit luminescence, of which excitation and emission maxima are shifted to longer wavelength as compared to those of the corresponding metal-free ligands. - GQ Bian; T Kuroda-Sowa; N Gunjima; M Maekawa; M MunakataINORGANIC CHEMISTRY COMMUNICATIONS ELSEVIER SCIENCE BV 8 (2) 208 - 211 1387-7003 2005/02 [Refereed]
Complex [Mn12O12(OAc)(16)(MeOH)(4)] having MeOH-coordination was synthesized and characterized, whose magnetic behaviors indicate it is a single-molecule magnet with the largest U-eff/k(B) of 76.2 K. (C) 2004 Elsevier B.V. All rights reserved. - SQ Liu; H Konaka; T Kuroda-Sowa; M Maekawa; Y Suenaga; GL Ning; M MunakataACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE BLACKWELL MUNKSGAARD 60 M1504 - M1506 1600-5368 2004/10 [Refereed]
The title compound, {[Ag-2(C16H16S2)(2)(C2H3N)(4)](C8F4O4) .2C(8)H(2)F(4)O(4).4C(2)H(3)N}(n) has been prepared from the reaction of 2,11-dithia[3.3]paracyclophane (dtpcp) and in situ silver(l) tetrafluoroterephthalate (TFTP2-) using an interface method. In the solid state the title compound forms two infinite chains, which are parallel to one another. One chain consists of [Ag-2(C16H16S2)(2)(C2H3N)4](n)(2n+) and the other is formed from TFTP2- and H2TFTP via O-c-H...O-c (c is carboxy) hydrogen- bonding interactions, with H...A distances of 1.72 (2) and 1.774 (19) Angstrom. The Ag-I ion is tetrahedrally coordinated by two acetonitrile N atoms and two dtpcp S atoms. The cyclophanes have inversion symmetry. - M Maekawa; T Minematsu; H Konaka; K Sugimoto; T Kuroda-Sowa; Y Suenaga; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 357 (12) 3456 - 3472 0020-1693 2004/09 [Refereed]
New five mono- and dinuclear Ir hydrido complexes with polydentate nitrogen ligands, [Ir(H)(2)(PPh3)(2)(tptz)]PF6 (1), [Ir-2(H)(4)(PPh3)(4)(tptz)](PF6)(2.2)H2O (2.2H(2)O), [Ir(H)(2)(PPh3)(2)(tppz)]BF4 (3), [Ir-2(H)(4)(PPh3)(4)(tppz)](BF4)(2) (4) and [Ir-2(H)(4)(PPh3)(4) (bted)](BF4)(2).6CHCl(3) (5.6CHCl(3)), were systematically prepared by the reactions of the precursor Ir hydrido complex [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]X (X=PF6 and BF4) With 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz), 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) and 1,4-bis(2,2:6,2"-terpyridine-4'-yl)benzene (bted), and their structures and properties were characterized in the solid state and in solution. Each of the Ir hydrido complexes with polydentate nitrogen ligands crystallographically described a unique coordination mode. Their H-1 NMR spectra demonstrated unusual I H NMR chemical shifts of pyridyl rings that are likely induced by the ring current effect of neighboring ligands. (C) 2004 Elsevier B.V. All rights reserved. - SQ Liu; H Konaka; T Kuroda-Sowa; Y Suenaga; H Ito; GL Ning; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 357 (12) 3621 - 3631 0020-1693 2004/09Four copper(I) complexes of 2,11-dithia[3.3]paracyclophane (dtpcp), [CuI(dtpcp)] . MeCN (1), [CuBr(dtpcp)] . MeCN (2), [CuCl(dtpcp)] . MeCN (3) and [Cu2I2(dtPCP)(2)] . Me-thf (4) (Me-thf = 2-methyltetrahydrofuran), have been synthesized and their molecular structures determined by X-ray crystallography. Complexes I and 2 are isostructural, and exhibit 31) networks with elliptical channels along a-axis, which are constructed by dtpcp molecules bridging zigzag CuI and CuBr chains, respectively. Complexes 3 and 4 are 21) porous sheet networks constructed by bridging the zigzag copper-dtpcp chains via rhombic ring of Cu2X2 (X = Cl or 1). All sheets in 3 are packed in an eclipsed manner through pi-pi stackings to generate channels along the a-axis. However, the 2D porous sheets in 4 are packed in an offset mode such that channels are not formed along c-axis. Complexes I and 2 can reversibly incorporate guest acetonitriles without collapse of structures, and the original frameworks of I and 2 are completely recovered after incorporation of guests which are confirmed by X-ray powder diffraction (XRPD) pattern and H-1 NMR spectrum. Additionally, complex I exhibits selectivity in size and polarity for guest inclusion. (C) 2004 Elsevier B.V. All rights reserved.
- M Wen; M Munakata; Y Suenaga; T Kuroda-Sowa; M Maekawa; Kodai, IPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 23 (13) 2117 - 2123 0277-5387 2004/08 [Refereed]
Three silver(I) coordination complexes of diaza- and dibenzo-crown ethers, [Ag(DDAc)](CF3SO3) (1), [Ag-2(DDAC)(CF3SO3)(2)] (2) and [Ag-2(DB24C8)(CF3SO3)(2)] (3) have been synthesized by using different molar ratios of ligand to silver triflate salt, and characterized structurally. A large excess of DDAC ligand leads to mononuclear complex 1, and a large excess of silver triflate gives rise to dinuclear complex 2, based on metal-heteroatom and metal-oxygen interactions. Ligand DB24C8 coordinates two silver(I) ions to afford dinuclear complex 3. (C) 2004 Elsevier Ltd. All rights reserved. - GQ Bian; T Kuroda-Sowa; H Konaka; M Hatano; M Maekawa; M Munakata; H Miyasaka; M YamashitaINORGANIC CHEMISTRY AMER CHEMICAL SOC 43 (16) 4790 - 4792 0020-1669 2004/08 [Refereed]
The preparation and physical characterization are reported for a novel single-molecule magnet [Mn12O12(OAc)(12)(dPP)(4)] (dppH = diphenyl phosphate) with no coordinating water molecules. The crystal structure analysis reveals that there are four five-coordinate Mn-III ions with Mn...H approaches. Addition of water in CD2Cl2 solution was monitored by H-1 NMR, which showed that H2O could coordinate to a vacant site of a five-coordinate Mn-III ion in solution. The measurements and analyses of magnetization hysteresis and ac magnetic susceptibility indicate that the title complex is a single-molecule magnet with a quantum tunneling behavior, whose ground state was tentatively assigned to S = 10 with g = 1.78 and D -0.60 K. - GQ Bian; T Kuroda-Sowa; H Konaka; M Maekawa; M MunakataACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS BLACKWELL MUNKSGAARD 60 M338 - M340 0108-2701 2004/07 [Refereed]
The title compound, [Mn-2(mu-O)(C6H3NO3)(2)(C5H5N)(4)].H2O, was isolated from the reaction of 2,6-pyridinedicarboxylic acid with [Mn12O12(CH3COO)(16)(H2O)(4)] in pyridine. The dimanganese complex has twofold symmetry; the Mn-III atoms are bridged by one oxo and two amidate ligands and show compressed octahedral Jahn-Teller distortion. The molecular packing comprises a three-dimensional structure constructed by means of extensive intermolecular interactions, including three kinds of hydrogen bonds and pi-pi interactions. - SQ Liu; H Konaka; T Kuroda-Sowa; M Maekawa; Y Suenaga; GL Ning; M MunakataACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE WILEY-BLACKWELL 60 M865 - M867 1600-5368 2004/06 [Refereed]
The title compound, {[Ag(C16H16S2)(C2H3N)(2)](C6HF8O4)}(n), forms two infinite chains, which are approximately perpendicular to each other. One chain consists of [Ag(C16H16S2)(C2H3N)(2)](n)(n+), and the other is formed from HOFA(-). (HOFA(-) is hydrogen octafluoroadipate) units via O-c - H ... Oc (c is carboxy) hydrogen-bonding interactions, with an H ... A distance of 1.66 (5) Angstrom. Each silver(I) cation lies on a crystallographic twofold rotation axis and has a tetrahedral geometry, defined by two N atoms belonging to two acetonitrile molecules and two S atoms from two 2,11-dithia[3.3]paracyclophane molecules. The cyclophanes have inversion symmetry. - T Kuroda-Sowa; T Handa; T Kotera; M Maekawa; M Munakata; H Miyasaka; M YamashitaCHEMISTRY LETTERS CHEMICAL SOC JAPAN 33 (5) 540 - 541 0366-7022 2004/05 [Refereed]
The first Mn-12 complex with mu(3)-methanesulfonate bridge was observed and its single-molecular magnetic property was characterised. - GL Ning; Cheng, X; M Munakata; WT Gong; M Maekawa; T KamikawaJOURNAL OF ORGANIC CHEMISTRY AMER CHEMICAL SOC 69 (4) 1432 - 1434 0022-3263 2004/02 [Refereed]
Phenyl-substituted cyclopentadienes are proved to form phenylated pyrylium cations in the presence of silver(l) perchlorate by insertion of an oxygen atom into the cyclopentadiene-ring. Three phenylated pyrylium compounds, [(Ph5C5O+)(ClO4-)](2)(CH2Cl2) (1), Ag(ClO4)(ClO4)(Ph4HC5O+) (ClO4-) (2), and (Ph3H2C5O+)(ClO4-) (3) have been synthesized and characterized. A possible reaction pathway and formation mechanism of the pyrylium cation are proposed and discussed. - Masahiko Maekawa; Hisashi Konaka; Kunihisa Sugimoto; Yusaku Suenaga; Takayoshi Kuroda-Sowa; Megumu MunakataAnalytical Sciences: X-ray Structure Analysis Online Japan Society for Analytical Chemistry 20 (2) x71 - x72 1348-2238 2004 [Refereed]
The title Cu(II) complex, [Cu(phen)2Cl]BF4 (phen = 1,10-phenanthroline), was characterized crystallographically, which shows the most near regular trigonal bipyramidal geometry in the five-coordinate [Cu(phen)2Cl]+ series. 2004 © The Japan Society for Analytical Chemistry. - Masahiko Maekawa; Yusaku Suenaga; Takayoshi Kuroda-Sowa; Megumu MunakataAnalytical Sciences: X-ray Structure Analysis Online Japan Society for Analytical Chemistry 20 (1) x11 - x12 1348-2238 2004 [Refereed]
Colorless single crystals of a dinuclear Ir complex, [Ir2(Cp*)2(μ-Cl)3]BF4 (Cp* =η5-C5Me5), were obtained with a reaction of [Ir(Cp*)(Me2CO)3]2+ and triptycene under Ar. The crystal structure was determined using CCD single crystal XRD data. The two Ir atoms are μ2-bridged by three chloride atoms to provide a dinuclear structure with a unique trigonal-bipyramidal Ir2Cl3 core. 2004 © The Japan Society for Analytical Chemistry. - M Munakata; SQ Liu; H Konaka; T Kuroda-Sowa; Y Suenaga; M Maekawa; H Nakagawa; Y YamazakiINORGANIC CHEMISTRY AMER CHEMICAL SOC 43 (2) 633 - 641 0020-1669 2004/01 [Refereed]
Reaction of [2.2]paracyclophane (pcp) with silver(l) trifluoroacetate (AgCF(3)CO(2)) and silver(l) pentafluoroproprionate (AgC(2)F(5)CO(2)) has led to isolation of three novel intercalation polymers: [Ag(4)(PCP)(CF(3)CO(2))(4)](C(6)H(6)) (1), [Ag(4)(pcp)(CF(3)CO(2))(4)](C(6)H(3)Me(3)) (2), and [Ag(4)(PCP)(C(2)F(5)CO(2))(4)](PCP) (3). Structure studies using single crystal X-ray diffraction have shown that all compounds contain two-dimensional layered frameworks based on cation-pi interactions, in which pcp exhibits an unprecedented mu-tetra-eta(2) Coordination mode. Guest molecules which weakly interact with the host pcp via C-H(...)pi interactions are intercalated between layers. The guest-eliminated complexes (1a and 2a) and guest-reincorporated ones (1b or 1c and 2b or 2c), accompanied by small structural changes, were confirmed by (1)H NMR, thermogravimetric analysis, mass spectra, and X-ray powder diffraction patterns. The structural changes from 1 --> 1a --> 1c (=11) can take place reversibly in the process of exposure of 1 a to benzene vapor, The original framework of complex 2 is also completely recovered by immersing 2a in mesitylene as well as exposing it to mesitylene vapor. - M Maekawa; Y Suenaga; T Kuroda-Sowa; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 357 (1) 331 - 338 0020-1693 2004/01 [Refereed]
Novel two iridium terphenyl complexes were prepared and their structures were characterized crystallographically. The reaction of [Ir(cod)(2)]BF4 with p-terphenyl (p-tp) in CH2C2, was carried out to afford dinuclear Ir(I) complex {[Ir-2(p-tp)(cod)(2)](BF4)(2) (.) 2CH(2)Cl(2)}(3) (cod = 1, 5-cyclooctadiene) (1 (.) 2CH(2)Cl(2)), whereas the reaction of the intermediate [Ir(eta(5)-C5Me5)(MeCO)(3)](3+) in Me2CO with m-terphenyl (m-tp) was done to provide mononuclear Ir(III) complex [Ir(m-tp)(eta(5)-C5Me5)](BF4)(2) (2). In complex 1 (.) 2CH(2)Cl(2) two Ir atoms are eta(6)-coordinated to both sides of terminal benzene rings from the upper and lower sides in the p-tp ligand, while one Ir atom is eta(6)-coordinated to one side of the terminal benzene ring in the m-tp ligand in complex 2. Each crystal structure describes the first coordination mode found in metal complexes with the m- and p-tp ligands. (C) 2003 Elsevier B.V. All rights reserved. - T Kuroda-Sowa; T Nogami; H Konaka; M Maekawa; M Munakata; H Miyasaka; M YamashitaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 22 (14-17) 1795 - 1801 0277-5387 2003/07 [Refereed]
The preparation and physical characterization are reported for novel Mn-12 single-molecule magnets having thiophenecarboxylate bridges, [Mn12O12(O2CC4H3S)(16)(H2O)(4)] (1), and its PPh4 salt (2). The reaction of the excess amount of 2-thiophenecarboxylic acid (tpcH) and [Mn12O12(OAc)(16)(H2O)(4)] in CH2Cl2 gave black crystals of 1, which could be reduced by PPh4I to give 2. From the crystal structure analysis of 2, it is revealed that there are two five-coordinated Mn ions, one of which is assigned to a Mn-II ion being in the vicinity of the tetraphenylphosphoniurn cation. Both complexes exhibit out-of-phase a.c. magnetic susceptibility (chi(M)'') signals in the 5.0-6.5 K range at 997 Hz a.c. frequency, which indicate that they are single-molecule magnets. From Arrhenius plots of the frequency dependence of the temperature of the chi(M)'' peaks, the effective energy barriers U-eff were estimated to be 69 and 57 K for high-temperature phases of 1 and 2, respectively, and 40 K for the low-temperature phase of 1. The reduced magnetization measurement and its analysis indicate that 2 has S = 19/2 ground state with g = 1.99 and D = -0.61 K. (C) 2003 Elsevier Science Ltd. All rights reserved. - Y Suenaga; H Konaka; K Kitamura; T Kuroda-Sowa; M Maekawa; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 351 379 - 384 0020-1693 2003/07 [Refereed]
The silver(I) complex of octakis(cyclohexylsulfanyl)-naphthalene (ochsn), [Ag-4(ochsn)(CF3COO)(4)](CH2Cl2) (1), has been prepared and its molecular structure was determined by X-ray crystallography. In 1, the silver ion prefers a tetrahedral coordination geometry comprised of two S atoms from the ochsn molecules and the two O atoms from the counter anion then producing two-dimensional sheet structure. Interestingly, the naphthalene ring in the complex has large deviations from planarity and end-to-end twists on the order of 35degrees. In contrast, the central naphthalene ring of ochsn shows almost a planar structure in the solid state. (C) 2003 Elsevier Science B.V. All rights reserved. - GQ Bian; QY Zhu; J Dai; Wang, X; W Yang; ZM Yan; ZR Sun; M Munakata; M MaekawaCHINESE JOURNAL OF CHEMISTRY SCIENCE CHINA PRESS 21 (5) 537 - 543 1001-604X 2003/05 [Refereed]
A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)(2)[M(Ln)(SPh)(2)] (M = Cd and Zn, L1 = dmit = 1, 3-dithiole-2-thione-4, 5-dithiolate, L2 = dmid = 1, 3-dithiole-2-one-4, 5-dithiolate, SPh = thiophenolate) (1-4) were characterized by, elemental analysis, ER, UV NMR spectra and so on. The advantages of this method am summarized in two aspects: (1) the preparation is very convenient; (2) the reaction usually completed giving the product with high,purity. The crystal structure of 1 showed that the bond distances of Cd(II) to the sulfur of the thiophenolate group are shorter than those of Cd(II) to the sulfur of dmit, so that the thiophenolate group does not be replaced in the reaction and the mixed ligand complexes are the dominant products. The dmit complexes showed well third-order NLO properties, but not of the dmid complexes, although druid is an analogue to dmit. - S Himeno; M Takamoto; A Higuchi; M MaekawaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 348 57 - 62 0020-1693 2003/05 [Refereed]
A 12-tungstovanadate complex, [VW12O40](3-) was prepared as the tetrabutylammonium (n-Bu4N+) salt by heating a 50 mM (M = mol dm (-3)) W(VI)-50 mM V(V)-1.5 M HCl-80% (v/v) CH3CN system at 70degreesC for 24 h. The alpha-Keggin structure was confirmed by (15)3W NMR spectroscopy. Besides, the n-Bu4N+ salt of its monovanadium-substituted derivative, [V(VW11)O-40](4-) was also prepared from a 50 mM W(VI)-50 mM V(V)-0.5 M HClO4-50% (v/v) CH3CN system. Both Keggin-type complexes were characterized voltammetrically. A reversible one-electron redox wave due to the central V atom was obtained at potentials more positive than the reduction wave due to the peripheral W atom. Their formation and conversion processes were also elucidated with a combined Raman and voltammetric study. (C) 2002 Elsevier Science B.V. All rights reserved. - Y Suenaga; A Ueda; T Kuroda-Sowa; M Maekawa; M MunakataTHERMOCHIMICA ACTA ELSEVIER SCIENCE BV 400 (1-2) 87 - 94 0040-6031 2003/04 [Refereed]
The conformational properties of octakis(phenylsulfanyl)naphthatene (ophn) were examined by their X-ray structural and thermal analyses. Ophns have been prepared in two different conformations, i.e. the red and yellow forms. The yellow form consists of the aabbaabb and bbaabbaa isomers (the descriptions a and b denote side-chain phenyl moieties projecting above or below, respectively). Both isomers are alternately arrayed in the direction parallel to the c-axis. This crystal structure will not be formed with only the chiral compounds. From the DTA results, the crystal melting point (T-m1) of the red form appeared at around 201.3 degreesC, for the yellow form, T-m2 appeared at around 174.5 degreesC and the crystallization point (T,2) is 114.5 degreesC. Both crystals indicate an amorphous phase during cooling after melting, then the T-g = 60 degreesC. The phase transformation observed for the red and yellow forms is summarized on the basis of the thermal analysis and powder X-ray diffraction pattern. (C) 2002 Elsevier Science B.V. All rights reserved. - M Munakata; LP Wu; T Kuroda-Sowa; M Maekawa; Y Suenaga; T Ohta; H KonakaINORGANIC CHEMISTRY AMER CHEMICAL SOC 42 (8) 2553 - 2558 0020-1669 2003/04 [Refereed]
As a continuation of the study on the construction of the multidecker aromatic compounds with pi-pi interactions, the anthracene derivatives 9,10-dimethylanthracene (dman), 9,10-diphenylanthracene (dpan), and 7,12-dimethylbenz[a]anthracene (dmban) have been studied toward complexation with the silver(l) ion. The crystal structures of [Ag(dman)(0.5)(p-xylene)(ClO4)], [Ag-2(dpan)(0.5)(C6H6)(0.5)(CF3SO3)(2)], and [Ag-2(dmban)(2)(ClO4)(2)](p-xylene), together with the metal-free ligand dpan, have been determined by single-crystal X-ray diffraction. These pi-electron-rich aromatic compounds are found to have great promise as an approach to the effective! self-assembly of high nuclearity in a multilayer fashion. - Y Suenaga; H Konaka; T Sugimoto; T Kuroda-Sowa; M Maekawa; M MunakataINORGANIC CHEMISTRY COMMUNICATIONS ELSEVIER SCIENCE BV 6 (4) 389 - 393 1387-7003 2003/04 [Refereed]
The silver(l) complex [Ag-2(3bsb)(2)(ClO4)(2)] (1) (3bsb; 1,3,5-tris(benzylsulfanyl)benzene) has been prepared and its molecular structure was determined by X-ray crystallography. In 1, the silver ion prefers a tetrahedral coordination geometry and produces a two-dimensional sheet structure containing dimeric units. Irradiation of this complex 1 with light changes its color from white to pink; heat or exposure to acetone vapor makes the irradiated sample revert back to white. However, only 3bsb has no characteristic like this photochromism. (C) 2003 Elsevier Science B.V. All rights reserved. - H Konaka; LP Wu; M Munakata; T Kuroda-Sowa; M Maekawa; Y SuenagaINORGANIC CHEMISTRY AMER CHEMICAL SOC 42 (6) 1928 - 1934 0020-1669 2003/03 [Refereed]
Five novel silver(l) coordination polymers with cis-1, 2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene (cis-dbe) were synthesized and are characterized in this paper. Treatment of AgCF3SO3 or AgCF3CO2 with cis-dbe afforded [Ag-2(cis-dbe)(CF3SO3)(2)] (1) and [Ag2(cis-dbe)(CF3CO2)(2)] (2), and both complexes exhibit a 1-D infinite chain structure with two cyano groups and two thienyl groups of the ligand bridging four metal ions. Reaction of AgCnF2n+1CO2 with cis-dbe gave rise to an unprecedented cocrystallization of a 2-D sheet structure, [Ag-2(cis-dbe)(CnF2n+1CO2)(2)], where n = 2 (3), 3 (4), and 4 (5). Upon irradiation with 450 nm light, these five silver(l) complexes turned orange or red from yellow, and the color reverted to yellow on exposure to 560 nm light, indicative of the reversible cyclization/ring-opening reaction occurring in the crystalline phase. Furthermore, different anions gave not only the different structural dimensions but also the different photoresponsive patterns. The correlation between the crystal structures and the photochromic reactivity is discussed. - M Maekawa; N Hashimoto; K Sugimoto; T Kuroda-Sowa; Y Suenaga; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 344 143 - 157 0020-1693 2003/02 [Refereed]
We systematically prepared nine [2.2]paracyclophane complexes of Rh and It, [Rh(eta(6)-PCP)(C2H4)(2)]BF4.THF 1 . THF (pcp = [2.2]paracyclophane),[Rh(il pcp)(diene)]BF4 (diene = 1,5-cyclooctadiene (cod) 2-CH2O2; 2,5-norbornadiene (nbd) 3), [RhAyl, Ti pcp)(diene)(2)](BF4)(2) (diene = cod 4; nbd 5), [Ir(eta(6)-PCP)(cod)]X (X = BF4 6a; ClO4 6b . CH2Cl2) and [Ir-2(eta(6), eta(6)-pcp)(cod)(2)]X-2 (X = BF4 7a; ClO4 7b), seven structures of which were crystallographically characterized. In complexes 1 . THF, 2 . CH2Cl2, 3 and 6b CH2Cl2, each of the Rh or It atoms are eta(6)-bonded to the upper side of the two decks in the pcp ligand to afford a mononuclear structure. The Rh or Ir atoms are supported by ethylene or diene ligands. The average C(pcp)=C(pcp) distance with the Rh or Ir atom of 1.411 (1.THF), 1.413 (2.CH2Cl2), 1.411 (3) and 1.419 Angstrom (6b.CH2Cl2) is longer than those (1.393, 1.393, 1.390 and 1.400 Angstrom) without a Rh or Ir atom, respectively. The average interannular distances between the two decks are 3.03 (1 . THF), 3.01 (2 . CH2Cl2), 3.04 (3) and 3.01 A (6b . CH2O2), respectively. In contrast, in complexes 4, 5 and 7b, two Rh or Ir atoms are eta(6)-coordinated to the upper and lower decks in the pcp ligand to provide a dinuclear structure. The Rh or Ir atoms are similarly supported by diene ligands. Two coordinating cod ligands in pcp complexes 4 and 7b are located in a staggered conformation against the pcp ligand, whereas two nbd ligands in complex 5 are located in an eclipse conformation. The average C(pcp)=C(pcp) distances with the Rh or Ir atom of 1.416 (4), 1.417 (5) and 1.420 Angstrom (7b) are longer than that (1.385 Angstrom) of the metal-free pcp ligand. The average interannular distances between the two decks are 3.04 (4), 3.05 (5) and 3.05 A (7b), respectively. On complexes 1.THF-7b, the average interannular distances of 3.01-3.05 A between the two decks were found to be shorter than that (3.09 A) of the metal-free pcp ligand, suggesting that the repulsive pi-interaction between the two decks is reduced by the coordination of the metal fragment with the diene ligand to the pcp ligand. In addition, the relationships between the intramolecular distances and the configuration of the two ethylenic bridges were quite obvious. If the interannular distance was shorter than 3.05 Angstrom, the configuration of the two ethylenic bridges was more likely a twisted cross type, and if the interannular distance was shorter than 3.01 Angstrom, the configuration was more likely a parallel type, accompanying with the structure conversion of the two ethylenic bridges and the slide of the two decks. In the 1 H NMR study, the stoichiometric 1: 1 reaction solution of [M(diene)](+) (M = Rh and It; diene = cod and nbd) and the pcp ligand in CD2Cl2 or (CD3)(2)CO at 23 degreesC showed two kinds of H-1 NMR signals, which led to assign as a major mononuclear pcp complex [M(eta(6)-pcp)(diene)] (+) and a minor metal-free pcp ligand. On the other hand, the stoichiometric 2:1 reaction solution of [M(diene)](+) and the pcp ligand in CD2Cl2 or (CD3)(2)CO at 23 degreesC revealed two kinds of H-1 NMR signals, which led to assign as a minor dinuclear pcp complex [M-2(eta(6)-pcp)(diene)(2)](2+) and a major mononuclear pcp complex [M(eta(6)-pcp)(diene)](+). These results suggest that the mononuclear pcp complex [M(eta(6)-pcp)(diene)](+) is more stable in solution. (C) 2002 Elsevier Science B.V. All rights reserved. - JC Zhong; M Munakata; M Maekawa; T Kuroda-Sowa; Y Suenaga; H KonakaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 342 202 - 208 0020-1693 2003/01 [Refereed]
For the purpose of investigation on the reactivity of silver(l) with multiphenyl diene and the effect of counteranions on silver(l) complexes, we selected several silver(l) salts to react with trans,trans-1,4-diphenyl-1,3-butadiene (dpbd). The treatment of AgClO4.H2O with dpbd afforded a I-D W-type chain silver(l) coordination polymer [Ag(dpbd)(ClO4)] (1) and while the reaction of AgCF3CO2 with dpbd gave rise to a co-crystallization structure [Ag-3(CF3CO2)(3)].(dpbd) (2) in which silver(I) and trifluoroacetate form a 1-D supramolecular ladder chain. The measurements of electric conductivity show that polymer I exhibits semiconductive behavior and while polymer 2 is an insulator. The effect of counteranions and steric hindrance on the formation of these silver(I) complexes is also discussed. (C) 2002 Elsevier Science B.V. All rights reserved. - M Wen; M Munakata; Y Suenaga; T Kuroda-Sowa; M MaekawaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 340 8 - 14 0020-1693 2002/11 [Refereed]
On the basis study of porous silver(l) complex of triptycene (tpty), [Ag-3(tpty)(3)(ClO4)(3)](toluene)(2) (1), its toluene desorbed complex (2) and absorbed complex (3) have been synthesized and confirmed by H-1 NMR spectra and X-ray powder diffraction. In complex 1, a 3D architecture with triptycene exhibits an unprecedented mu-eta(2)-eta(2) or mu-eta(2)-eta(2)-eta(1) coordination mode depending on the steric requirements of the network. The desorption and absorption of guest molecules occur in this complex accompanying the structure change. The potential study of these complexes for the rational control and synthesis of porous organometallic coordination network is discussed. (C) 2002 Elsevier Science B.V. All rights reserved. - M Wen; M Maekawa; M Munakata; Y Suenaga; T Kuroda-SowaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 338 111 - 118 0020-1693 2002/10 [Refereed]
Three silver(I) coordination complexes of crown ethers, [Ag([15]C6)(ClO4)(2)](THF) (1), [Ag(DB[21]C7)(H2O)](2)(ClO4)(2) (2) and [Ag(DB[24]C8)(CF3SO3)](2)(acetone)(2) (3) have been synthesized in different solvents and characterized structurally. The mononuclear complex 1 and two different dinuclear complexes 2 and 3 are shown in this work. Silver(l) ions are situated in a distorted pentagonal pyramidal geometry and form close dinuclear complex with DB[21]C7 based on cation-pi interaction in eta(2)-fashion. This coordination unit involves sigma bonding at a part oxygen atoms of ligand oxygen base cavity and pi-pi interaction between two parallel phenyl groups. But in 3, each DB[24]C8 host contained two silver(l) ions as guest without cation-pi and pi-pi interaction. (C) 2002 Elsevier Science B.V.. All rights reserved. - JC Zhong; M Maekawa; T Kuroda-Sowa; Y Suenaga; T Ohta; M MunakataANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEMISTRY 18 (7) 851 - 852 0910-6340 2002/07 [Refereed]
- T Kuroda-Sowa; S Fukuda; S Miyoshi; M Maekawa; M Munakata; H Miyasaka; M YamashitaCHEMISTRY LETTERS CHEMICAL SOC JAPAN 682-683 (7) 682 - 683 0366-7022 2002/07 [Refereed]
Diphenylphosphate anions can replace with benzoate anions of [Mn12O12(O2CPh)(16)(H2O)(4)] to afford a novel Mn-12 single-molecule magnet (SMM) with mixed bridging ligands. - XY Yu; M Maekawa; T Morita; HC Chang; S Kitagawa; GX JinPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 21 (16) 1613 - 1620 0277-5387 2002/07 [Refereed]
Reactions of the Rh hydrido complex [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 (1) With nitrogen ligands such as 2-(4-thiazolyl)benzimidazole (tbz). pyridazine (pdz), imidazole (im) and pyrimidine (pmd) in CH,Cl, afforded Various mononuclear Rh hydrido complexes, [Rh(H)(2)(PPh3)(2)(tbz)]CIO4 (2), [Rh(H)(2)(PPh3)(2)(pdZ)(2)]ClO(4)(.)2CH(2)Cl(2) (3). [Rh(H)Cl(PPh3)(2)(pdz)(2)](ClO4CH2Cl2)-C-. (4). [Rh(H)(2)(PPh3)(2)(im)(2)]ClO(4)(.)2CH(2)Cl(2) (5). [Rh(H)Cl(PPh3)(2)(im)(2)](ClO4CH2Cl2)-C-. (6). [Rh(H)(2)(PPh3)(2)(pmd)(2)](ClO4CH2Cl2)-C-. (7) and the Rh non-hydrido complex [RhCl2(pmd)(4)]ClO4 (8). The Rh complexes 2. 3, 5 and 6 were crystallographically characterized. The formation process was monitored by H-1 NMR and UV-Vis spectra. In all the Rh hydrido complexes, the Rh atom is coordinated by two PPh3. ligands in trans-positions and two nitrogen ligands in the cis-positions. The remaining sites Lire occupied by one or two hydride atoms to form a saturated 18-electron framework in a slightly distorted octahedral geometry. For complex 2 an appreciable inter-molecular pi interaction is observed between planes of tbz and PPh3 ligands, while an intra-molecular hydrogen bonding interaction between C-H and Cl atoms is found in complex 6. (C) 2002 Elsevier science Ltd. All rights reserved. - M Wen; M Munakata; Y Suenaga; T Kuroda-Sowa; M MaekawaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 332 18 - 24 0020-1693 2002/04 [Refereed]
Three silver(I) complexes of dibenzo-18-crown-6-ether (DB[18]C6), [Ag(DB[18]C6)(ClO4)](THF) (1), [Ag(DB[18]6)(CF3SO3)](2)-(acetone), (2) and [Ag(DB[IS]C6)(CF3COO)](2)(AgCF3COO)(2) (3) have been synthesized in different solvents and characterized structurally. In each complex, silver ions prefer an octahedral coordination geometry and form close dinuclear complex with DB[18]C6 based on cation-pi interaction in eta(2)-fashion. In particular, the coordination unit involving a bonding at an oxygen group and pi-pi bonding between two benzene rings is quite unique. (C) 2002 Elsevier Science B.V. All rights reserved. - XY Yu; M Maekawa; T Morita; HC Chang; S Kitagawa; GX JinBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 75 (2) 267 - 275 0009-2673 2002/02 [Refereed]
Reactions of Rh and Ir hydrido complexes. [Rh(H)(2)(PPh3)(2)(solv)(EtOH)]ClO4 (solv = Me2CO, 1a; EtOH, 1b) and [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]BF4 (2), with various N,N'-donor bridging ligands, such as pyrazine (pyz), 4,4'-trimethylenedipyridine (tmdp) and di(4-pyridyl) disulfide (dpds), in some solvents were examined, and their reaction products were characterized by X-ray crystal structure analysis. IR, H-1 NMR and UV-vis spectra. Rh hydrido complexes, la or 1b, formed a dinuclear Rh complex, [Rh-2(PPh3)(2) {(eta(6)-C6H5PPh2}(2)] (ClO4)(2).6CH(2)Cl(2) (3.6CH(2)Cl(2)), in dichloromethane with a reductive elimination of hydrogen. The reactions of 1a or 1b with the pyz ligand in dichloromethane and tetrahydrofuran gave triangular Rh-3 complexes, [Rh-3(PPh3)(6)(pyz)(3)](ClO4)(3).CH2Cl2 (5.CH2Cl2) and [Rh-3(PPh3)(6)(pyz)(3)](ClO4)(3).EtOH (5.EtOH), respectively, in contrast to the formation of a dinuclear Rh hydrido complex, [Rh-2(H)(4)(PPh3)(4)(Me2CO)(2)(pyz)](ClO4)(2).EtOH A-EtOH). in acetone. The reactions of la or 1b with the tmdp ligand in dichloromethane and 3-methyl-2-butanone also afforded dinuclear Rh complexes, [Rh-2(PPh3)(4)(tmdp)(2)](ClO4)(2) (6) and [Rh-2(PPh3)(4)(tmdp)(2)](ClO4)(2).4MeCOCHMe(2) (6.4MeCOCHMe(2)), respectively. On the other hand, Ir hydrido complex 2 reacted with pyz and dpds ligands in dichloromethane to afford dinuclear Ir complexes, [Ir-2(H)(4)(PPh3)(4)(Me2CO)(2)(pyz)]- (BF4)(2).3CH(2)Cl(2) (7.3CH(2)Cl(2)) and [Ir-2(H)(4)(PPh3)(4)(dpds)(2)](BF4)(2).3CH(2)Cl(2).H2O (8.3CH(2)Cl(2).H2O), respectively, without any reductive elimination of hydrogen. Based on structural studies in solution and in the solid state. it was demonstrated that various Rh and Ir complexes were selectively produced depending on the choice of solvents and N,N'-donor bridging ligands. - GQ Bian; J Dai; QY Zhu; W Yang; ZM Yan; M Munakata; M MaekawaCHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY 1474-1475 (14) 1474 - 1475 1359-7345 2002 [Refereed]
Novel binuclear dithiolate complexes (Me4N)(2)[M-2-(SPh)(2)(S2TTF(SMe)(2))(2)] (M = Cd and Zn) have been synthesized by a new cluster-cracking method. - T Kuroda-Sowa; T Nogami; M Maekawa; M MunakataMOLECULAR CRYSTALS AND LIQUID CRYSTALS TAYLOR & FRANCIS LTD 379 179 - 184 1058-725X 2002 [Refereed]
Magnetic properties of [Mn-12] complexes with sulfer-containing carboxylates, [Mn12O12(tha)(16)(H2O)(4)] (2) and [Mn12O12(tpc)(16)(H2O)(4)] (3) (thaH = trans-3-(3-thienyl)acrylic acid,. tpcH = 2-thiophenecarboxylic acid), are investigated. Both complexes showed frequency-dependent out-of-phase signals in ac susceptibility, indicating they are single-molecule magnets (SMMs). The energy barrier heights for reversing its magnetization from spin "up" to spin "down" are estimated to be 67 K and 68K for 2 and 3., respectively. - H Kumagai; S Kitagawa; M Maekawa; S Kawata; H Kiso; M MunakataJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 2390-2396 (11) 2390 - 2396 1472-7773 2002 [Refereed]
Dinuclear vanadium(III) complexes, [V-2(mu-O)(phen)(4)Cl-2]Cl-2.2Me(2)CO (1) and [V-2(mu-O)(dpya)(4)Cl-2]Cl-2 (2) [phen=1,10-phenanthroline; dpya=bis(2-pyridyl) amine], have been synthesized from the reaction of VCl3 or VCl3(THF)(3) with bidentate nitrogenous ligands. The ligand substitution reaction between NaNCS and 2 yields a brown dinuclear complex, [V-2(mu-O)(dpya)(3)(NCS)(4)].2THF (3), in which each vanadium ion has a different coordination environment, and an orange mononuclear complex, [V(dpya)(NCS)(4)].(Hdpya).THF (4). Complexes 1-3 contain singly bridged [V-O-V](4+) cores. From the temperature dependence of the magnetic susceptibilities, weak magnetic interactions are observed for 1-3. UV-Vis and resonance Raman spectra of these complexes are described. The H-1 NMR spectrum of 1, in which two vanadium ions are coupled antiferromagnetically, and those of its analogs have been measured and assigned. - M Maekawa; N Hashimoto; T Kuroda-Sowa; Y Suenaga; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 328 254 - 258 0020-1693 2002/01 [Refereed]
Mononuclear [2.2]paracyclophane complexes of Rh and Ir, [M(eta(6)-pcp)(eta(5)-C5Me5)](BF4)(2) (M = Rh (1) and Ir (2); pcp = [2.2]paracyclophane) were crystallized and their structures were first characterized crystallographically. On both pep complexes the metal atom is bonded to the benzene ring on one side of the pep ligand in the eta(6)-coordination mode. The metal atom is also supported by the eta(5)-C5Me5 ligand to afford a triple-decker sandwich structure. In Rh pep complex I the average Rh-C(pep) and Rh-C(C5Me5) distances are 2.284(2) and 2.161(2) Angstrom, respectively. The average C(pcp) = C(pcp) distance of 1.407(4) Angstrom with the Rh atom is longer than that (1.388(4) Angstrom) without a Rh atom. Similarly, the average Ir-C(pcp) and Ir-C(C5Me5) distances in Ir pcp complex 2 are 2.275(3) and 2.174(3) Angstrom, respectively. The average C(pcp) = C(pcp) distance of 1.410(4) Angstrom with the Ir atom is longer than that (1.388(4) Angstrom) without an Ir atom. It is interesting that the average interannular distances of 2.97 Angstrom for 1 and 2 between two decks of the pep ligand are shorter than that (3.09 Angstrom) of the metal-free pep ligand, indicative of the decrease of the repulsive pi-interaction between benzene rings. The Rh pep complex gave the well-resolved H-1 NMR signals of [Rh(eta(6)-pcp)(n(5)-C5Me5)](2+), whereas the Ir pep complex exhibited two kinds of H-1 NMR signals which were assigned as [Ir(eta(6)-pcp)(eta(5)-C5Me5)](2+) and [Ir-2(eta(6)-pcp)(eta(5)-C5Me5)(2)](4+) in (CD3)(2)CO at 23 degreesC. (C) 2002 Elsevier Science B.V. All rights reserved. - Y Suenaga; K Kitamura; T Kuroda-Sowa; M Maekawa; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 328 105 - 110 0020-1693 2002/01 [Refereed]
Silver(l) complexes of hexakis (tolylsulfanyl) benzene (htsb), [Ag(htsb)](PF6) (1), have been prepared and their molecular structures were determined by X-ray crystallography. In 1, the silver ion prefers a square planar coordination geometry comprized of four S atoms from two different htsb molecules and producing a zigzag chain structure of Ag-S in the silver coordination polymer, Based on the thermo-gravimetry analysis results, two tolylsulfanyl groups were easily eliminated at approximately 211 degreesC. However, [Ag(htsb)(2-butanone)] (PF6) (2), which were obtained by the reactions in different solvents, showed a different colors and thermal degradation behaviors. (C) 2002 Elsevier Science B.V. All rights reserved. - JC Zhong; Y Misaki; M Munakata; T Kuroda-Sowa; M Maekawa; Y Suenaga; H KonakaINORGANIC CHEMISTRY AMER CHEMICAL SOC 40 (27) 7096 - + 0020-1669 2001/12 [Refereed]
The novel silver(I) coordination polymer with 2,5-bis(4',5'-bis(methylthio)-1',3'-dithiol-2'ylidene)-1,3,4,6-tetrathiapentalene (TTM-TTP), [Ag(TTM-TTP)(CF3SO3)](n) (1), which consists of 1-D waving chains, was synthesized and characterized. Polymer 1 can be also regarded as a 3-D supramolecular network formed via many shorter side-by-side and face-to-face (SS)-S-... contacts. This polymer and its iodine-doped compound 2 behave as semiconductors with σ(25&DEG;C) values of 7.1 x 10(-6) and 0.85 S cm(-1), respectively. [GRAPHICS] - M Munakata; JC Zhong; T Kuroda-Sowa; M Maekawa; Y Suenaga; M Kasahara; H KonakaINORGANIC CHEMISTRY AMER CHEMICAL SOC 40 (27) 7087 - + 0020-1669 2001/12 [Refereed]
A novel silver(I) coordination polymer of I-methylpyrene (mpyr) with double-decker motifs, {[Ag-2(mpyr)(2)(ClO4)(2)]0.5benzene}(n) (1), was synthesized and characterized. Polymer I consists of I-D double-decker chains, which are formed by dimeric double-decker units ([Ag(mpyr)(ClO4)](2)) through the linkage of the perchlorate groups. In addition, the dimeric moieties between the adjacent chains are stacked to lead to column π-π stacks. Therefore, complex 1 can also be regarded as a 2-D stacking polymer, The effects of substituting groups, and other factors, on the structure of silver(I) complexes with polycyclic aromatic hydrocarbons are also discussed. [GRAPHICS] - J Dai; MY Zhou; GQ Bian; Wang, X; Qing-Feng; Xu; M Munakata; M MaekawaJOURNAL OF CHEMICAL RESEARCH-S SCIENCE REVIEWS LTD 482-484 (11) 482 - 484 0308-2342 2001/11 [Refereed]
An unexpected reaction forming 4,8-bis(4,5-dimethylthio-1,3-dithiol-2-ylidene)-1,2,3,5,6,7-hexathiocane is described. - M Maekawa; N Hashimoto; T Kuroda-Sowa; Y Suenaga; M MunakataANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEMISTRY 17 (11) 1361 - 1362 0910-6340 2001/11 [Refereed]
Crystal structure of eta<sup>5</sup>-pentamethylcyclopentadienyl-eta<sup>6</sup>-toluene Rhodium tetrafuloroborate,[Rh(Cp<sup>*</sup>)(eta<sup>6</sup>-C<sub>6</sub>H<sub>5</sub>Me)](BF<sub>4</sub>)<sub>2</sub>(Cp<sup>*</sup>=eta<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>) - A novel 2-D silver(I)-acyclic polyene coordination polymer assembled with linear unsaturated bridgesJC Zhong; M Munakata; T Kuroda-Sowa; M Maekawa; Y Suenaga; H KonakaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 322 (1-2) 150 - 156 0020-1693 2001/10 [Refereed]
A novel 2-D silver(I) coordination polymer of 1,8-diphenylocta-1,3,5,7-tetraene was synthesized, and characterized by X-ray single crystal analysis. Reaction of 1,8-diphenylocta-1,3,5,7-tetraene (dpot) with silver(I) perchlorate at 60 degreesC afforded [Ag-2(dPot)(ClO4) (1). In this structure, silver(I) adopts a distorted tetrahedral geometry and the dpot molecules link the silver(I) ions in a trans-mu -tetra-eta (2) manner to generate 1-D chains with metallocyclophane motifs. Further, the silver(I) ions between the two neighboring chains are bridged by perchlorate groups to give a novel 2-D (3,4)-connected polymeric network with (4,6(2))(2)(4(2),6(2),8(2)) topology. Additionally, the main plane of the phenyl moiety makes an angle of 33.08 degrees with the topology through the polyene portion in 1, and thus the coordination of silver(I) to dpot results in the distortion of the dpot molecule. To the best of our knowledge, this is the first example of a silver(I) complex with acyclic polyene. (C) 2001 Elsevier Science B.V. All rights reserved. - M Wen; M Munakata; Y Suenaga; T Kuroda-Sowa; M Maekawa; SG YanINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 322 (1-2) 133 - 137 0020-1693 2001/10 [Refereed]
The silver(I) complexes of 2,2',3,3'-tetrahydro-4,4'-dithia-1,1'-binaphthylidene (ttp) having a nine-member S-Ag-S chelating ring, [Ag(ttp)(ClO4)](n) (1) and [Ag-2(ttp)(2)(CF3SO3)(2)](n) (2), have been synthesized and characterized by single-crystal X-ray diffraction. The ttp is found to offer a potential coordination site for complexation, which can be utilized to generate an interesting array of silver(l) complexes with a one-dimensional chain and a chiral chain. (C) 2001 Elsevier Science B.V. All rights reserved. - M Munakata; M Wen; Y Suenaga; T Kuroda-Sowa; M Maekawa; M AnahataPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 20 (18) 2321 - 2327 0277-5387 2001/08 [Refereed]
For the purpose of furthering the understanding of steric structure effects upon coordination behavior and exploring the possibility of non-planar complexation in the triazine system for formation of extended polymeric structures, 2,4,6-triphenoxy-1,3,5-triazine(tpotz) has been reacted with silver(I) perchlorate and trifluoromethanesulfonate. The crystal structures of [Ag(2)(tpotz)(3)(ClO(4))(2)] and [Ag(2)(tpotz)(2)(CF(3)SO(3))(2)(THF)] have been determined by single-crystal X-ray diffraction. Tpotz is rich in organic components that can offer potential sites for complexation, which can be utilized to generate an interesting array of organometallic compounds with one-dimensional chains. (C) 2001 Elsevier Science Ltd. All rights reserved. - A bent two-coordinate silver(I) complex with 2,2 ',3,3 '-tetrahydro-4,4 '-dithia-1,1 '-binaphylideneM Wen; M Munakata; Y Suenaga; T Kuroda-Sowa; M Maekawa; SG YanACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE MUNKSGAARD INT PUBL LTD 57 m246 - m247 1600-5368 2001/06 [Refereed]
The Ag I complex of 2,2',3,3' -tetrahydro-4,4'-dithia-1,1'-binaphylidene (ttp) has been synthesized and its molecular structure determined as its PF6- salt, i.e. (2,2',3,3'-tetrahydro4,4'-dithia-1,1'--binaphylidene)silver(I) hexafluorophosphate, [Ag(C18H16S2)]PF6. The Ag-I ion has a distorted linear geometry comprised of the two S atoms of ttp, with an Ag-S distance of 2.4889 (8) Angstrom and an S-Ag-S angle of 157.48 (4)degrees; the cation has twofold symmetry. This coordination mode results in the formation of a nine-membered ring. - M Munakata; M Wen; Y Suenaga; T Kuroda-Sowa; M Maekawa; M AnahataPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 20 (15-16) 2037 - 2043 0277-5387 2001/06 [Refereed]
Reactions of silver(I) perchlorate and triflate with the triazine ligands 2,4,6-trimethoxy-1,3,5-triazine (L-1) and 2,4,6-triphenyl-1,3,5-triazine (L-2) have provided three novel silver complexes: [Ag(L-1)(2)](ClO4) (1), [Ag(L-1)(2)](CF3SO3) (2) and [Ag-2(L-1)(CF3SO3)(2)] (3). The crystal structures of these complexes have been determined by single-crystal X-ray diffraction. Each complex exhibits distinct coordination behavior and different frameworks. Complex 1 has a 1D stepped framework in which one crystallographically independent metal center interacts with two L-1 molecules and strong pi-pi interactions between the triazine planes of two L-1 molecules exist. On the other hand, complex 2 has a herringbone-like molecular packing in which the triflate ions are arranged between mononuclear complex cations. In complex 3, L-2 molecules are suspended between two double chains of silver triflate through the coordination to silver(I) ions to form the 2D sheet network structure. The factors that influence the crystal structure and packing are discussed. (C) 2001 Elsevier Science Ltd. All rights reserved. - JC Zhong; M Munakata; T Kuroda-Sowa; M Maekawa; Y Suenaga; H KonakaINORGANIC CHEMISTRY AMER CHEMICAL SOC 40 (13) 3191 - 3199 0020-1669 2001/06 [Refereed]
Three novel silver(I) complexes with benzopyrene derivatives were synthesized and characterized in this paper. Treatment of AgClO4.H2O with 7-methylbenzo[a] pyrene (L-1) afforded [Ag-2(L-1) (toluene)(0.5)(ClO4)(2)](n) (1) which exhibits a 2-D sheet structure with double-stranded helical motifs. Reaction of AgCF3SO3 with dibenzo[b,def]chrysene (L-2) gave rise to an unprecedented cocrystallization structure, {[Ag-2(L-2)(CF3SO3)(2)][Ag-2(toluene)(2)(CF3SO3)(2)]}(n) (2)1 formed by a 2-D neutral lamellar polymer and a 1 D neutral rodlike one. The ligand benzo[e]pyrene (L-3) coordinated to silver(I) ions generating a closed triple-decker tetranuclear complex [Ag-4(L-3)(4)(p-xylene)(ClO4)(4)] (3) which can be regarded as a stacking polymer owing to existing intermolecular pi-pi stack interactions. The structural diversity of the silver(I) coordination polymers with polycyclic aromatic hydrocarbons is not only related to the stacking patterns of free polycyclic aromatic hydrocarbons in the crystalline state, but also the geometric shapes of the molecules for these free ligands. In addition, the coordination of solvents to metal ions plays a crucial role in the formation of the unprecedented coordination polymeric architectures. The ESR spectroscopic results, conductivity, and synthesis properties are also discussed. - M Munakata; JC Zhong; Ino, I; T Kuroda-Sowa; M Maekawa; Y Suenaga; N OijiINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 317 (1-2) 268 - 275 0020-1693 2001/05 [Refereed]
Two unprecedented bimetallic Ag(II) coordination polymers were synthesized and characterized in this paper. Treatment of [Ag(cyclam)](ClO4)(2) and K-2[Pd(CN4)]. 3H(2)O generated [Ag(cyclam)Pd(CN)(2)(mu -CN)(2)](n) (1). Reaction of [Ag(cyclam)](ClO4)(2) with K-2[Pt(CN)(4)]. 3H(2)O afforded [Ag(cyclam)Pt(CN)(2)(mu -CN)(2)](n) (2). The structures of 1 and 2 are similar and consist of 1-D zigzag chains which are linked via intermolecular hydrogen bonding interactions to give rise to 3-D networks. The structural features, IR, ESR and magnetic properties are discussed, respectively. To our knowledge, the complexes reported here are the first example of bimetallic Ag(II) coordination polymers with weak antiferromagnetic spin coupling. The primary results presented here can give an insight into the assembly of Ag(II) coordination polymers. (C) 2001 Elsevier Science B.V. All rights reserved. - XY Yu; M Maekawa; M Kondo; S Kitagawa; GX JinCHEMISTRY LETTERS CHEMICAL SOC JAPAN 168-169 (2) 168 - 169 0366-7022 2001/02 [Refereed]
Never di- and trinuclear Rh complexes, [Rh-2(PPh3)(4)(H)(4)(Me2CO)(2)(mu -pyz)](ClO4)(2). EtOH and [Rh-3(PPh3),(mu -pyz)(3)](ClO4)(3). EtOH were selectively isolated from the reaction of [Rh(PPh3)(2)(H)(2)(Me2Co)(EtOH)]ClO4 with pyrazine (pyz) in Me2CO and THF, respectively. Their structures were crystallographically characterized. - S Himeno; M Yoshihara; M MaekawaINORGANIC CHEMISTRY COMMUNICATIONS ELSEVIER SCIENCE BV 4 (1) 5 - 8 1387-7003 2001/01 [Refereed]
A novel voltammetrically active isopolyoxotungstate anion, [H6W18O60](6-) was prepared as a tetrapropylammonium (n-Pr4N+) salt from a freshly prepared solution (pH 4.0) of 500 mM (M = mol dm(-3)) W(VI) at ambient temperature. The [H6W18O60](6-) complex was obtained as a transient intermediate in the transformation of [W10O32](4-) into alpha-[H2W12O40](6-), and the formation conditions were elucidated in relation to those of [W10O32](4-) and alpha-[H2W12O40](6-). The [H6W18O60](6-) complex was characterized by W-183 NMR and voltammetric behaviors. (C) 2001 Elsevier Science B.V. All rights reserved. - J Dai; CQ Bian; Wang, X; QF Xu; MY Zhou; M Munakata; M Maekawa; MH Tong; ZR Sun; HP ZengJOURNAL OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 122 (44) 11007 - 11008 0002-7863 2000/11 [Refereed]
- Ino, I; LP Wu; M Munakata; T Kuroda-Sowa; M Maekawa; Y Suenaga; R SakaiINORGANIC CHEMISTRY AMER CHEMICAL SOC 39 (24) 5430 - 5436 0020-1669 2000/11 [Refereed]
For the purpose of investigating the coordination behavior of the sterically congested alkenes and exploring the possibility of cofacial complexation in the polycyclic aromatic system for formation of extended polymeric networks, tetraphenylethylene (tphe) and 1,1,4,4-tetraphenyl-1,3-butadiene (tphb) have been studied with regard to their complexation with a silver(I) ion. The crystal structures of [Ag(tphe)(ClO4)(p-xylene)], [Ag-2(tphe)(ClO4)(2)], [Ag-4(tphe)(CF3SO3)(4)], [Ag-2(tphb)(ClO4)(2)], and [Ag-2(tphb)(CF3SO3)(2)], together with the metal-free ligands tphe and tphb, have been determined by single-crystal X-ray diffraction. The pi -electron-rich cleft in organic components is found to offer a potential site for complexation, which can be utilized to generate an interesting array of organometallic compounds with one- and two-dimensional frameworks. - Y Suenaga; T Kamiya; T Kuroda-Sowa; M Maekawa; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 308 (1-2) 17 - 21 0020-1693 2000/10 [Refereed]
The silver(I) complexes of pyrazine-2,3-dicarbonitrile (2,3-dcpz), [Ag(2,3-dcpz)(ClO4)] (1a) and pyrazine-2,5-dicarbonitrile (2,5-dcpz), [Ag(2,5-dcpz)(X)] (2a: X=ClO4, 2b: X = CF3SO3) have been prepared and their molecular structure has been determined by X-ray crystallography. The silver ion in la prefers an octahedral coordination geometry and forms a two-dimensional square mesh structure. On the other hand, the silver ion in both 2a and 2b prefers a distorted square pyramidal coordination geometry that forms a three-dimensional structure with a cavity. By changing the bridging angle of the ligands and the size of the solvent, we could successfully control the crystal structure of the silver(I) coordination polymers. (C) 2000 Elsevier Science S.A. All rights reserved. - Ino, I; JC Zhong; M Munakata; T Kuroda-Sowa; M Maekawa; Y Suenaga; Y KitamoriINORGANIC CHEMISTRY AMER CHEMICAL SOC 39 (19) 4273 - 4279 0020-1669 2000/09 [Refereed]
This paper presents novel and distinctive organosilver polymers with intriguing structure motifs, constructed from iodoacetonitrile (L-1), 1-(isocyanidomethyl)-1H-benzotriazole (L-2), 1,3-bis(dicyanomethylidene)indan (L-3), and silver(I) salts, respectively. Treatment of L-1 with AgClO4 generated [Ag(L-1)(ClO4)](n) (1), whose X-ray determination revealed a 2-D wavy sheet structure with square grids. Reaction of L-2 With AgPF6 gave rise to a novel 2-D wavy interwoven network, {[Ag(L-2)(PO2F2)(0.5)](PF6)(0.5)}(n) (2) The complex [Ag-2(L-3)(2)](n) (3) obtained by reaction of AgClO4 with L-3 can be regarded as unprecedented 3-D 5-fold interpenetrating nets with columnar aromatic stacks and indicates semiconductive behavior. The IR, ESR spectroscopic results, conductivities, and structural features of the complexes are discussed, respectively. The present findings may provide insight into the coordination versatility of silver(I) and polynitrile ligands and an inspiration for the self-assembly of novel supramolecular networks with multifunctional ligands. Crystal data: 1, C2H2AgINClO4, orthorhombic, Pca2(1) (No. 29), a = 14.503(1) Angstrom, b = 5.104(2) Angstrom, c = 10.2019(9) Angstrom, Z = 4; 2, C8H6AgN4PF4O, orthorhombic, Pnna (No. 52), a = 12.2705(3) Angstrom, b = 21.150(1) Angstrom, c = 10.040(1) Angstrom, Z= 8; 3, C30H10Ag2N8, triclinic, P (1) over bar (No. 2), a = 14.920(2) Angstrom, b = 11.896(2) Angstrom, c = 7.400(4) Angstrom, alpha = 8.55(2)degrees, beta = 80.87(2)degrees, gamma = 74.47(1)degrees, Z= 2. - Ino, I; LP Wu; M Munakata; M Maekawa; Y Suenaga; T Kuroda-Sowa; Y KitamoriINORGANIC CHEMISTRY AMER CHEMICAL SOC 39 (10) 2146 - 2151 0020-1669 2000/05 [Refereed]
This paper reports novel silver polymers, built with iodine--silver interactions, with interesting structural motifs. Four silver(I) coordination polymers of the aryl iodide derived ligands, triiodobenzoic acid (HLL), tris(4-iodophenyl)-amine (L-2), and 5,7-diiodo-8-hydroxyquinoline (HL3), have been synthesized and characterized by X-ray crystallography. Treatment of Ag(CH3COO) with HL1 yielded [Ag(L-1)] (1), whose structural analysis revealed 2D layers of ladders connected through weak Ag ... I interaction. Reactions of AgClO4 and L-2 in benzene and nitrobenzene afforded, respectively, two different products, [Ag(L-2)(H2O)]ClO4. C6H6 (2) and [Ag(L-2)(ClO4)] (3). While the structure of 2 could be described as a 2D layer of square and octagons perpendicular to [100], complex 3 is formed by 2D layers of the same topology of 2 (8(2). 4), alternating as ABAB. In contrast, complex 4, [Ag-2(H2L3)(CK3SO3)(3)], obtained by reaction of Ag(CF3SO3) and HL3, was found to consist of a 2D layer based on columnar arrays AgH2L3-Ag(triflate). The solid-state FT-IR and Ag-109 NMR- spectra of theses complexes are discussed on the basis of their crystal structures. - K Sugimoto; T Kuroda-Sowa; SG Yan; M Maekawa; M MunakataACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS MUNKSGAARD INT PUBL LTD 56 414 - 415 0108-2701 2000/04 [Refereed]
The title triangular tripalladium cluster, [Pd3Cl5(C18H15P)(3)].- C3H6O, (I), has a trigonal-bipyramidal framework of Pd-3(mu(3)- Cl)(2), with the two Cl atoms in apical positions. Each Pd atom in the framework has two additional coordination sites to establish square-planar cis-PdL2(mu(3)-Cl)(2) geometry. Three P atoms are located on the same side of the plane defined by the Pd-3 triangle, which leads to a pseudo-C-3 nu symmetry for the core framework of Pd-3(mu(3)-Cl)(2)P3Cl3. The average Pd-Cl distance trans to PPh3 is 2.473 (8) Angstrom, which is significantly longer than the average Pd-Cl distance of 2.294 (4) Angstrom for those trans to terminal Cl, due to the strong trans effect of a P atom compared with a Cl atom. Compound (I) has 49 valence electrons and shows a rhombic electron-spin resonance signal, indicating an S = 1/2 ground state. - K Sugimoto; T Kuroda-Sowa; T Goto; M Maekawa; M MunakataBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 73 (3) 651 - 655 0009-2673 2000/03 [Refereed]
Two triangular tripalladium compounds, [Pd-3(mu(3)-Cl)(2)(HqnS)(6)]Cl-2 (1) (HqnS = quinoline-2(1H-thione), and [Pd-3(mu(3)- Cl)(2)(Et(2)dtc)(2)(PPh3)(2)]. C6H6 (2) (Et(2)dtc = N,N'-diethyldithiocarbamate anion), were prepared. Their single crystal X-ray structure analyses revealed they have a similar trigonal bipyramidal framework of Pd-3(mu(3)-Cl)(2) with two chlorine atoms in apical positions. Each Pd atom in all clusters has two additional coordination sites to establish a square planar cis-PdL2(mu(3)-Cl)(2) geometry. In compound 1, six sulfur atoms of six HqnS ligands with thion form are coordinated to the vacant sites of the Pd-3(mu(3)-Cl)(2) core. Two coordination sites of one of the three Pd atoms in 2 are occupied by two triphenylphosphines and those of the other two are coordinated by two S atoms of Et(2)dtc. Although both compounds have 50 valence electrons, only 1 shows paramagnetic behavior. Crystallographic data are as follows. 1: Pd3Cl4S6N6C54H42, triclinic, <P(1)over bar>, a = 14.988(5), b = 17.328(3), c = 12.642(1) Angstrom, alpha = 93.61(1), beta = 96.06(2), gamma = 71.79(2)degrees, V = 3099(1) Angstrom(3), and Z = 2. 2: Pd3Cl2P2S4N2C52H56, monoclinic, P2(1), a = 12.278(5), b = 17.426(6), c = 12.630(3) Angstrom, beta = 94.65(3)degrees, V = 2693(2) Angstrom(3), and Z = 2. - K Sugimoto; T Kuroda-Sowa; M Maekawa; M MunakataBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 73 (2) 391 - 394 0009-2673 2000/02 [Refereed]
Oxidation of [Pd(mnt)(2)](2-) by H2O2 produces a sulfonyl-containing [Pd(mnt){O2S2C2(CN)(2)}](2-) (1(2-)). Addition of AgClO4 to 1(2-) results in the formation of [AgPd(mnt){O2S2C2(CN)(2)}](2)(2-) (2(2-)). Both compounds crystallize with a bulky cation Bu4N+ to form (Bu4N)(2)1 and (Bu4N)(2)2, which are characterized by single crystal X-ray analyses. 1(2-) retains a planar structure except for the sulfonyl oxygen atoms. The electronic absorption band observed at 387 nm (sh) is assigned to d-d transition. 2(2-) has a double-decker structure consisting of two [Pd(mnt){O2S2C2(CN)(2)}](2-) anions bridged by two Ag(I) ions through Ag-S bonds. Two terminal CN groups in 2(2-) coordinate to the neighboring Ag(I) ions, forming a one-dimensional chain structure. Crystallographic data are as follows. (Bu4N)(2)1: PdS4O2N6C40H72, triclinic, P (1) over bar, a = 12.145(2), b = 10.991(3), c = 10.156(2) Angstrom, alpha = 65.09(2), beta = 88.93(2), gamma = 84.97(2)degrees, Z = 1. (Bu4N)(2)2: Ag2Pd2S8O4N10C48H72, monoclinic, P2(1)/c, a = 9.649(2), b = 13.235(2), c = 25.107(2) Angstrom, beta = 91.03(1)degrees, Z = 2. - S Himeno; M Yoshihara; M MaekawaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 298 (2) 165 - 171 0020-1693 2000/02 [Refereed]
A new route to the preparation of voltammetrically-active isopolyoxotungstate complexes was developed by the presence of CH3CN in aqueous W(VI) solutions. In the presence of 40% (v/v) CH3CN as an auxiliary solvent, the [W6O19](2 -) complex was formed in equilibrium with the [W10O32](4 -) complex, which was subsequently transformed into the previously unknown alpha-Keggin-type [H4W12O40](4 -) complex at weaker acidities. The alpha-[H4W12O40](4 -) complex was characterized by voltammetric and spectroscopic behaviors. (C) 2000 Elsevier Science S.A. All rights reserved. - M Munakata; GL Ning; Y Suenaga; T Kuroda-Sowa; M Maekawa; T OhtaANGEWANDTE CHEMIE-INTERNATIONAL EDITION WILEY-V C H VERLAG GMBH 39 (24) 4555 - + 1433-7851 2000 [Refereed]
- Y Suenaga; T Kuroda-Sowa; M Maekawa; M MunakataJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 3620-3623 (20) 3620 - 3623 1470-479X 2000 [Refereed]
Silver(I) complexes of hexakis(phenylsulfanyl)benzene (hphb), [Ag-2(hphb)][PF6](2) 1 and [Ag(hphb)(NO3)] 2, have been prepared and their molecular structures determined by X-ray crystallography. In 1 the silver ion adopts a tetrahedral co-ordination geometry comprising four S atoms from two different hphb molecules and giving an eight-membered Ag-S ring structure in a co-ordination polymer. This ring (6.46 x 6.79 Angstrom) forms a three-dimensional framework with pockets. On the other hand, for 2, the silver(I) ion has a square pyramidal environment with four S atoms and one O atom of a NO3- anion. The complex forms a linear-chain structure with an alternating arrangement of silver ions and hphb. - M Maekawa; H Konaka; Y Suenaga; T Kuroda-Sowa; M MunakataJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 4160-4166 (22) 4160 - 4166 1472-7773 2000 [Refereed]
Four copper(I) and six silver(I) novel co-ordination polymers linked by 1,4-bis(4-pyridyl)butadiyne (4-bpbd) or 1,4-bis(2-pyridyl)butadiyne (2-bpbd) were prepared and seven structures crystallographically characterized, in order to illustrate the structural versatility of co-ordination polymers assembled by the Group 11 metal ions and rod-like nitrogen bidentate ligands with long spacers. Reaction of appropriate copper(I) and silver(I) salts with the 4-bpbd ligand affords 2-D interwoven copper(I) co-ordination polymers {[Cu(2)(4-bpbd)(3)(CH(3)CN)(2)]X(2)}(n) (X=PF(6) 1a . 2H(2)O or BF(4) 1b) and 1-D straight chain silver(I) co-ordination polymers {[Ag(4-bpbd)]X}(n) (X=NO(3) 2a . CH(3)CN, ClO(4) 2b . (CH(3))(2)CO or CF(3)SO(3) 2c . (CH(3))(2)CO), respectively. On the other hand, reaction of suitable salts with the 2-bpbd ligand provides a 3-D diamondoid copper(I) co-ordination polymer {[Cu(2-bpbd)(2)]BF(4)}(n) 3b, a 1-D zigzag chain silver(I) co-ordination polymer {[Ag(2-bpbd)(NO(3))]}(n) 4a and a 2-D braid sheet silver(I) co-ordination polymer {[Ag(2-bpbd)(CF(3)SO(3))]}(n) 4c, respectively. On the basis of these structural studies, the unique structural features and the dimensionality of the copper(I) and silver(I) co-ordination polymers are revealed. - Masahiko Maekawa; Hisashi Konaka; Yusaku Suenaga; Takayoshi Kuroda-Sowab; Megumu MunakatabJournal of the Chemical Society, Dalton Transactions Royal Society of Chemistry (22) 4160 - 4166 1470-479X 2000 [Refereed]
Four copper(i) and six silver(i) novel co-ordination polymers linked by 1,4-bis(4-pyridyl)butadiyne (4-bpbd) or 1,4-bis(2-pyridyl)butadiyne (2-bpbd) were prepared and seven structures crystallographically characterized, in order to illustrate the structural versatility of co-ordination polymers assembled by the Group 11 metal ions and rod-like nitrogen bidentate ligands with long spacers. Reaction of appropriate copper(i) and silver(i) salts with the 4-bpbd ligand affords 2-D interwoven copper(i) co-ordination polymers {[Cu2(4-bpbd)3(CH3CN)2]X2} (X = PF6 la-2H2O or BF4 Ib) and 1-D straight chain silver(i) co-ordination polymers {[Ag(4-bpbd)]X} (X = NO3 2a-CH3CN, C1O4 2b-(CH3)2CO or CF3SO3 2c-(CH3)2CO), respectively. On the other hand, reaction of suitable salts with the 2-bpbd ligand provides a 3-D diamondoid copper(i) co-ordination polymer {[Cu(2-bpbd)2]BF4} 3b, a 1-D zigzag chain silver(i) co-ordination polymer {[Ag(2-bpbd)(NO3)]} 4a and a 2-D braid sheet silver(i) co-ordination polymer {[Ag(2-bpbd)(CF3SO3)]}4c, respectively. On the basis of these structural studies, the unique structural features and the dimensionality of the copper(i) and silver(i) co-ordination polymers are revealed. ©The Royal Society of Chemistry 2000. - SUENAGA Y; KURODA‐SOWA T; MAEKAWA M; MUNAKATA M┣DBJ. Chem. Soc., Dalton Trans.(/)-┫DB (20) 3620 - 3623 1472-7773 2000
- Masahiko Maekawa; Kunihisa Sugimoto; Takayoshi Kuroda-Sowa; Yusaku Suenaga; Megumu MunakataJournal of the Chemical Society - Dalton Transactions Royal Society of Chemistry (24) 4357 - 4362 0300-9246 1999/12 [Refereed]
Novel dinuclear rhodium(I) complexes, [Rh2(2-bpbd)2(cod)2]X2 (X = BF4 1a, PF6 1b or ClO4 1c cod = cyclo-octa-1,5-diene) and 1-D rhodium(I) co-ordination polymers with the linkage of square-planar rhodium(I) centers, {[Rh(4-bpbd)(cod)]X}n (X = BF4 2a, PF6 2b or ClO4 2c) and {[Rh(4-bpe)(cod)]X}n (X = BF4 3a, PF6 3b or ClO4 3c), were systematically synthesized using 1,4-bis(2-pyridyl)butadiyne (2-bpbd), 1,4-bis(4-pyridyl)butadiyne (4-bpbd) and tran-1,2-bis(4-pyridyl)ethylene (4-bpe). The structures of 1a, 2a, 2b and 3a were crystallographically characterized. In 1a each Rh atom is bridged by two N atoms of 2-bpbd to afford a unique dinuclear structure with an 18-membered Rh2N4C12 framework. In 2a, 2b and 3a, each Rh atom is bonded to two N atoms of 4-bpbd (2a and 2b) or 4-bpe (3a) and two C=C bonds of cod in a square-planar geometry. The square-planar centers are in turn linked by 4-bpbd or 4-bpe ligands to form a 1-D zigzag-chain structure. The zigzag chains are located in parallel 9.6, 9.9 and 10.7 Å apart in 2a, 2b and 3a, respectively, and no effective intermolecular interactions were found. © The Royal Society of Chemistry 1999. - M Munakata; LP Wu; K Sugimoto; T Kuroda-Sowa; M Maekawa; Y Suenaga; N Maeno; M FujitaINORGANIC CHEMISTRY AMER CHEMICAL SOC 38 (25) 5674 - 5680 0020-1669 1999/12 [Refereed]
Reactions of silver(I) perchlorate with the nonplanar aromatic compounds triptycene (L-1), 9,9-bifluorenylidene (L-2), (R)-(+)-1,1-bi-2-naphthol (L-3) and 2,5-norbornadiene (L-4) have isolated four novel hydrocarbon-bridged polymeric complexes: [Ag-3(L-1)(3)(ClO4)(3)]. 2C(6)H(5)Me (1), [Ag-2(L-2)(2)(ClO4)(2)]. C6H4Me2 (2), [Ag-2(L-3)(C6H6)(2)(ClO4)(2)] (3), and [Ag(L-4)(ClO4)] (4). Structural studies using single-crystal X-ray diffraction have shown that all compounds contain extended two- or three-dimensional structures based on cation-rr interactions. While complex 1 in the solid stale contains a three-dimensional architecture in which die triangular molecule triptycene exhibits an unprecedented mu-eta(2)-eta(2) or mu-eta(2)-eta(2)-eta(1) coordination mode depending on the steric requirements of the network, 3 represents the first example of pi coordination of naphthol-containing micropores in its metal complexes. Infinite chains consisting of alternating silver ions and hydrocarbon molecules observed in both 2 and 4 are linked together by perchlorates, affording 2-D frameworks. The potential use of these pi complexes for the rational control and synthesis of polymeric organometallic materials is discussed. Crystal data: 1, C74H58Ag3Cl3O12, monoclinic, Cc, a = 37.951(4) Angstrom, b = 8.047(4) Angstrom, c = 20.882(5) Angstrom, beta = 93.72(1)degrees, V= 6365(3) Angstrom(3), Z = 4; 2, C60H42Ag2Cl2O8. monoclinic, P2(1)/n, a = 12.317(4) Angstrom, b = 7.961(1) Angstrom, c = 24.741(1) Angstrom, beta = 100.015(1)degrees, V = 2389(6) Angstrom(3) , Z = 2; 3, C32H26Ag2Cl2O10, tetragonal, P4(1)2(1)2, a = 8.759(6) Angstrom, c = 39.967(8) Angstrom V= 3065(3) Angstrom(3), Z = 4; 4, C7H8-AgClO4 monoclinic, p2(1)/n, a = 9.847(4) Angstrom, b = 9.0543 Angstrom, c = 10.662(3) Angstrom, beta = 106.72(2)degrees, V= 910.3(4) Angstrom(3), Z = 4. - GL Ning; M Munakata; LP Wu; M Maekawa; Y Suenaga; T Kuroda-Sowa; K SugimotoINORGANIC CHEMISTRY AMER CHEMICAL SOC 38 (25) 5668 - 5673 0020-1669 1999/12 [Refereed]
This paper describes three novel and distinctive organosilver(I) complexes with propeller ligand, hexaphenylbenzene (HPB), whose structures are controlled by selected solvents and anions. Treatment of HPB with AgClO4 and AgCF3SO3 in toluene gave, complexes [Ag-4(HPB)(ClO4)(4)] 1 and [Ag-2(HPB)(CF3SO3)(2)(toluene)] 2, respectively. The single-crystal X-ray analysis revealed that 1 contains 2-D sheet framework whereas 2 consists of l-D chain structure. In both complexes the anions play the role of linkers instead of spacers in the construction of polymeric structures. In contrast, complex [Ag-2(HPB)(ClO4)(2)(THF)(2)] 3, obtained by using tetrahydrofuran (THF) ill place of toluene in the synthetic process of 1, exhibits a discrete dimer. The fundamentals of the synthesis of these complexes, influences of anions and solvents on their coordination networks, and physicochemical properties are discussed. The present findings may serve as a basis for understanding the construction of solid-state materials with designed architecture in crystal engineering. Crystallographic data are as follows. 1: C21H15Ag2Cl2O8, monoclinic, P2(1)/c, a = 10.543(2) Angstrom, b = 11.934(4) Angstrom, c = 16.224(3) Angstrom, beta = 94.08(2)degrees, Z = 4. 2: C51H38-Ag2S2F6O6, monoclinic, C2/c, a = 18.200(4) Angstrom, b = 16.831(7) Angstrom, c = 16.244(3) Angstrom, beta = 110.96(2)degrees, Z = 8. 3: C25H23AgClO5, monoclinic, P2(1)/c, a = 11.321(3) Angstrom, b = 12.511(4) Angstrom, c = 16.357(3) Angstrom, beta = 99.98(2)degrees, Z = 4. - M Maekawa; K Sugimoto; T Kuroda-Sowa; Y Suenaga; M MunakataJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 4357-4362. (24) 4357 - 4362 1472-7773 1999/12 [Refereed]
Novel dinuclear rhodium(I) complexes, [Rh(2)(2-bpbd)(2)(cod)(2)]X(2) (X=BF(4) 1a, PF(6) 1b or ClO(4) 1c; cod=cycloocta-1,5-diene) and 1-D rhodium(I) co-ordination polymers with the linkage of square-planar rhodium(I) centers, {[Rh(4-bpbd)(cod)]X}(n)(X=BF(4) 2a, PF(6) 2b or ClO(4) 2c) and {[Rh(4-bpe)(cod)]X}(n) (X=BF(4) 3a, PF(6) 3b or ClO(4) 3c), were systematically synthesized using 1,4-bis(2-pyridyl)butadiyne (2-bpbd), 1,4-bis(4-pyridyl)butadiyne (4-bpbd) and trans-1,2-bis(4-pyridyl)ethylene (4-bpe). The structures of 1a, 2a, 2b and 3a were crystallographically characterized. In 1a each Rh atom is bridged by two N atoms of 2-bpbd to afford a unique dinuclear structure with an 18-membered Rh(2)N(4)C(12) framework. In 2a, 2b and 3a, each Rh atom is bonded to two N atoms of 4-bpbd (2a and 2b) or 4-bpe (3a) and two C=C bonds of cod in a square-planar geometry. The square-planar centers are in turn linked by 4-bpbd or 4-bpe ligands to form a 1-D zigzag-chain structure. The zigzag chains are located in parallel 9.6, 9.9 and 10.7 Angstrom apart in 2a, 2b and 3a, respectively, and no effective intermolecular interactions were found. - Y Suenaga; T Kuroda-Sowa; M Maekawa; M MunakataACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS MUNKSGAARD INT PUBL LTD 55 1623 - 1625 0108-2701 1999/10 [Refereed]
The silver(I) complex of tetrakis(isopropylthio)-p-benzoquinone (tpq), catena-poly [silver(I)-mu-[2,3,5,6-tetrakis (isopropylthio)-p-benzoquinone-S-2,S-3:S-5,S-6]] perchlorate acetone solvate, {[Ag(C18H28S4O2)]ClO4. C3H6O}(n), has been prepared and the molecular structure determined. The silver ion prefers a tetrahedral coordination geometry comprising four S atoms from two different tpq molecules, giving a linear-chain structure of alternating metal cations and organic ligands. Also, the four isopropyl groups of the tpq molecule lie in the perpendicular direction of the plane of the benzoquinone ring. - M Maekawa; S Kitagawa; Y Nakao; S Sakamoto; A Yatani; W Mori; S Kashino; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 293 (1) 20 - 29 0020-1693 1999/10 [Refereed]
Four dicopper(II) oximato complexes of 2-[2-(alpha-pyridyl)methyl]imino-3-butanone oxime (pmiboH) and 2-[2-(alpha-pyridyl)ethyl]imino-3-butanone oxime (peiboH), [Cu-2(pmibo)(2)](ClO4)(2) (1), [Cu-2(pmibo)(2)](NO3)(2). CH3OH, (2), [Cu-2(peibo)(2)](ClO4)(2). CH3OH (3) and [Cu-2(peibo)(2)(H2O)(2)](ClO4)(2) (4), were prepared and characterized structurally and magnetically. All the dicopper(II) oximato complexes have a common cationic structure in which the two Cu atoms are bridged through two N-O bridges of the oximato ligand to afford a dinuclear structure. The cation moieties of 1 and 2 consist of one six-membered Cu2N2O2 chelate ring and four five-membered (CuN2C2 and CuNC2N) chelate rings, providing a planar configuration. The cation moieties of 3 and 4 are also composed of three six-membered (Cu2N2O2 and CuNC3N) chelate rings and two five-membered CuN2C2 chelate rings, giving a twisted-boat configuration. The -2J values (H = -2JS(1)S(2)) are 835, 825, 550 and 510 cm(-1) for 1, 2, 3 and 4, respectively, indicative of a strong antiferromagnetic interaction in the solid state. All the dicopper(II) oximato complexes show seven H-1 NMR signals at 23 degrees C in the range of -0.5 to 30 ppm with the linewidths at half-height, Delta v(1/2) of 60-1500 Hz, which is characteristic of antiferromagnetic species and indicates that the dinuclear structure is kept in solution. The -2J values reflect the degree of distortion from the planarity of the Cu-2 framework. The -2J values roughly correlate with the H-1 NMR parameters; the larger the -2J values, the smaller the chemical shifts and linewidths. Complexes 1 and 2 were found to undergo an autoreduction reaction in dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA), and their behaviors were first monitored by UV-Vis and H-1 NMR methods. (C) 1999 Elsevier Science S.A. All rights reserved. - Y Suenaga; T Kuroda-Sowa; M Maekawa; M MunakataJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 2737-2741. (16) 2737 - 2741 0300-9246 1999/08 [Refereed]
Silver(I) complexes of 2,3,5,6-tetrakis(methylsulfanyl)pyridine (tmp), [Ag-3(tmp)(4)][ClO4](3). C3H6O 1 and [Ag-2(tmp)(2)][C2F5CO2](2) 2, have been prepared and their molecular structures determined by X-ray crystallography. In both complexes two tmp ligands are positioned face to face by two Ag atoms and form a box structure. In 1 three types of silver(I) ion are present depending on the co-ordination numbers. One tmp molecule acts as a bridge between box structures leading to a tape arrangement. The pi-pi stackings between pyridine rings give a two-dimensional network. In 2, by contrast, the silver(I) ion has a trigonal planar environment with three thioether S atoms; each tmp acts as a ligand bridging metal centres resulting in a two-dimensional sheet. - M Munakata; GL Ning; Y Suenaga; K Sugimoto; T Kuroda-Sowa; M MaekawaCHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY 1545-1546. (16) 1545 - 1546 1359-7345 1999/08 [Refereed]
A 2-D double-strand helical complex with a strand of polycyclic aromatic hydrocarbons and a strand of silver(I) perchlorate has been isolated and crystallographically characterised. - GL Ning; LP Wu; K Sugimoto; M Munakata; T Kuroda-Sowa; M MaekawaJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 2529-2536. (15) 2529 - 2536 0300-9246 1999/08 [Refereed]
For the purpose of exploring the structural relations of organometallic compounds to their organic components, a series of linear polycyclic aromatic hydrocarbons (PAHs) benzo[a]phenanthrene (L-1), dibenz[a,h]anthracene (L-2), benz[a]anthracene (L-3), and naphtho[2,3- a]pyrene (L-4), have been studied towards complexation with silver(I) ion. The crystal structures of [Ag-3(L-1)(ClO4)(3)(H2O)(2)] 1, [Ag-2(L-2)(ClO4)(2)] 2, [Ag-2(L-3)(ClO4)(2)(H2O)] 3, and [Ag-2(L-4)(CF3SO3)(2)] 4 have been determined by single-crystal X-ray diffraction. Although each of these complexes exhibits distinct co-ordination behavior and different frameworks, all of them retain or partially keep the herringbone-packing pattern of their metal-free aromatic ligands in the crystalline state, and display similar two-dimensional multilayer architectures on a given plane. The fundamentals of the synthesis, possible formation mechanism of these polymeric networks and some properties are discussed. - LP Wu; M Munakata; T Kuroda-Sowa; M Maekawa; Y Suenaga; Y KitamoriINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 290 (2) 251 - 255 0020-1693 1999/07 [Refereed]
The reactions of silver perchlorate and tetraiodoethylene in different solvents, namely, benzene and toluene, isolated two silver(I)-iodocarbon complexes, [Ag(C2I4)(C6H6)(2)(ClO4)] (1) and [Ag(C2I4)(ClO4)] (2). Both compounds contain intact iodoalkenes which coordinate via sigma-donation of a halogen lone pair and retain their carbon-iodine bonds. Owing to the participation of the benzene molecules in coordination, complex 1 is found to be a discrete monomer in which the five-coordinate geometry of the silver ion is comprised of two benzene molecules, one C2I4 group and one perchlorate ion. In contrast, the unsaturated coordination environment of the metal ion in 2 is filled by the second iodocarbon group leading to a two-dimensional framework. The coordinated tetraiodoethylene molecules involve severe twisting of the C=C double bond, causing the C=C stretching band to move to a lower frequency. (C) 1999 Elsevier Science S.A. All rights reserved. - M Maekawa; M Munakata; T Kuroda-Sowa; Y Suenaga; K SugimotoINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 290 (2) 153 - 158 0020-1693 1999/07Two novel tetracopper(I) and tetrasilver(I) complexes [Cu-4(atdz)(6)](ClO4)(4). 2CH(3)OH (1) and [Ag-4(atdz)(6)](ClO4)(4) (2), have been prepared using 2-amino-1,3,4-thiadiazole (atdz), and their crystal structures and properties have been determined. On each tetranuclear complex, two Cu or Ag atoms (M) are bridged by two atdz ligands to form a six-membered N2M2N2 framework. The two N2M2N2 frameworks are in parallel linked by another atdz ligand to provide the tetranuclear structure with a rectangular M-4 core. The four Cu or Ag atoms possess a trigonal-square geometry. The two adjacent M...M separations are (3.096(1) and 3.412(1) Angstrom) and (3.316(2) and 3.658(2) Angstrom) for 1 and 2, respectively. On both tetranuclear complexes there are two species of hydrogen bonds between the ClO4- anions and the NH2 group of atdz ligands. It is proposed that the hydrogen bonds are related to the stabilization of the tetranuclear structure during the crystallization process. (C) 1999 Elsevier Science S.A. All rights reserved.
- M Munakata; LP Wu; GL Ning; T Kuroda-Sowa; M Maekawa; Y Suenaga; N MaenoJOURNAL OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 121 (21) 4968 - 4976 0002-7863 1999/06 [Refereed]
A new class of metal sandwich complexes of silver derived from silver(I) perchlorate and fluoranthene (L-1), benzo[ghi]perylene (L-2), [2,2]paracyclophane (L-3), and decacyclene (L-4) was prepared. The idea behind the use of polycyclic aromatic compounds as an alternative approach for construction of organometallic sandwich systems is to combine the plasticity of the metal ion and planarity and coordinative diversity of the hydrocarbons. Structural studies by single-crystal X-ray diffraction have shown that all compounds contain extended one- to three-dimensional structures in which several metal atoms are sandwiched between two fused polycyclic systems. While complex 1, [Ag-3(L-1)(2)(ClO4)(3)], exists in the solid state as a two-dimensional W-type architecture in which AgClO4 layers are separated by two sheets of hydrocarbon, complex 2, [Ag(L-2)(ClO4)](4). toluene, contains two double-decker polymeric chains coupled via extensive aromatic pi-pi stackings. Pillared brick sandwiched framework was observed in 3, [Ag(L-3)(ClO4)], whereas the multidecker sandwich complex 4, [Ag-2(L-3)(ClO4)(2)(benzene)], is reminiscent of ladder. The structure of L-1 has been redetermined and that of L-2 reported; the structural data are used for discussion of the silver-pi interactions. The electrochemical behavior and ESR spectra are consistent with formation of the organic radical species in the system. The present findings may represent an alternative approach for predesigning the multilayered systems in organometallic chemistry. - GL Ning; M Munakata; LP Wu; M Maekawa; T Kuroda-Sowa; Y Suenaga; K SugimotoINORGANIC CHEMISTRY AMER CHEMICAL SOC 38 (7) 1376 - + 0020-1669 1999/04 [Refereed]
A silver(I) compound with the propeller ligand hexaphenylbenzene has been synthesized, which shows the high degree of silver ions ordering around the peripheral rings of each propeller, forming a 2-D sheet framework. - K Sugimoto; T Kuroda-Sowa; M Maekawa; M MunakataCHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY 455-456 (5) 455 - 456 1359-7345 1999/03 [Refereed]
Crystal structure analyses of the title compounds revealed that they have almost the same structure with a novel eight-membered Cu4I4 ring supported by an M(mnt)(2) moiety, two cyano groups out of the four of which coordinate to two copper(I) ions in neighboring molecules, resulting in the formation of a unique doubly-bridged one-dimensional chain structure. - M Munakata; LP Wu; T Kuroda-Sowa; M Maekawa; Y Suenaga; K Sugimoto; Ino, IJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 373-378. (3) 373 - 378 0300-9246 1999/02 [Refereed]
The reactions of C-methylcalix[4]resorcinarene (L-1), calix[6]arene (L-2) and calix[4]arene (L-3) With silver(I) salts have resulted in the isolation and structural characterization of three dimeric and one polymeric silver derivatives of calixarene based on cati on pi interactions. The dinuclear cation in [Ag-2(L-1)(C6H6)(2)][ClO4](2). 5C(4)H(8)O 1 contains two symmetry-related metal centers, each involving a rather distorted tetrahedral co-ordination with, in addition to one benzene molecule, both the aryl OH groups and the aromatic rings of resorcinarene. The two dimeric calix[6]arene structures, {[Ag(L-2)X]. 2C(6)H(6)}(2,) where X = ClO4- 2 or CF3SO3- 3, display similar characteristics with two ligand groups inversely linked by the co-ordination of the silver ion to the phenyl carbons. The solvent molecules or the counter anions are not included in the cavity generated by the dimeric unit, but intercalated into calixarene or resorcinarene bilayers. In the calix[4]arene complex [Ag-2(L-3)(ClO4)(2)] 4 each of the four phenyl rings is bound to one metal atom which in turn bridges between the two calixarenes leading to an infinite two-dimensional arrangement. The polyoxo anion bridging between silver ions partially caps the container cavity of the calixarene. The factors controlling the selectivity of complexation and inclusion properties of calixarenes are discussed. - Y Suenaga; T Kuroda-Sowa; M Munakata; M Maekawa; H MorimotoPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 18 (3-4) 429 - 436 0277-5387 1999 [Refereed]
Copper(I) and silver(I) complexes of hexakis(methylthio)-benzene (hmb), [Cu(hmb)]PF6 (1) and [Ag(hmb)]PF6 (2), have been prepared and their molecular structures determined by X-ray crystallography. In 1 the copper ion prefers a tetrahedral coordination geometry comprising four sulfur atoms from two different hmb molecules and giving a linear chain structure of alternating metal cations and organic ligands. The para-position two sulfur atoms of hmb are not coordinated to copper. In 2 silver ion is of similar coordination geometry to copper ion but the shortest S ... S distance between inter-chain S atoms no coordinated with silver is 3.57 Angstrom. Therefore. complex 2 forms two-dimensional network through S ... S contacts. (C) 1998 Elsevier Science Ltd. All rights reserved. - Inorg. Chim. Acta 290, 153-158. 1999 [Refereed]
- Y Suenaga; T Kuroda-Sowa; M Munakata; M Maekawa; H MorimotoACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS MUNKSGAARD INT PUBL LTD 54 1566 - 1569 0108-2701 1998/11 [Refereed]
In the structure of catena-poly [copper(I)-mu-[hexakis(methylthio)benzene-S-1,S-2:S-4,S-5]] hexafluorophosphate, {[Cu(C12H18S6)]PF6}(n), each Cu atom is coordinated to four S atoms of two hexakis(methylthio)benzene ligands in a tetrahedral arrangement to give a cationic linear-chain polymer. The electrical resistivity of compacted pellets was measured by the conventional two-probe technique. Iodine-doped black products in powder form behave as a semiconductor with a conductivity of 1.5 x 10(-6) S cm(-1). - M Maekawa; M Munakata; T Kuroda-Sowa; Y SuenagaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 281 (1) 116 - 119 0020-1693 1998/10 [Refereed]
The reaction of [Pd-2(mu-dppm) (2)](2+) With 4-mercaptopyridine (pySH) in methanol produced the dipalladium(I) dppm complex [Pd-2( mu-dppm)(2)(HpyS)(2)] (ClO4)(2). CH3OH (1), and its structure and properties were characterized by a single crystal X-ray structure analysis, UV-Vis, IR and NMR spectra. The two Pd atoms are doubly-bridged by two dppm ligands to form an eight-membered Pd2P4C2 framework, in a twist-chair conformation. The HpyS ligand in the thione mode is also coordinated to each Pd atom, forming the Pd2P4C2 framework in a side-by-side conformation. The average Pd-S and Pd-P distance is 2.403(2) and 2.299(2) Angstrom, respectively. The Pd-Pd distance of 2.6645(6) Angstrom is shorter than that (2.75 Angstrom) in Pd metal, which is indicative of a direct Pd-Pd bond. The results of IR, NMR and W-Vis spectra supported that the dinuclear structure of 1 is kept in solid and solution. (C) 1998 Elsevier Science S.A. All rights reserved. - LP Wu; J Dai; M Munakata; T Kuroda-Sowa; M Maekawa; Y Suenaga; Y OhnoJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 3255-3261. (19) 3255 - 3261 1472-7773 1998/10 [Refereed]
The reactions of 2-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-4,5-bis(2-cyanoethylsulfanyl)-1,3-dithiole (CM-TTF) with copper(II) and silver(I) salts resulted in the isolation and structural characterization of S ... S contact assembled co-ordination polymers, [Cu(CM-TTF)][ClO4]. thf 1 and [Ag(CM-TTF)(CF3SO3)] 2, and radical cation salt, [CM-TTF][CuCl2] 3. Both 1 and 2 are 1:1 metal-ligand complexes in which the metal ions and CM-TTF molecules are alternately linked forming two-dimensional networks and infinite linear chain structures, respectively, which are further reinforced by close intermolecular S ... S interactions. The structure of 3 consists of segregated stacks of CM-TTF.+ donors and CuCl2- accepters associated via short S ... Cl contacts leading to an alternate donor-acceptor-donor columnar arrangement. The complexes were additionally characterized by IR, UV/VIS and ESR spectra as well as electrical resistivity measurements. All the complexes and their corresponding air-oxidized species are poor electrical conductors, but they show typical charge-transfer ESR signals and electronic absorptions. Complex 3 was found to exhibit transition from antiferro- to ferro-magnetic coupling upon air oxidation. - M Munakata; GL Ning; T Kuroda-Sowa; M Maekawa; Y Suenaga; T HorinoINORGANIC CHEMISTRY AMER CHEMICAL SOC 37 (21) 5651 - 5656 0020-1669 1998/10 [Refereed]
This paper describes two copper(I) supramolecules with the same anion and cation but quite different topologies and properties. The reaction of [Cu(CH3CN)(4)]PF6 and 1,2,4,5-tetracyanobenzene (TCNB) leads to two novel polymeric coordination compounds, [Cu-2(TCNB)(3)](PF6)(2)(Me2CO)(4) (1) and [CU2(TCNB)(3)](PF6)(2) (2), depending on the solvents used. The crystal structures have been determined by single-crystal X-ray diffraction. Crystal data are as follows, 1: C21H15N6O2CuPF6, monoclinic, P2(1)/a, a = 11.553(4) Angstrom, b = 16.135(7) Angstrom, c = 15.046(3) Angstrom, beta = 108.08(2)degrees, Z = 4. 2: C15H3N6CuPF6, orthorhombic, Cmcm, a = 28.282(3) Angstrom, b =10.337(3) Angstrom, c = 16.285(4) Angstrom, Z = 16. In both polymers, copper(I) ions have similar pseudotetrahedral environments and the four coordination sites are fully occupied by the four bridging ligands, two mu(2)-TCNB and two mu(4)-TCNB groups. Polymer 1, obtained in acetone, revealed a two-dimensional zigzag sheet network between copper(I) ions, whereas 2, synthesized in methylethyl ketone, displayed a three-dimensional porous framework with different functional groups (or atom) in different cavities. The redox, magnetic, and conductive behaviors of both complexes are discussed. It is demonstrated that the two complexes give different physicochemical properties. - M Munakata; LP Wu; T Kuroda-Sowa; M Maekawa; Y Suenaga; GL Ning; T KojimaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 120 (34) 8610 - 8618 0002-7863 1998/09 [Refereed]
Four organosilver(I) complexes of polycyclic aromatic hydrocarbons (PAHs) have been investigated crystallographically. The aim was to establish whether a favorable combination of cation-pi interactions and aromatic stackings might produce functional organometallic solid materials with novel networks. Complete structures of the silver(I) perchlorate with 9,10-diphenylanthracene (L-1), rubrene (L-2), benzo[a]pyrene (L-3), and coronene (L-4) were determined by X-ray diffraction. All compounds are organometallic species based on cation-pi interactions. While complex 1 with L-1 revealed a discrete mononuclear structure, complex 2 with rubrene displayed a ct-bonded 3-D polymer. Complexes 3 and 4 can be regarded as both coordination polymer and stacking polymer, and the detailed differences in the geometries and the stacking patterns of 1,3 and L-4 gave helical and triple-decker networks, respectively. The ESR spectroscopic results and conductivity of the compounds are also discussed. The present findings may serve as a basis for understanding specific interactions responsible for self-assembly of multinuclear aggregates involving PAHs. - T Kuroda-Sowa; M Hirata; M Munakata; M MaekawaCHEMISTRY LETTERS CHEMICAL SOC JAPAN 499 (6) 499 - 500 0366-7022 1998/06 [Refereed]
The X-ray crystal structure analysis of a copper(I) coordination compound, [Cu(dmtpn)(2)(TTF)(0.5)](ClO4) revealed the novel two-dimensional polymer framework bridged by dmtpn and TTF, which is the first example of bridging TTF coordinated. to transition metal ions. - M Munakata; HY He; T Kuroda-Sowa; M Maekawa; Y SuenagaJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 1499 (9) 1499 - 1502 0300-9246 1998/05 [Refereed]
Three dicopper complexes of 4-amino-2,1,3-benzothiadiazole (abt) have been isolated and structurally characterized. The reaction of [Cu(CH3CN)(4)][PF6] with abt in THF produced [Cu-2(abt)(2)(CH3CN)(4)][PF6](2) . C6H12 1 . C6H12, while in acetone, Cu-I template Schiff-base condensation of the amino group of abt with solvent was found to give [Cu-2(ibt)(2)(CH3CN)(4)][PF6](2) 2 (ibt = 4-isopropylideneamino-2,1,3-benzothiadiazole). In complex 1 there are two crystallographically independent monomeric units in each of which Cu-I is co-ordinated by one N atom on the ring of abt and two acetonitrile molecules; two units are linked to each other by weak binding of the amino group of abt with Cu-I to give a cyclic dinuclear complex. In complex 2 tetrahedral Cu-I centers are bridged by two ibt molecules in a head-to-tail fashion as in 1. Both 1 and 2 have the same metallocyclophane skeletons showing an intramolecular stacking interaction between two parallel aromatic rings and a considerably long Cu ... Cu separation [7.220(5) Angstrom for 1, 6.542(4) Angstrom for 2]. Following the same synthetic strategy as used for the synthesis of 2 another dicopper complex [Cu-2(ibt)(2)][ClO4](2) 3 was obtained, which presents a structural contrast with 2: two Cu-I centers are linearly co-ordinated by two ibt molecules in a head-to-head arrangement which leads to a twisted conformation with a shorter Cu ... Cu distance of 2.699(2) Angstrom. In addition, H-1 NMR measurements reveal that 2 can also be formed directly from 1 in acetone solution. - M Munakata; SG Yan; Ino, I; T Kuroda-Sowa; M Maekawa; Y SuenagaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 271 (1-2) 145 - 150 0020-1693 1998/04 [Refereed]
A novel bis(thianthrene)disilver(I)bis(perchlorate), [Ag-2(TA)(2)(ClO4)(2)] (1) (TA = thianthrene), was prepared and characterized by single-crystal X-ray diffraction methods, H-1 and C-13 NMR: IR and UV spectra analysis. Complex 1 is triclinic, space group <P(1)over bar>, a = 9.244(1), b = 9.275(1), c = 8.343(2) Angstrom, alpha = 101.22(1)degrees, beta = 110.63(1)degrees, gamma = 97.15(i)degrees, V = 679.8(2) Angstrom(3), Z = 2, R = 0.028 and R-w = 0.042. The silver is tetrahedrally coordinated to an oxygen of ClO4-, a phenylene ring of one TA, and to two sulfur atoms of the other TA. The average distance of silver to the phenylene ring in complex 1 is 2.55 Angstrom. Both H-1 and C-13 NMR Studies indicate that the silver-phenylene ring bond is broken in acetone solution. The complex 1 is an insulator, while the I-2-doped blue complex shows a new absorption band at 478 nm and an electric conductivity of 5.0 x 10(-4) S cm(-1). (C) 1998 Elsevier Science S.A. - M Maekawa; M Munakata; S Kitagawa; T Kuroda-Sowa; Y Suenaga; M YamamotoINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 271 (1-2) 129 - 136 0020-1693 1998/04 [Refereed]
Two novel ternary dicopper(I) complexes bridged by 1,8-naphthyridine (napy), [Cu-2(napy)(2)(Me2CO)](PF6)(2) . 2Me(2)CO (1) and [Cu-2(napy)(2)(dppm) (CH3CN)] (PF6)(2) (2), have been prepared and their structures have been determined crystallographically. Complex 1: space group P2(1)/a, a = 12.281(4), b = 21.154(3), c = 13.891(3) Angstrom, beta = 112.74(2)degrees, Z= 4, R = 0.079 and R-w = 0.093. Complex 2: space group Cc, a = 19.572(7), b = 13.708(7), c = 18.457(3) Angstrom, beta= 108.56(2)degrees, Z= 4, R= 0.064 and R-w = 0.066. On complex 1 two Cu atoms are doubly bridged by two napy ligands to provide a dinuclear structure, which has a close Cu(I)... Cu(I) separation of 2.533(2) Angstrom. Two Cu atoms on 2 are also triply bridged by two napy and one dppm ligands to give a dinuclear structure with a close Cu(I)... Cu(I) separation of 2.607(3) Angstrom On these dicopper(I) complexes the most remarkably structural feature is that the coordination environment around each Cu atom is different: complex 1 has one linear and one T-shaped copper, and 2 has one distorted trigonal and one distorted tetrahedral copper. It was structurally found that the Cu(I)Cu(I) separation greatly depends on the coordination arrangement around each Cu atom: the Cu(I)... Cu(I) distance should be longer in the order of the coordination arrangements of {two linear coppers}, {one linear and one T-shaped copper}, {two trigonal coppers}, {one trigonal and one tetrahedral copper}, and {two tetrahedral coppers}. (C) 1998 Elsevier Science S.A. - Y Suenaga; SG Yan; LP Wu; Ino, I; T Kuroda-Sowa; M Maekawa; M MunakataJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 1121 (7) 1121 - 1125 1472-7773 1998/04 [Refereed]
Copper(I) and silver(I) complexes of 2-[bis(methylsulfanyl)methylene]propanedinitrilel (bmmp), [Cu(bmmp)(2)]ClO(4) 1 and [Ag(bmmp)(2)]ClO(4) 2, have been prepared and their molecular structures determined by X-ray crystallography. The network topology of bmmp is found to depend on the metal-ion stereochemical preference. In 1 the copper(I) ion prefers a tetrahedral co-ordination geometry comprising four nitrogen atoms from four different bmmp molecules and each bmmp in turn bridges two copper(I) centres leading to a square-grid arrangement of alternating metal cations and organic ligands. In 2, by contrast, the silver(I) ion involves an elongated octahedral environment with four N atoms forming a basal plane and two thioether S atoms occupying the axial positions; each bmmp acts as a non-chelating tridentate ligand bridging three metal centres, resulting in a three-dimensional channel structure. The influence of the metal-ion stereochemical preference on the co-ordination networks of bmmp is discussed. - M Maekawa; M Munakata; T Kuroda-Sowa; Y SuenagaANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 14 (2) 451 - 453 0910-6340 1998/04 [Refereed]
- M Maekawa; M Munakata; T Kuroda-Sowa; Y SuenagaANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 14 (2) 447 - 449 0910-6340 1998/04 [Refereed]
- M Munakata; LP Wu; T Kuroda-Sowa; M Yamamoto; M Maekawa; K MoriwakiINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA 268 (2) 317 - 321 0020-1693 1998/02 [Refereed]
The synthesis and characterization of a mixed-valence copper complex [Cu-II(bpy)(2)Cl](2)[(CuCl2)-Cl-I](2)(C6O6H4), where bpy=2,2'-bipyridine, is described. The structure contains discrete copper(II) cation and copper(I) anion groups. In the cation each divalent copper is Linked to two bpy molecules and one chloride ion in a trigonal bipyramidal fashion, whereas in the anion each monovalent copper is linearly bound to two chlorine atoms. The mixed-valence Cu(I/II) system is associated by multiple hydrogen bonding through tetrahydroxybenzoquinone, leading to an infinite chain structure of the complex. The complex was also characterized by spectroscopic studies. (C) 1998 Elsevier Science S.A. - Y Suenaga; T Kuroda-Sowa; M Munakata; M MaekawaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 17 (13-14) 2207 - 2211 0277-5387 1998 [Refereed]
The crystal and molecular structure of a dinuclear copper(II) complex with 3,4,9,10-perylenetetracarboxylic acid (H(4)ptca) and ethylenediamine (en) [Cu-2(en)(4)(mu-ptca)] (EtOH)(2)(H2O)(6) has been determined by X-ray structural analysis. Each copper atom is coordinated by four-nitrogen atoms of two en molecules, one oxygen atom of bridging ptca(4-) and one water molecule in an octahedral arrangement. The resulting dinuclear copper(II) complex forms two-dimensional network through intermolecular hydrogen bonds between carboxylate of ptca4- and the water. (C) 1998 Elsevier Science Ltd; All rights reserved. - J Dai; M Munakata; GQ Bian; QF Xu; T Kuroda-Sowa; M MaekawaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 17 (13-14) 2267 - 2270 0277-5387 1998 [Refereed]
Two mercury(II) complexes of 4,5-ethylenedithio-1,3-dithiole-2-thione (C5H4S5), [Hg-2(C5H4S5)(2)Cl-4] (1) and [Hg-2(C5H4S5)(2)Br-4] (2), were synthesized and the structure of complex 1 was characterized crystallographically. Complex 1 has a dimeric structure, in which each mercury atom takes a tetrahedral geometry and is coordinated by two bridging chloride, one terminal chloride and one thiocarbonyl sulfur atom (C=S) of the ligand. These dimers are further packed to form a one dimensional ribbon structure via intermolecular S ... S and S ... Cl contacts. All of the ligands in the ribbon are co-planar and weakly conjugated. (C) 1998 Elsevier Science Ltd. All rights reserved. - M Maekawa; M Munakata; T Kuroda-Sowa; Y SuenagaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 17 (20) 3657 - 3663 0277-5387 1998 [Refereed]
Reaction of the intermediate [Pd-2(mu-dppm)(2)](2+) which was prepared from [Pd-2(mu-dppm)(2)X-2] (X = Cl, Br and I) and AgClO4 in ethanol with 2-vinylpyridine (vpy) afforded dinuclear Pd(I) dppm complex [Pd-2(mu-dppm)(2)(vpy)Cl] (1). When the intermediate [Pd-2(mu-dppm)(2)](2+) was allowed to stand for a few days, tetranuclear Pd dppm complex [Pd-4(mu-dppm)(4)(mu-X)(2)](ClO4)(2) (X = Cl (2); Br (3) and I (4)) was systematically formed. The structure for 1 and 2 were crystallographically determined. On complex 1 two Pd atoms are doubly bridged by two dppm ligands to form an eight-membered Pd2P4C2 framework in a twist-chair conformation. Each Pd atoms is also coordinated by the Cl atom and the N atom of vpy in unsymmetrical side-by-side mode. The Pd-Pd distance is 2.597(2) Angstrom and the torsion angle between two Pd2P4 plane is 43.2 degrees. On the other hand four Pd atoms on 2 are bridged by four dppm ligands to form a rectangular Pd-4 core, which is composed of the shorter Pd-Pd separations (2.590(1) Angstrom) and the close Pd ... Pd separations (3.818(2) Angstrom). The later Pd ... Pd separation is also bridged by the Cl atom. The Pd-P distance (2.351(1) Angstrom) bridging the close Pd ... Pd separation is rather longer than that (2.238(2) Angstrom) bridging the shorter Pd-Pd separation. (C) 1998 Elsevier Science Ltd. All rights reserved. - Y Suenaga; T Kuroda-Sowa; M Munakata; M MaekawaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 18 (1-2) 191 - 195 0277-5387 1998 [Refereed]
Silver(I) complex of pyrazine-2,3-dicarbonitrile (dcpz)] [Ag(dcpz)](ClO4) have been prepared and the molecular structure determined by X-ray crystallography. The silver ion prefers an octahedral coordination geometry comprising four nitrogen atoms from four different dcpz molecules and two oxygen atoms from ClO4- anion molecule. Each dcpz in turn bridges four Ag(I) centres leading to a square mesh arrangement of alternating metal cations and organic ligands. The square mesh sheet accumulates along the c-axis direction, consisting of a channel structure. (C) 1998 Elsevier Science Ltd. All rights reserved. - T Kuroda-Sowa; T Horino; M Yamamoto; Y Ohno; M Maekawa; M MunakataINORGANIC CHEMISTRY AMER CHEMICAL SOC 36 (27) 6382 - 6389 0020-1669 1997/12 [Refereed]
With the use of three dicyanobenzene derivatives as bridging ligands, four copper(I) coordination polymers, [Cu(dchq)(2)](ClO4)(Me2CO)(2) (1; dchq = 1,2-dicyanohydroquinone), [Cu(ipn)(2)[(PF6)(Me2CO) (2; ipn = 1,3-dicyanobenzene), and [Cu(dmtpn)(2)](X)(dmtpn)(THF) (3a (X = BF4), 3b (X = ClO4); dmtpn = 2,5-dimethylterephthalonitrile) were synthesized and characterized. Single-crystal X-ray analyses revealed that all copper(I) ions in these complexes have tetrahedral geometry and are coordinated by four ligands which also coordinate to the next copper ions, resulting in the formation of coordination polymer compounds. The polymer framework of 1 consists of one-dimensional chains that run along the a-axis direction and weakly interact with each other through pi-pi interactions between the dchq molecules and through hydrogen bonding. 2 has a two-dimensional sheet with a square arrangement of copper(I) ions. Stacking of the square lattice in the c-axis direction forms cavities in which the acetone molecules and PF6- anions are incorporated. Both 3a and 3b are isostructural and have triply interpenetrated three-dimensional diamond-like frameworks with pi-pi stacking columns of alternately coordinated and uncoordinated dmtpn molecules. It is demonstrated that the dimensionality of the polymer structures can be successfully controlled by the relative positions of two CN groups in the bridging Ligands. Crystallographic data are as follows. 1: C22H20CuCIN4O10, monoclinic, C2/c, a = 19.514(2) Angstrom, b = 10.526(2) Angstrom, c = 12.276(1) Angstrom, beta = 96.839(8)degrees, Z = 4. 2: C19H14CUF6N4OP, orthorhombic, P2(1)2(1)2(1), a = 12.743(2) Angstrom, b = 15.026(3) Angstrom, c = 11.362(2) Angstrom, Z = 4. 3a: C34H32BCuF4N6), monoclinic, Cc, a = 9.599(3) Angstrom, b = 27.298(5) Angstrom, c = 13.367(3) Angstrom, beta = 105.45(2)degrees, Z = 4. 3a: C34H32ClCuN6O5, monoclinic, Cc, a = 9.590(7) Angstrom,b = 27.429(3) Angstrom, c = 13.416(4) Angstrom, beta = 105.80(3)degrees, Z = 4. - Y Suenaga; M Maekawa; T Kuroda-Sowa; M Munakata; H Morimoto; N Hiyama; S KitagawaANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 13 (6) 1047 - 1049 0910-6340 1997/12 [Refereed]
- M Munakata; LP Wu; T KurodaSowa; M Maekawa; K Moriwaki; S KitagawaINORGANIC CHEMISTRY AMER CHEMICAL SOC 36 (23) 5416 - 5418 0020-1669 1997/11 [Refereed]
- M Munakata; SG Yan; M Maekawa; M Akiyama; S KitagawaJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 4257 (22) 4257 - 4262 0300-9246 1997/11 [Refereed]
A series of gold(I) complexes [Au(PPh3)L]ClO4 (L = pyridine 1a, 2,6-dimethylpyridine 1b, 2,6-di-tert-butylpyridine 1c, quinoline 1d, acridine 1e, benzo[h]quinoline 1f, naphthyridine 2a, 1,10-phenanthroline 2b, 2,2'-biquinoline 2c, di-2-pyridyl ketone 2d, di-2-pyridylamine 3a or 2-(2-pyridyl)bemimidazole 3b) were prepared by reaction of L with [Au(PPh3)(ClO4)] which was synthesized in situ. All complexes were characterized by IR, UV/VIS and H-1 NMR spectroscopy. The crystal and molecular structures of Ib, 2a and 3b were investigated by single-crystal X-ray diffraction techniques. The gold(I) is co-ordinated to one nitrogen atom and one phosphine atom. Detailed H-1 NMR studies suggested that linear two-co-ordinated structures persist in solution and further that all the complexes [Au(PPh3)L]ClO4, (2a-2d), are fluxional species in which the co-ordination site of gold(I) rapidly exchanges between two nitrogen atoms of the ligand. - M Munakata; LP Wu; T KurodaSowa; M Maekawa; Y Suenaga; K SugimotoINORGANIC CHEMISTRY AMER CHEMICAL SOC 36 (21) 4903 - 4905 0020-1669 1997/10 [Refereed]
- M Yamamoto; XM Gan; T KurodaSowa; M Maekawa; Y Suenaga; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 261 (2) 169 - 174 0020-1693 1997/09 [Refereed]
Two-linear coordination polymers composed of copper(I) cations and tetrakis(ethylthio)tetrathiafulvalene (TTC2-TTF) and tetrakis(propylthio)tetrathiafulvalene (TTC3-TTF) molecules have been synthesized by the reaction of copper(I) tetrafluoroborate with TTC2-TTF and copper(I) perchlorate with TTC3-TTF, respectively, in acetone under argon. The compounds, [Cu(TTC2-TTF)]BF4 (i) and [Cu(TTC3-TTF)]ClO4 (2), were characterized by spectroscopic and X-ray crystallographic methods. They are 1:I metal-ligand complexes in which each of the copper(I) ions is tetrahedrally coordinated by four sulfur atoms from the bridging TTC2-TTF or TTC3-TTF molecules to form coordination polymeric chains. 1 and 2 were doped with iodine to afford {[Cu(TTC2-TTF)]BF4}(I-3)(0.33) and {[Cu(TTC3-TTF)]ClO4}(I-3)(0.33), which exhibit conductivities of 2x10(-5) and 4x10(-5) S cm(-1), respectively, at 25 degrees C for compacted pellets. - Y Suenaga; M Maekawa; T KurodaSowa; M MunakataANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 13 (4) 647 - 649 0910-6340 1997/08 [Refereed]
- Y Suenaga; M Maekawa; T KurodaSowa; M Munakata; H Morimoto; N Hiyama; S KitagawaANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 13 (4) 651 - 652 0910-6340 1997/08 [Refereed]
- J Dai; T KurodaSowa; M Munakata; M Maekawa; Y Suenaga; Y OhnoJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 2363 (13) 2363 - 2368 0300-9246 1997/07 [Refereed]
Two silver(I) complexes of 4,5-ethylenedithio-1,3-dithiole-2-thione (C5H4S5), [{Ag(C5H4S5)(3)}ClO4 . CH3CN](2) and [Ag(C5H4S5)CF3SO3](infinity) have been synthesized and characterized crystallographically. They have unique dimeric and two-dimensional structures respectively and are assembled by S ... S contacts. The finding of the shortest S ... S contacts (3.284 and 3.262 Angstrom) in these complexes indicated that the co-ordination linkage in metal complexes containing these types of sulfur donor compounds could be expected to control the intra- or inter-molecular interactions. The co-ordination mode of the C5H4S5 ligand has also been discussed. - J Dai; M Yamamoto; T KurodaSowa; M Maekawa; Y Suenaga; M MunakataINORGANIC CHEMISTRY AMER CHEMICAL SOC 36 (12) 2688 - 2690 0020-1669 1997/06 [Refereed]
- M Yamamoto; LP Wu; T KurodaSowa; M Maekawa; Y Suenaga; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 258 (1) 87 - 91 0020-1693 1997/05 [Refereed]
The crystal structures of dtpcpI(4) (1), [CuCl2(dtpcp)(EtOH)] (2) and [CuBr2(dtpcp)(MeOH)] (3), where dtpcp = 2,11-dithia[3,3]-paracyclophane, have been determined by X-ray crystallography. Complex 1 contains two crystallographically independent I(2)dtpcpI(2) molecules in the unit cell, each having crystallographical -1(C-i) symmetry. The structures of both 2 and 3 consist of a one-dimensional array of copper(II) ions linked via dithia-bridged paracyclophane. While 1 is an electric insulator at room temperature, the iodine oxidation of 2 and 3 produced charge-transfer complexes which gave conductivities 10(-5.5) and 10(-6.9) S cm(-1), respectively. Both 2 and 3 show the typical ESR signals and normal magnetic moments for a dilute copper(II) ion at room temperature, but exhibit an antiferromagnetic coupling at low temperature through the conjugated rr system of the bridging ligand. - M Maekawa; T KurodaSowa; Y Suenaga; M MunakataANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 13 (2) 319 - 320 0910-6340 1997/04 [Refereed]
- Y Suenaga; LP Wu; T KurodaSowa; M Munakata; M MaekawaPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 16 (1) 67 - 70 0277-5387 1997 [Refereed]
A ternary copper(I) complex with ethylene and tetramethylethylenediamine (tmen) has been prepared and the structure characterized by the single crystal X-ray method. The copper atom is coordinated to two nitrogen atoms of tmen and an ethylene molecule in a trigonal-planar arrangement. The C=C bond distance of 1.36(1) Angstrom is slightly longer than that of the free ethylene (1.33 Angstrom ). In the H-1 NMR study, chemical shifts of ethylene protons at 5.46 ppm move upfield (4.16 ppm) upon coordination to copper(I). This indicates that the pi back donation from copper to the ethylene is rather weak compared with other metal-ethylene systems. Copyright (C) 1996 Elsevier Science Ltd - LP Wu; M Munakata; T KurodaSowa; M Maekawa; Y SuenagaINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 249 (2) 183 - 189 0020-1693 1996/08 [Refereed]
Three lanthanide complexes with mellitic acid, [Ce-2{C-6(COO)(6)}(H2O)(8)]. H2O (1), [Eu-2{C-6(COO)(6)}(H2O)(8)]. H2O (2) and [Yb-2{C-6(COO)(6)}(H2O)(10)]. 2H(2)O (3), have been synthesized and structurally characterized by X-ray crystallography and magnetic properties. The three compounds crystallize in the monoclinic space group P2(1)/n, with unit cell, dimensions of: a = 8.627(2), b = 13.218(2), c = 9.650(1) Angstrom, beta = 95.93(1)degrees and Z = 2 for 1; a = 8.505(2), b = 13.145(1), c = 9.536(2) Angstrom, beta = 94.73(2)degrees and Z = 2 for 2; a = 8.420(1), b = 9.224(4), c = 16.229(1) Angstrom, beta = 100.267(9)degrees and Z = 2 for 3. All three structures consist of an extended network of metal ions, coordinated to mellitate anions and water molecules linked by a complex hydrogen bonding. 1 and 2 are isomorphous with near isostructural [M(2){C-6(COO)6}(H2O)(8)] units in which the metal ion is coordinated by four water molecules and five oxygen atoms of the mellitate anions, and each mellitate group involves a tetrakis(bidentate) and bis(unidentate) coordination mode bridging six metal ions forming a threedimensional framework. In 3 the ytterbium atom is bound with five water molecules and three oxygen atoms of the mellitate anion, and each mellitate moiety bridges four dodecahedral Yb(III) ions yielding a two-dimensional sheet structure. The magnetic susceptibility of 1 and 3 as a function of temperature (5.0-300 K) exhibits a sharp maximum at 6.0 K for both compounds. - LP Wu; Y Suenaga; T KurodaSowa; M Maekawa; K Furuichi; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 248 (2) 147 - 152 0020-1693 1996/07 [Refereed]
Two palladium(II) complexes with the photochromic ligand 4-methoxyazobenzene (MeOazbH), [Pd(MeOazb) (PhCN) (H2O)] (ClO4) (1) and [Pd(MeOazbH)(2)Cl-2] (2) were prepared and their molecular structures determined by X-ray crystallography. 1: triclinic, <P(1)over bar>, a=9.684(3), b=11.833(2), c=9.731(3) Angstrom, alpha=102.41(1), beta=94.54(3), gamma=94.82(2)degrees, V=1079.7(4) Angstrom(3), Z=2. 2: triclinic, P (1) over bar, a=9.497(3), b=9.719(4), c=8.226(3) Angstrom, alpha=96.43(4), beta=109.24(3), gamma=62.13(2)degrees, V=632.9(4) Angstrom(3), Z=1. The molecular structure of complex 1 shows a significantly distorted square planar coordination around the Pd atom and the MeOazb group forms a five-membered chelate ring with the metal ion by means of a sigma-bond at an ortho-carbon atom and the lone pair of the further nitrogen. In complex 2 the palladium atom lies on an inversion center, surrounded in an essentially square planar fashion by the symmetry related two MeOazbH ligands and two chloride ions. In contrast with the ortho-metalation reaction in 1, MeOazbH in 2 acts as a monodentate ligand to bind the metal center via a Pd-N sigma-bond. Electronic spectroscopic studies of the two complexes together with the free ligand were carried out in solution at room temperature and upon irradiation of light; while rigidity imparted to the MeOazb linkage by palladation in 1 inhibits its photochromic reaction, the monodentate-coordinated MeOazbH in 2 shows a trans-cis photoisomerization. - LP Wu; M Yamamoto; T KurodaSowa; M Maekawa; Y Suenaga; M MunakataJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 2031 (10) 2031 - 2037 0300-9246 1996/05 [Refereed]
Reaction of the appropriate copper(I) salt with 3-cyano-6-methylpyridin-2(1H)-one (Hcmp) gave three polymeric co-ordination compounds, [Cu(cmp)(Hcmp)(3)]. C5H12 1, [Cu-2(Hcmp)(4)(Me(2)CO)(2)][BF4](2) 2 and [Cu-5(cmp)(4)]ClO4 3, the structures of which have been determined by X-ray crystallography. Complex 1 contains a three-dimensional supramolecular framework of tetrahedral CuN4 centres linked by intermolecular hydrogen bonds through the pyridone N and O atoms. The open square microchannels created enclathrate n-pentane as the guest molecule. Complex 2 contains a dimeric unit weakly bound by the bridging acetone oxygen atoms. Each Hcmp moiety in the dimer is hydrogen-bonded pairwise to one adjacent Hcmp molecule belonging to the other dimer giving a one-dimensional array of copper atoms. The unique structural feature of complex 3 is that it does not involve hydrogen bonding as in 1 or 2, instead each cmp monoanion employs all its three functional groups bridging three copper atoms forming a supramolecular channel architecture containing a Cu-4 cluster. The results are discussed in terms of designing new inorganic solids by the self-assembly of copper(I) complexes. - LP Wu; T KurodaSowa; M Maekawa; Y Suenaga; M MunakataJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 2179 (10) 2179 - 2180 0300-9246 1996/05 [Refereed]
The tetranuclear copper(II) complex [{Cu(O(2)CMe)(OMe)}(4)] has been found to contain an unusual open cubane Cu4O4 framework defined by two interpenetrating copper and oxygen planes rather than two tetrahedra; it also shows strong antiferromagnetic coupling. - M Munakata; LP Wu; T KurodaSowa; M Maekawa; Y Suenaga; K FuruichiJOURNAL OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 118 (13) 3305 - 3306 0002-7863 1996/04 [Refereed]
- One-, two- and three-dimensional copper(I) and silver(I) complexes of 2,11-dithia[3.3]paracyclophaneM Munakata; LP Wu; T KurodaSowa; M Maekawa; Y Suenaga; S NakagawaJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 1525 (8) 1525 - 1530 0300-9246 1996/04 [Refereed]
Two copper(I) and one silver(I) complex of 2,11-dithia[3.3]paracyclophane (dtpcp), [Cu2Br2(dtpcp)(MeCN)(2)] 1, [Cu2I2(dtpcp)(2)] . thf 2 and [Ag(dtpcp)(NO3)] 3, have been synthesized and their molecular structures determined by X-ray crystallography. All three structures contain an infinite network comprising metal cations linked via ditha-bridged paracyclophane and the counter anions. Complexes 1 and 2 are not isostructural. The repeating dinuclear units [Cu2Br2(dtpcp)(MeCN)(2)] joined by dtpcp in 1 generate a one-dimensional polymeric chain running parallel to a diagonal axis of the triclinic cell. Complex 2 is a two-dimensional sheet structure in which a large ring containing six copper atoms includes a tetrahydrofuran molecule as guest inside the open cavity. The one-nitrate oxygen bridging two metal centres in complex 3 yields a unique three-dimensional channel framework of silver(I) ions. The iodine-doped black products of compounds 1-3 at room temperature exhibited conductivities of 10(-5.9), 10(-5.1) and 10(-4.7) S cm(-1), respectively. - R Shiozaki; E Nishio; M Morimoto; H Kominami; M Maekawa; YA KeraAPPLIED SPECTROSCOPY SOC APPLIED SPECTROSCOPY 50 (4) 541 - 544 0003-7028 1996/04 [Refereed]
- M Munakata; LP Wu; M Yamamoto; T KurodaSowa; M MaekawaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 118 (13) 3117 - 3124 0002-7863 1996/04 [Refereed]
This paper describes four novel hydrogen-bonded copper(I) supramolecules with channel structures. The reactions of copper(I) salt with 3-cyano-6-methyl-2(1H)-pyridinone (Hcmp) in acetone have isolated four polymeric coordination products [Cu(Hcmp)(4)]X, where X = ClO4- (1), BF4- (2), PF6- (3), and CF3SO3- (4). All four compounds crystallized in the tetragonal system. Each structure contains a three-dimensional framework of tetrahedral CuN4 centers linked by intermolecular hydrogen bonds through pyridone N and O atoms in a head-to-tail mode. The very special structural features of the four compounds are related to the two types of hydrogen-bonding. Complexes 1 and 2 with smaller counteranions involve each Hcmp group hydrogen-bonded to two adjacent others (type A), which generates an open square channel filled with aligned ClO4- or BF4- ions, whereas 3 and 4 involve 1:1 pairwise hydrogen-bonding of Hcmp (type B) which results in four independent interpenetrating diamond-like frameworks with big cavities to accommodate larger anions of PF6- and CF3SO3-. Novel insight into the unique role played by the hydrogen-bonding mode and distances on the architecture of the network is discussed. The study indicates that the metal complex supramolecular structures can be rationally designed via hydrogen-bonding interactions. - R Shiozaki; A Inagaki; A Nishino; E Nishio; M Maekawa; H Kominami; Y KeraJOURNAL OF ALLOYS AND COMPOUNDS ELSEVIER SCIENCE SA LAUSANNE 234 (2) 193 - 198 0925-8388 1996/02 [Refereed]
A series of sodium lanthanide decatungstates, Na(7)H(2)Ln(III)(W5O18)(2) . nH(2)O (Ln = La-Yb) was synthesized and characterized by spectroscopic analyses. The W-183-NMR chemical shifts for the W adjacent to Ln(III) correlated well. with the contact parameter in the lanthanide induced shifts, (Sz), which had been theorized by Golding. The FT-Raman stretching frequencies for the Ln-O-W bonding also correlated with the theoretical magnetic moments induced from the 4f(n) electrons in the lanthanide ions in addition to the ionic radii of Ln(III). A direct contribution of the 4f(n) electrons to the bonding interaction among Ln(III) and the oxotungstates is suggested. - T KurodaSowa; M Yamamoto; M Munakata; M Seto; M MaekawaCHEMISTRY LETTERS CHEMICAL SOC JAPAN 349 (5) 349 - 350 0366-7022 1996 [Refereed]
Two novel coordination polymer compounds, [Cu(DMTPN)(2)]X(DMTPN)(thf) (DMTPN = 2, 5-dimethylterephthalonitrile, X = BF4 (1) and ClO4 (2)) are prepared and characterized by single crystal X-ray analysis; both are isostructural and have three-fold interpenetrated diamondoid structure with pi-pi stacking column of alternate coordinated and uncoordinated DMTPN. - T KurodaSowa; A Hirota; M Munakata; M MaekawaMOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS GORDON BREACH SCI PUBL LTD 285 69 - 74 1058-725X 1996 [Refereed]
One-electron oxidation of tetrakis(methylthio)tetrathiafulvalene (TTC1TTF) by CuBr2 yields a black copper(I) coordination compound, [(TTC1TTF)CuBr2](2) (1), whose structure has been determined by means of X-ray crystallography. 1 has a dimer structure consisting of a Cu2Br2 rhomboid with terminal Br- and TTC1TTF+ which coordinate to Cu(I) through one of four SMe groups. TTC1TTF+ form columnar stacks with the shortest S ... S contact of 3.44 Angstrom. Since most of TTC1TTF+ cation radicals in crystal form spin-pairs, a weak ESR signal observed at g = 2.008 is attributed to TTC1TTF+ radicals remain as free from pair formation located at crystal surface. Crystal Data: triclinic (P (1) over bar), a = 10.053(1) Angstrom, b = 10.618(1) Angstrom, c = 9.722(2) Angstrom, alpha = 90.85(1)degrees, beta = 91.04(1)degrees, gamma = 110.487(9)degrees, V = 971.7(3) Angstrom(3), Z = 1, R = 0.036, R(W) = 0.036. - LP Wu; M Munakata; M Yamamoto; T KurodaSowa; M MaekawaJOURNAL OF COORDINATION CHEMISTRY GORDON BREACH SCI PUBL LTD 37 (1-4) 361 - 369 0095-8972 1996 [Refereed]
The crystal and molecular structure of a lanthanum(III) mellitate, La2C12H22O23, has been determined by X-ray structural analysis using a combination of direct and heavy atom methods. The complex crystallizes in the monoclinic space group P2(1)/n with unit-cell dimensions of a = 6.723(4), b = 11.368(5), c = 29.813(4) Angstrom and beta = 95.851(3)degrees. Block-diagonal least-squares refinement using automated diffractometer-collected data resulted in R = 2.5 and R-w = 3.4. The crystal structure consists of layers perpendicular to the a axis. Each layer is formed by an extended network of lanthanum ions coordinated with mellitate anions and water molecules, and linked through a complex three-dimensional hydrogen-bonding network. Among the six carboxylate groups of the mellitate anion, five form coordination bonds to six lanthanum atoms. The two independent lanthanum ions are both nine-coordinate and the configuration around lanthanum is a tricapped trigonal prism with the La-O bond distances ranging from 2.457 Angstrom to 2.704 Angstrom. - LP Wu; XM Gan; M Munakata; T KurodaSowa; M Maekawa; Y SuenagaMOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS GORDON BREACH SCI PUBL LTD 285 75 - 82 1058-725X 1996 [Refereed]
Oxidation of tetrakis(ethylthio)tetrathiafulvalene (TTC2-TTF) with CuCl2 and CuBr2 in acetonitrile yielded the organic radical cation salts, (TTC2-TTF)2[Cu2Cl6] 1 and (TTC2-TTF)(2)[Cu2Br6] 2, whose structures have been determined by X-ray structure analysis. Both 1 and 2 crystallize in the triclinic system, space group P (1) over bar with one molecule per unit cell. 1: a = 12.065(4), b = 12.644(3), c = 8.988(2) Angstrom, alpha = 103.54(2), beta = 90.24(2), gamma = 112.42(2)degrees. 2: a = 12.330(3), b = 12.647(2), c = 8.956(2) Angstrom, alpha = 101.72(2), beta = 94.66(2), gamma = 111.69(1)degrees. Both structures consist of two segregated stacks of TTC2-TTF+ donors and Cu(2)X(6)(2-) accepters associated via short S ... X contacts. Consistent with the structural results, the two compounds exhibit low electrical conductivities with sigma 25 degrees C being 4 x 10(-8) and 8 x 10(-8) S cm(-1) for 1 and 2, respectively. - J Dai; XD Yang; JP Sun; ZR Lu; M Munakata; M MaekawaJOURNAL OF COORDINATION CHEMISTRY GORDON BREACH SCI PUBL LTD 38 (4) 281 - 285 0095-8972 1996 [Refereed]
Two palladium(II) complexes with aminopyrene and a derivative have been synthesized and characterized. In complex 1, Pd(apyr)(2)Cl-2 (apyr = 1-aminopyrene), the pyrenyl-pi-electrons do not conjugate with d-electrons of the metal, whereas complex 2, Pd(pmpa)Cl-2 (pmpa = N-(2-pyridylmethylene)-1-pyrenylamine) is a conjugated, planar molecule. Due to this, the oxidation potential and the electronic spectrum of the pyrenyl group of pmpa is significantly influenced by formation of the complex. Both iodine doped complexes show semiconductor properties (2.4 x 10(-4) S cm(-1) for 1 and 1.0 x 10(-4) S cm(-1) for 2). TG-DTG curves for 1 shows a single step decomposition. However, curves for complex 2 show a two-step decomposition, corresponding to the organic ligand pmpa. The iodine doped compounds are more stable than the original complexes. The quantity of doped iodine for 1 and 2 is 23 and 14%, respectively. - M Munakata; LP Wu; M Yamamoto; T KurodaSowa; M Maekawa; S Kawata; S KitagawaJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 4099 (24) 4099 - 4106 0300-9246 1995/12 [Refereed]
Two silver(I) and one copper(ii) complex with 3,5-bis(2-pyridyl) pyrazole (Hbpypz) have been synthesized and their molecular structures determined by X-ray crystallography. In the dinuclear complex [Ag-2(Hbpypz)(4)][ClO4](2) . 2Me(2)CO there are two crystallographically independent monomeric units linked by intramolecular hydrogen bonds. In each unit Hbpypz only uses two of its four nitrogen atoms, acting as a typical bidentate chelate ligand. In the polymeric complex {[Ag(Hbpypz)] ClO4}(infinity) each silver(I) ion is co-ordinated to three nitrogen atoms of two different Hbpypz molecules and each ligand in turn bridges two separate Ag atoms forming an infinite-chain structure of macrocations with non-interacting ClO4- anions. The tetranuclear complex [Cu-4(bpypz)(4)(ClO4)(4)]. 2H(2)O consists of two weakly associated dimeric units coupled via stacking between the pyridine and pyrazole rings with an average spacing of 3.50 Angstrom, which gives rise to charge-transfer absorption bands in the near-UV region. The temperature dependence of the ESR spectrum and magnetic susceptibility indicates the presence of an antiferromagnetic interaction in the system. While Hbpypz is strictly planar in the copper(ii) complex, a non-coplanar conformation is observed in both silver(I) complexes, indicative of the unique co-ordinative versatility of the pyrazole derivative. - M Maekawa; M Munakata; T KurodaSowa; T GotoINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 239 (1-2) 159 - 163 0020-1693 1995/11 [Refereed]
We have prepared the tetranuclear palladium complex [Pd-4(mu-dppm)(4)(mu(4)-S)] (1) capped by a mu(4)-bonded sulfide and crystallographically characterized it. Four Pd atoms are bridged by four dppm ligands to form the rectangular Pd-4 core, which are capped by the mu(4)-bonded sulfide from the side above the Pd-4 plane. It was suggested that the mu(4)-bonded S atom is derived from the cleavage of the C-S bond of diethyldithiocarbamate. Complex 1 has the following crystal data: monoclinic, C2/c, a = 30.503(8), b = 12.061(2), c = 31.686(7) Angstrom, beta = 118.25(2)degrees, V = 10268(8) Angstrom(3), Z = 4, R = 0.051, R(w) = 0.070. - LP Wu; M Yamamoto; T KurodaSowa; M Maekawa; J Fukui; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 239 (1-2) 165 - 169 0020-1693 1995/11 [Refereed]
The crystal and molecular structure of manganese(II) mellitate, [Mn-2{C-6(COO)(6)}(H2O)(6)][Mn(H2O)(6)]. 2H(2)O, has been determined by X-ray structure analysis, The complex crystallizes in the monoclinic system, space group C2/c, with cell constants a = 23.298(3), b = 6.456(3), c = 17.072(2) Angstrom, beta = 101.01(1)degrees and Z = 4. The structure was solved and refined to R = 0.029 (R(w) = 0.036). There are two types of manganese ions in the structure. Mn(1) is situated on a crystallographic center of symmetry and bound to six water molecules while Mn(2) is coordinated octahedrally by three water molecules and three carboxylate oxygen atoms. The major structure feature is that the polyanion formed by Mn(2) ions and the mellitate hexanions with composition of [Mn-2{C-6(COO)(6)}(H2O)(6)](2n-)(n) possesses a two-dimensional layered structure which is linked through a complex three-dimensional hydrogen bonding associated with the Mn(1) cation [Mn(H2O)(6)](2+) and the water of crystallization. Analysis of variable-temperature magnetic susceptibility data (5.0-300 K) shows that the complex displays antiferromagnetic exchange. - LP Wu; M Yamamoto; T KurodaSowa; M Maekawa; J Fukui; M MunakataINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 239 (1-2) 165 - 169 0020-1693 1995/11The crystal and molecular structure of manganese(II) mellitate, [Mn-2{C-6(COO)(6)}(H2O)(6)][Mn(H2O)(6)]. 2H(2)O, has been determined by X-ray structure analysis, The complex crystallizes in the monoclinic system, space group C2/c, with cell constants a = 23.298(3), b = 6.456(3), c = 17.072(2) Angstrom, beta = 101.01(1)degrees and Z = 4. The structure was solved and refined to R = 0.029 (R(w) = 0.036). There are two types of manganese ions in the structure. Mn(1) is situated on a crystallographic center of symmetry and bound to six water molecules while Mn(2) is coordinated octahedrally by three water molecules and three carboxylate oxygen atoms. The major structure feature is that the polyanion formed by Mn(2) ions and the mellitate hexanions with composition of [Mn-2{C-6(COO)(6)}(H2O)(6)](2n-)(n) possesses a two-dimensional layered structure which is linked through a complex three-dimensional hydrogen bonding associated with the Mn(1) cation [Mn(H2O)(6)](2+) and the water of crystallization. Analysis of variable-temperature magnetic susceptibility data (5.0-300 K) shows that the complex displays antiferromagnetic exchange.
- M MUNAKATA; LP WU; M YAMAMOTO; T KURODASOWA; M MAEKAWAJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 3215 (19) 3215 - 3220 0300-9246 1995/10 [Refereed]
The crown thioether silver(I) complexes {[AS{(OH)(2)[16]aneS(4)}]NO3}infinity 1 and {[Ag{(OH)(2) [16]aneS(4)}][O(2)CMe]}infinity 2 and the copper(II) complex [Cu{(OH)(2)[16]aneS(4)}][CIO4](2) 3, where (OH)(2)[16]aneS(4) = 1,5,9,13-tetrathiacyclohexadecane-3,11-diol, have been prepared by reaction of have been prepared by reaction of (OH)(2)[16]aneS(4) with the appropriate metal salt. The two silver structures are not isomorphous. Complex 1 crystallizes in the monoclinic space group C2 with a = 13.500(4). b = 9.178(2), c = 8.695(4) Angstrom, beta = 121.99(2)degrees and Z = 2. Silver(I) is tetrahedrally bound with four thioether groups from four symmetry-related macrocycles and each ligand molecule in turn co-ordinates to four separate silver(I) ions in an exodentate fashion to yield a three-dimensional tetrahedral polymeric network. Complex 2 crystallizes in the orthorhombic space group Pccn with a = 14.121(9), b = 17.203(8), c = 15.940(3) Angstrom and Z = 8. it contains two types of crystallographically different silver(I) ions. both of which are co-ordinated by four sulfur atoms from four symmetry-related macrocycles in a rather distorted-tetrahedral fashion. The silver atoms are in a two-dimensional sheet arrangement interconnected by the macrocycle. Complex 3 crystallizes in the monoclinic space group P2(1)/c with a = 7.820(2), b = 13.853(2), c = 9.627(2) Angstrom, beta = 90.85(2)degrees and Z = 2. The molecule is a discrete monomer in which the tetradentate macrocycle is in the endodentate conformation with four thioether donors in a precisely square-planar arrangement around the copper. - M MAEKAWA; M MUNAKATA; T KURODASOWA; K HACHIYAPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 14 (20-21) 2879 - 2885 0277-5387 1995/09 [Refereed]
Novel trinuclear nickel(0) complexes [Ni-3(L)(cod)(3)] (cod = 1,5-cyclooctadiene) with L = 1,4-bis(trimethylsilyl)-1,3-butadiyne (1) and 1,4-diphenyl-1,3-butadiyne (2) have been prepared and their structures have been crystallographically determined. These trinuclear nickel(0) complexes are the first unsymmetrical trinuclear complexes with the 1,3-butadiynes in the monodentate and mu(2)-eta(2),eta(2)-coordination mode. The acetylenic C-C distance of 1.343(7) and 1.33(2) Angstrom for 1 and 2 in the mu(2)-eta(2),eta(2)-bridging mode is rather larger than that of 1.267(7) and 1.26(2) Angstrom for 1 and 2 in the monodentate mode, indicative of a larger contribution of pi back donation. The weak nu(C=C) frequency was given at 1784 and 1782 cm(-1) for 1 and 2, respectively. - M MAEKAWA; M MUNAKATA; T KURODASOWA; K HACHIYAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 236 (1-2) 181 - 184 0020-1693 1995/08 [Refereed]
A novel trinuclear nickel (0) complex [Ni-3(tmsb)(cod)(3)] (cod = 1,5-cyclooctadiene) with 1,4-bic(trimethylsilyl)-1,3-butadiyne (tmsb) in the monodentate and mu(2)-eta(2),eta(2)-bridging modes has been prepared and characterized crystallographically. The complex is triclinic, P $($) over bar$$ 1, a = 11.947(2), b = 15.407(3), c = 10.213(2) Angstrom, alpha = 96.47(2), beta = 102.32(2), gamma = 107.05(1)degrees, V = 1724.7(6) Angstrom(3), Z = 2, R = 0.046 and R(w) = 0.052. The acetylenic C-C distance of 1.343(7) Angstrom in the mu(2)-eta(2),eta(2)-bridging mode is considerably larger than that (1.267(7) Angstrom) in the monodentate mode. A weak nu (C=C) frequency was found at 1784 cm(-1). - T KURODASOWA; M MUNAKATA; H MATSUDA; S AKIYAMA; M MAEKAWAJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY (13) 2201 - 2208 0300-9246 1995/07 [Refereed]
Four novel copper(I) phenazine (phz) compounds, [{Cu(phz)(NO3)}(infinity)] 1, [{Cu(acr)(2)(NO3)}(2)(phz)-(H2O)] 2 (acr = acridine). [{Cu-2(phz)(PFO3)}(infinity)] 3 and [{[Cu(phz)(MeCN)](2)(C16H10)(PF6)(2)}(infinity)] 4 (C16H10 = pyrene) have been synthesized and their molecular structures and packing have been determined by single-crystal X-ray diffraction methods. The copper atoms in 1 are bridged by phz forming an infinite one-dimensional zigzag chain. These bridging phz molecules have a pi-pi interaction between neighbouring chains forming an infinite columnar stack of phz molecules. The monomer complex, 2, has an infinite columnar stack of metal-free phz and metal-co-ordinated acr. Copper(I) atoms in 3 are bridged by phz and PFO32- alternately. The resulting one-dimensional chains are connected through a tetradentate, asymmetric PFO32- bridge, with pi-pi interaction between the phz molecules forming an infinite two-dimensional sheet structure. The backbone of compound 4 is almost the same as in 1 except that a pyrene molecule is intercalated into every other phz stack in a one-dimensional chain. The electrical conductivity of compound 3 and [{[Cu(phz)(MeCN)](2)(C16H10)(PF6)(2)I-1.3}(infinity)] 5, obtained by iodine doping of compound 4 were 1 x 10(-7.6) and 1 x 10(-4.7) S cm(-1), respectively. The electronic absorption bands of compounds 1, 3 and 4 which appeared around 700 nm are characteristic of copper(I) co-ordination polymers with bridging phz. - XM GAN; M MUNAKATA; T KURODASOWA; M MAEKAWA; M YAMAMOTOPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 14 (12) 1647 - 1651 0277-5387 1995/06 [Refereed]
A new linear coordination polymer composed of copper(I) cations and tetrakis(ethylthio)tetrathiafulvalene (TTC2-TTF) molecules has been synthesized by the reaction of copper(I) perchlorate and TTC2-TTF in acetone under argon. The compound, [Cu(TTC2-TTF)]ClO4, was characterized by spectroscopic and X-ray crystallographic methods. It is a 1:1 metal-ligand complex in which each of the copper(I) ions is tetrahedrally coordinated by four sulphur atoms from the bridging TTC2-TTF molecules to form coordination polymeric chains which are separated from each other by the perchlorate anions in the crystal. The complex was doped with iodine to afford {[Cu(TTC2-TTF)] ClO4}I, which exhibits a conductivity of 6 x 10(-4) S cm(-1) at 25 degrees C for a compacted pellet. - XM GAN; M MUNAKATA; T KURODASOWA; M MAEKAWA; Y MISAKIPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 14 (10) 1343 - 1350 0277-5387 1995/05 [Refereed]
Two copper(I) complexes with tetrakis(ethylthio)tetrathiafulvalene (TTC2-TTF), [(CuCl)(2)TTC2-TTF] (1) and [(CuBr)(2)TTC2-TTF] (2), have been synthesized and characterized by spectroscopic and X-ray crystallographic methods. Both 1 and 2 are neutral 2:1 (metal/ligand) complexes in which each metal ion is coordinated in a distorted tetrahedral geometry to two bridging halide ions and two sulphur atoms from TTC2-TTF. The crystal of 1 has a two-dimensional structure in which TTC2-TTF molecules are connected between novel helical CuCl frames, while the crystal of 2 has a one-dimensional polymeric chain structure. The average Cu-Cl and Cu-S bond lengths are 2.282(2) and 2,405(2) Angstrom in 1 and Cu-Br and Cu-S bond lengths are 2,445(2) and 2,349(1) Angstrom in 2, respectively. Compounds 1 and 2 were doped with iodine to afford [(CuCl)(2)TTC2-TTF]I (3) and [(CuBr)(2)TTC2-TTF]I (4) which exhibit electrical conductivities of 6 x 10(-7) and 3 x 10(-7) S cm(-1), respectively, at 25 degrees C for compacted pellets. - M MAEKAWA; M MUNAKATA; T KURODASOWA; K HACHIYAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 233 (1-2) 1 - 4 0020-1693 1995/05 [Refereed]
The cleavage of the central C-C bond of 1,4-diphenyl-1,3-butadiyne (dpbd) was caused by the reaction of [Ni(cod)(2)](cod=1,5-cyclooctadiene), dpbd and bis(diphenylphosphino)methane (dppm) to form the triangular trinickel complex [Ni-3(mu-dppm)(3) (mu(3)-eta(1)-C=CPh)(2)] (2) bicapped by two resulting phenylacetylides. We have determined the crystal structure and properties of complex 2. The complex is monoclinic, P2(1)/m, a = 14.227(6), b = 21.651(5), c = 14.497(2) Angstrom, beta = 97.76(3)degrees, V = 4425(2) Angstrom(3), Z=2,R=0.079 and R(W)=0.116. The C=C frequency of the coordinating acetylide was observed at 1933 cm(-1). - M MUNAKATA; T KURODASOWA; M MAEKAWA; A HIROTA; S KITAGAWAINORGANIC CHEMISTRY AMER CHEMICAL SOC 34 (10) 2705 - 2710 0020-1669 1995/05 [Refereed]
Three copper (I) complexes with tetrakis(methylthio)tetrathiafulvalene (TMT-TTF), [(Cu-2(mu-X)(2)(mu-TMT-TTF)](infinity) (X = Cl, 1; X = Br, 2; and X = I, 3) were synthesized and their molecular structures and packing were determined by using single crystal X-ray diffraction methods. 1 is 2D sheet composed of TMT-TTF molecules arranged between new zigzag frames of CuCl and 3D structure is formed through S ... S contacts of 3.53 and 3.63 Angstrom between the 2D sheets. 2 has a 2D structure in which TMT-TTF molecules are connected between novel helical frames of CuBr and the S ... S contacts of 3.68 Angstrom exist between the neighboring molecules. The methyl thioether groups of TMT-TTF in 3 are coordinated to the coppers of rhomboid Cu2I2 to give linear chains. The black I-2-doped compounds 1-3 show a new broad band at ca 880 nm indicative of the oxidation of TMT-TTF molecules and gave electric conductivities of 10(-3.6), 10(-2.1), and 10(-1.7) S cm(-1), respectively. Crystal data: 1, monoclinic P2(1)/n, a = 6.657(8) Angstrom, b = 6.23(1) Angstrom, c = 24.067(8) Angstrom, beta = 91.77(7)degrees, V = 998(2) Angstrom(3), Z = 4, 1913 reflections, R = 0.028; 2, monoclinic C2/c; a = 15.443(3) Angstrom, b = 4.906(4) Angstrom, c = 26.686(1) Angstrom, beta = 96.36(1)degrees, V = 2009(2) Angstrom(3), Z = 8, 1304 reflections, R = 0.037; 3, monoclinic C2/m, a = 7.921(3) Angstrom, b = 13.266(6) Angstrom, c = 10.498(6) Angstrom, beta = 107.79(4)degrees, V = 1052(2) Angstrom(3), Z = 8, 1072 reflections, R = 0.027. - T KURODASOWA; M MUNAKATA; M MIYAZAKI; M MAEKAWAPOLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 14 (8) 1003 - 1009 0277-5387 1995/04 [Refereed]
Methylisothiocyanate, MeN=C=S, in ethanol reacted with copper(I) giving a tetranuclear complex [Cu{mu(3)-SC(=NMe)(OEt)}](4) (1). Similar reaction of allylisothiocyanate, CH2=CHCH2N=C=S, and copper(I) in methanol gave a hexanuclear complex, [Cu{mu(3)-SC(=NC3H5)(OMe)}](6) (2). They show tetrahedral Cu-4 and octahedral Cu-6 cores, respectively. There are two structural similarities in both complexes : (i) a thiolato moiety [-N=C(S-)-] which bridges three copper atoms with a monodentate nitrogen atom and a bridging sulphur atom and (ii) a trigonal planar geometry for copper(I) coordinated by one nitrogen atom and two sulphur atoms. Each iminomethanethiolato ligand is formed in situ in solvent. H-1 NMR shows the reaction is initiated by a coordination of an isothiocyanate to copper(I). - M MAEKAWA; M MUNAKATA; T KURODASOWA; K HACHIYAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 232 (1-2) 231 - 234 0020-1693 1995/04 [Refereed]
A novel nickel(0) ethylene complex [Ni(4,4'-bpy)(C2H4)(2)](2)[Ni-2(4,4'-bpy)(C2H4)(4) (1) (4,4'-bpy = 4,4'-bipyridine) which includes two species of mono- and dinuclear nickel(0) ethylene complex in a unit cell has been prepared and characterized crystallographically. Complex 1 is triclinic, space group P (1) over bar, a = 10.543(4), b = 12.546(4), c = 9.190(4) Angstrom, alpha = 109.64(3), beta = 98.57(4), gamma = 90.98(3)degrees, V = 1129.1(8) Angstrom(3), Z = 1, R = 0.037 and R(w) = 0.039. Each of three nickel atoms provide the trigonal geometry due to the coordination of the nitrogen atom of 4,4'-bpy and two ethylene molecules. Elongation of the C=C distance by similar to 0.03 Angstrom is smaller than that of the usual three-coordinate nickel(0) complexes with alkenes, suggesting that the contribution of pi back-donation is considerably weaker. - M MAEKAWA; M MUNAKATA; T KURODASOWA; K HACHIYAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 231 (1-2) 213 - 216 0020-1693 1995/03 [Refereed]
A novel tetranuclear nickel(0) complex [Ni-4(dpbd)(cod)4] (cod=1,5-cyclooctadiene) with 1,4-diphenylbutadiyne (dpbd) ln the eta(2),eta(2)-bridging mode has been prepared and then characterized crystallographically. Two nickel atoms are bridged by every C drop C bond of dpbd in the eta(2),eta(2)-bridging mode to give the tetranuclear structure. Each of four nickel atoms is also bonded to two C=C bonds of cod, providing a distorted tetrahedral geometry. The acetylenic C-C distance of the bridging dpbd is 1.35(1) Angstrom. The elongation of the C drop C distance indicates the contribution of the large pi back donation from nickel to dpbd. It was also found that the acetylenic C-C distances of the Ni(0) diyne complexes in the eta(2),eta(2)-bridging mode are longer than those in the monodentate mode. - M MAEKAWA; M MUNAKATA; T KURODASOWA; K HACHIYAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 230 (1-2) 249 - 252 0020-1693 1995/03 [Refereed]
A novel hexanickel(II) complex [Ni-6(NCCHCH2CH2CHCN)(6)] (2) with 1,4-dicyanobutane-1,4-diyl (L) which was produced by the metal-induced dimerization of acrylonitrile (AN) has been isolated and the structure has been determined crystallographically. Complex 2 is triclinic, space group P (1) over bar, a=9.998(2), b=10.363(2), c=9.960(3) Angstrom, alpha=110.35(2), beta=103.46(2), gamma=88.97(2)degrees U=938.7(4) Angstrom(3), Z=1, R=0.029 and R(w)=0.034. Each nickel atom is coordinated by two carbon atoms of L and two nitrogen atoms of the cyano group of two other L, providing a square-planar geometry. The six nickel atoms are bridged by the cyano group and carbon atom to form the slightly distorted octahedral Ni-6 core. - S KITAGAWA; M KONDO; S KAWATA; S WADA; M MAEKAWA; M MUNAKATAINORGANIC CHEMISTRY AMER CHEMICAL SOC 34 (6) 1455 - 1465 0020-1669 1995/03 [Refereed]
New binuclear macrocyclic systems of 1,6-bis(diphenylphosphino)hexane (dpph) and 1,4-bis(diphenylphosphino)-butane (dppb), [Cu-2(dppb)(2)(ClO4)(2)] (2), [Cu-2(dPPh)(2)(mu-X)(2)] (X = ClO4 (3), NO3 (4), PF2O2 (5), CH3CO2 (7), C2H5CO2 (8)), and [Ag-2(dpph)(2)(mu-ClO4)(2)] (6), have been synthesized and structurally characterized. A mononuclear copper(I) complex, [Cu-2(dppp)(2)]ClO4 (1) (dppp = 1,3-bis(diphenylphosphino)propane), was also prepared. The crystals of 1-6 are all triclinic, space group P $($) over bar$$ 1, with Z = 1 (2) and 2 (1, 3-5). Dimensions of the unit cells: 1, a = 12.221(6) Angstrom, b = 18.425(7) Angstrom, c = 11.981(7) Angstrom, alpha = 96.19(4)degrees, beta = 102.42(4)degrees, gamma = 70.57(4)degrees; 2, a = 11.978(8) Angstrom, b = 12.755(8) Angstrom, c = 19.372(4) Angstrom, alpha = 97.83(5)degrees, beta = 111.24(4)degrees, gamma = 64.85(5)degrees; 3, a = 12.154(7) Angstrom, b = 12.728(5) Angstrom, c = 10.007(7) Angstrom, alpha = 92.67(4)degrees; beta = 101.57(4)degrees, gamma = 101.56(6)degrees; 4, a = 15.421(3) Angstrom, b = 18.354(4) Angstrom, c = 10.066(4) Angstrom, alpha = 90.23(3)degrees, beta = 97.06(2)degrees, gamma = 89.27(2)degrees; 5, a = 12.060(2) Angstrom, b = 12.808(1) Angstrom, c = 10.120(1) Angstrom, alpha = 86.134(7)degrees, beta = 101.299(9)degrees, gamma = 102.367(8)degrees; 6, a = 12.035(7) Angstrom, b = 12.820(6) Angstrom, c = 10.240(5) Angstrom, alpha = 92.76(4)degrees, beta = 101.49(4)degrees, gamma = 101.39(4)degrees. For complexes of 3-5 each copper atom shares a tetrahedral geometry with the P2O2 donor set, giving a molecular structure having two rings: the common outer large ring of CuP(CH2)(6)PCuP(CH2)(6)P is composed of copper atoms and the bridging diphosphine ligands while the inner ring is CuOXOCuOXO (X = Cl, N, P) for 3-5, respectively. The distances of Cu-O fall within the shortest range for copper(I) complexes of each anion, indicating that copper-anion binding is strong even for anions having weak coordination ability. The size of cavity for the anion trap is estimated as the distance L between the two metal atoms in a molecule. The L values are 4.99-5.22 Angstrom for 3-5. Compound 1 shows a typical mononuclear structure with chelating dppp, while 2 gives a binuclear geometry, [Cu-2(mu-dppb)(2)(ClO4)(2)], with terminally coordinated ClO4 anions and a single macrocycle (L = 4.63 Angstrom) of CuP(CH2)(4)PCuP(CH2)(4)P. The ClO4- ion is prevented from bridging coordination, and this is accounted for by the ring size and spatial blocking of the phenyl groups of dppb. On this basis, the ligand having six methylene groups provides a cavity able to include anions such as tetrahedral ClO4- and Y-shaped NO3-. By P-31 NMR, the mononuclear and binuclear copper(I) compounds in solution were also examined, and their exchange processes are discussed. The silver compound (6) as a structural analog of 3 also affords the double ring, but the Ag-O distance is not so sufficiently short that the silver atom binds ClO4 as strongly as copper does. Other compounds with CH3CO2- (7), C2H5CO28, and VO3- (9) were also examined by IR and V-51 NMR spectroscopy. By using the copper(I) ion and diphosphine, we have succeeded in building large macrocyclic systems, where various small molecules or anions are included, proposing a new host-guest chemistry. - Takayoshi Kuroda-Sowa; Megumu Munakata; Hajime Matsuda; Shin-Ichi Akiyama; Masahiko MaekawaJournal of the Chemical Society, Dalton Transactions 2201 (13) 2201 - 2208 1472-7773 1995 [Refereed]
Four novel copper(I) phenazine (phz) compounds, [{Cu(phz)(NO3)}∞] 1, [{Cu(acr)2(NO3)}2(phz)(H2O)] 2 (acr = acridine), [{Cu2(phz)(PFO3)}∞] 3 and [{[Cu(phz)(MeCN)]2(C16H10)(PF6) 2}∞] 4 (C16H10 = pyrene) have been synthesized and their molecular structures and packing have been determined by single-crystal X-ray diffraction methods. The copper atoms in 1 are bridged by phz forming an infinite one-dimensional zigzag chain. These bridging phz molecules have a π-π interaction between neighbouring chains forming an infinite columnar stack of phz molecules. The monomer complex, 2, has an infinite columnar stack of metal-free phz and metal-co-ordinated acr. Copper(I) atoms in 3 are bridged by phz and PFO32- alternately. The resulting one-dimensional chains are connected through a tetradentate, asymmetric PFO32- bridge, with π-π interaction between the phz molecules forming an infinite two-dimensional sheet structure. The backbone of compound 4 is almost the same as in 1 except that a pyrene molecule is intercalated into every other phz stack in a one-dimensional chain. The electrical conductivity of compound 3 and [{[Cu(phz)(MeCN)]2(C16H10)(PF6) 2I1.3}∞] 5, obtained by iodine doping of compound 4 were 1 × 10-7.6 and 1 × 10-4.7 S cm-1, respectively. The electronic absorption bands of compounds 1, 3 and 4 which appeared around 700 nm are characteristic of copper(I) co-ordination polymers with bridging phz. - Megumu Munakata; Liang Ping Wu; Mikiko Yamamoto; Takayoshi Kuroda-Sowa; Masahiko MaekawaJournal of the Chemical Society, Dalton Transactions (19) 3215 - 3220 1472-7773 1995 [Refereed]
The crown thioether silver(I) complexes {[Ag{(OH)2[16]aneS4}]NO3}∞ 1 and {[Ag{(OH)2[16]aneS4}][O2CMe]}∞ 2 and the copper(II) complex [Cu{(OH)2[16]aneS4}][ClO4]2 3, where (OH)2[16]aneS4 = 1,5,9,13-tetrathiacyclohexadecane-3,11-diol, have been prepared by reaction of (OH)2[16]aneS4 with the appropriate metal salt. The two silver structures are not isomorphous. Complex 1 crystallizes in the monoclinic space group C2 with a = 13.500(4), b = 9.178(2), c = 8.695(4) Å, β = 121.99(2)°and Z = 2. Silver(I) is tetrahedrally bound with four thioether group from four symmetry-related macrocycles and each ligand molecule in turn co-ordinates to four separate silver(I) ions in an exodentate fashion to yield a three-dimensional tetrahedral polymeric network. Complex 2 crystallizes in the orthorhombic space group Pccn with a = 14.121(9), b = 17.203(8), c = 15.940(3) Å and Z = 8. It contains two types of crystallographically different silver(I) ions, both of which are co-ordinated by four sulfur atoms from four symmetry-related macrocycles in a rather distorted-tetrahedral fashion. The silver atoms are in a two-dimensional sheet arrangement interconnected by the macrocycle. Complex 3 crystallizes in the monoclinic space group P21/c with a = 7.820(2), b = 13.853(2), c = 9.627(2) Å, β = 90.85(2)°and Z = 2. The molecule is a discrete monomer in which the tetradentate macrocycle is in the endodentate conformation with four thioether donors in a precisely square-planar arrangement around the copper. - Megumu Munakata; Liang Ping Wu; Mikiko Yamamoto; Takayoshi Kuroda-Sowa; Masahiko Maekawa; Satoshi Kawata; Susumu KitagawaJournal of the Chemical Society, Dalton Transactions (24) 4099 - 4106 1472-7773 1995 [Refereed]
Two silver(I) and one copper(II) complex with 3,5-bis(2-pyridyl)pyrazole (Hbpypz) have been synthesized and their molecular structures determined by X-ray crystallography. In the dinuclear complex [Ag2(Hbpypz)4][CIO4] 2·2Me2CO there are two crystallographically independent monomeric units linked by intramolecular hydrogen bonds. In each unit Hbpypz only uses two of its four nitrogen atoms, acting as a typical bidentate chelate ligand. In the polymeric complex {[Ag(Hbpypz)]CIO4}∞ each silver(I) ion is co-ordinated to three nitrogen atoms of two different Hbpypz molecules and each ligand in turn bridges two spearate Ag atoms forming an infinite-chain structure of macrocations with non-interacting CIO4- anions. The tetranuclear complex [Cu4(bpypz)4(CIO4)4]·2H 2O consists of two weakly associated dimeric units coupled via intramolecular stacking between the pyridine and pyrazole rings with an average spacing of 3.50 Å, which gives rise to charge-transfer absorption bands in the near-UV region. The temperature dependence of the ESR spectrum and magnetic susceptibility indicates the presence of an antiferromagnetic interaction in the system. While Hbpypz is strictly planar in the copper(II) complex, a non-coplanar conformation is observed in both silver(I) complexes, indicative of the unique co-ordinative versatility of the pyrazole derivative. - M MAEKAWA; M MUNAKATA; T KURODASOWA; K HACHIYAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 227 (1) 137 - 143 0020-1693 1994/12 [Refereed]
Three nickel(0) acrylonitrile complexes with a bidentate N-donor ligand, [Ni(biL)(AN)(2)] (bit = 4,4'-dimethyl-2,2'-bipyridine (Me(2)bpy); 1, 2,2'-dipyridylamine (dpa); 2, 2,2'-pyridylbenzimidazole (pbi); 3, AN=acrylonitrile), have been prepared and characterized. The crystal structures have been determined by X-ray single-crystal diffraction. Complex 1 is triclinic, space group P1, with a=10.279(2), b=11.071(1), c=7.5409(9) Angstrom, alpha=95.68(1), beta=99.26(1), gamma=85.03(1)degrees, U=840.6(2) Angstrom(3), Z=2, R=0.032 and R(W)=0.038. The nickel atom of 1 is coordinated by two N atoms of Me(2)bpy and the C=C moiety of two AN molecules, providing a distorted tetrahedral geometry. Complexes 2 and 3 have the following crystal data: 2, monoclinic space group P2(1)/n, a=8.755(4), b=13.713(2), c=12.740(2) Angstrom, beta=92.94(2)degrees, U=1527.5(8) Angstrom(3), Z=4, R=0.038 and R(W)=0.039; 3, monoclinic space group P2(1)/n, a=12.829(3), b= 8.068(1), c=17.024(2) Angstrom, beta=107.62(1)degrees, U=1679.5(5) Angstrom(3), Z=4, R=0.033 and R(W)=0.036. The geometries of 2 and 3 are similar to that of 1 except for the dihedral angles. The average Ni-N distance is 2.004, 2.034 and 2.045 Angstrom for 1, 2 and 3, respectively. The average C=C distance of AN is 1.402(2), 1.403(6) and 1.409(4) Angstrom for 1, 2 and 3, respectively. These C=C distances are rather longer than that of free AN (1.343 Angstrom), indicating contribution from a large pi back-donation. The IR and H-1 NMR results also support the presence of pi back-donation. - M MAEKAWA; M MUNAKATA; T KURODASOWA; M MOTOKAWAANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 10 (6) 977 - 978 0910-6340 1994/12 [Refereed]
- M MAEKAWA; M MUNAKATA; T KURODASOWAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 227 (1) 149 - 151 0020-1693 1994/12 [Refereed]
The alkylation of 2-vinylpyridine (2-vpy) was produced by the reaction of [Ni(acac)(2)] (acac=acetylacetone), 2-vpy and AlEt(3) to isolate the dinickel(II) complexes with 1-pyridylbutanate (L). Two nickel atoms are bridged by the N atom and carbonate atom of L to form the binuclear complex. Each Ni atom is also coordinated by two O atoms of acetylacetonate, providing the square-planar geometry. The bridging mode of L is head-to-tail coordination, and the eight-membered ring Ni2N2C4 framework has a rare staggered conformation. - XM GAN; M MUNAKATA; T KURODASOWA; M MAEKAWABULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 67 (11) 3009 - 3011 0009-2673 1994/11 [Refereed]
The title complex was synthesized by the reaction of copper(I) iodide and tetrakis(ethylthio)-tetrathiafulvalene (TTC2-TTF) in acetonitrile under argon atmosphere. The new compound, [(CuI)(2)TTC2-TTF], crystallizes in the monoclinic system, space group P2(1)/m with unit-cell dimensions a=9.843(2), b=12.946 (2), c=10.079(1) Angstrom, beta=99.91(1)degrees, V=1265.2(4) Angstrom(3), and Z=2. It is a neutral 2:1 (metal/ligand) complex in which each metal ion is tetrahedrally coordinated by two bridging iodide ions and two sulfur atoms from TTC2-TTF to form coordination polymeric chains. The average Cu-I and Cu-S bond lengths are 2.601 and 2.369 Angstrom, respectively. The complex was doped with iodine to afford [(CuI)(2)TTC2-TTF]I-1.5 which exhibits a conductivity of 2x10(-3) Scm(-1) at 25 degrees C for a compacted pellet. - M MUNAKATA; J DAI; M MAEKAWA; KS TAKAYOSHI; JT FUKUIJOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY 2331 (20) 2331 - 2332 0022-4936 1994/10 [Refereed]
The first copper(i) complex with aminopyrene [Cu(apyr)3]ClO4.MeOH is synthesized and characterized crystallographically; the most remarkable feature of the compound is its 2D structure connected through intra- and inter-molecular stacking of the aromatic rings. - M MUNAKATA; T KURODASOWA; M MAEKAWA; A HONDA; S KITAGAWAJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 2771 (19) 2771 - 2775 0300-9246 1994/10 [Refereed]
Three copper(i) complexes with phenazine (phz), [{Cu2(mu-X)2(mu-phz))infinity] (X = 11, Br 2 or Cl 3) were synthesized and their molecular structures and packing determined by single-crystal X-ray diffraction methods. The copper atoms of the Cu2I2 rhomboid in 1 are bridged by phz molecules to give an infinite linear chain and the phz molecules overlap between the infinite chains with an interplanar spacing of 3.46 angstrom. Compounds 2 and 3 have two-dimensional sheets of hanging phz molecules between polymeric stair frameworks of CuBr and CuCl, respectively. The interplanar spacings of adjacent phz molecules for 2 and 3 are 3.40 and 3.36 angstrom, respectively. All three complexes exhibit an absorption band at about 710 nm characteristic of copper(i) co-ordination polymers with phz. - T KURODASOWA; M MUNAKATA; M MIYAZAKI; M MAEKAWAACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS MUNKSGAARD INT PUBL LTD 50 1026 - 1028 0108-2701 1994/07 [Refereed]
Tetrakis[mu3-ethoxy(N-methylimino)methane-thiolato]-1kappaN,2:4kappa2S,2kappaN, 1:3kappa2S;3kappaN, 1:4kappa2S;4kappaN,-2:3kappa2S-tetracopper, [Cu2(C4H8NOS)2]2, contains a tetrahedral Cu, core surrounded by four effectively tridentate ethoxy(N-methylimino)methanethiolato (or O-ethyl N-methylcarbonimidothioato) ligands, CH3N=C(OC2H5)S-. Each Cu atom is coordinated by an N atom and two S atoms in a trigonal planar environment. There are two kinds of Cu(I)-Cu(I) distances (average 2.616 and 2.845 angstrom), resulting in a butterfly structure for the Cu4 core. - M MUNAKATA; T KURODASOWA; M MAEKAWA; M NAKAMURA; S AKIYAMA; S KITAGAWAINORGANIC CHEMISTRY AMER CHEMICAL SOC 33 (7) 1284 - 1291 0020-1669 1994/03 [Refereed]
Three Cu(I) complexes and one Ag(I) complex with 2,1,3-benzothiadiazole (btd) and Cu(I) complexes with 5,6-benzopyrimidine (bpm), {[Cu2(btd)3(ClO4)](ClO6).2thF}infinity (1), [Cu(btd)(HPO3F)]infinity (2), [Cu(btd)(NO3)]infinity (3), {[Ag(btd)](ClO4)}infinity (4), and {[Cu2(bpm)2(C2H4)(Me2CO)](ClO4)2]infinity (5), were synthesized; their molecular structures and packing were determined by using single-crystal X-ray diffraction methods. Complex 1 is a 2D structure composed of six-membered rings of coppers interconnected by six btds, [Cu6(btd)6]6+. The coppers in the 2D sheet approximately lie in the same plane. The 2D sheet composed of the six-membered rings [Cu6(btd)4(HPO3F)4]2+ is still maintained in 2 although HPO3F- anions take part in the interconnecting as well as btd molecules. The Cu framework of the six-membered rings of coppers interconnected by btd and NO3-, [Cu6(btd)4(NO3)4]2+, in the 2D complex 3 is in a chair form and makes it possible to stack btd molecules within and between the 2D sheets, forming a layered structure similar to that of graphite. Ag atoms in 4 are coordinated to two nitrogen atoms of interconnecting btd molecules to give a linear chain, and the btd molecules partially overlap between the chains. Cu atoms in 5 are N-coordinated to the interconnecting bpm molecules to form a 1D compound. The roles of metal ion, ligand, and counteranion have been discussed in the construction of 2D sheets with the six-membered rings of metal ions interconnected by aromatic compounds and a layered structure composed of the 2D sheets. Crystal data: 1, monoclinic P2(1)/a, a = 17.817(2) angstrom, b = 11.220(2) angstrom, c = 18.186(3) angstrom, beta = 110.361(8)degrees, V = 3408(2) angstrom3, Z = 4, 4272 reflections, R = 0.051; 2, monoclinic P2(1)/a, a = 16.576(2) angstrom, b = 10.711(2) angstrom, c = 11.001(1) angstrom, beta = 101.29(1)degrees, V = 1915.4(8) angstrom3, Z = 4,2645 reflections, R = 0.045; 3, triclinic P1BAR, a = 9.757(2) angstrom, b = 11.593(3) angstrom, c = 8.124(2) angstrom, alpha = 110.23(2)degrees, beta = 101.20(2)degrees, gamma = 74.98(2)degrees, V = 827.1(3) angstrom3, Z = 2,1767 reflections, R = 0.030; 4, monoclinic C2/c, a = 13.483(5) angstrom, b = 20.384(3) angstrom, c = 7.278(7) angstrom, beta = 98.90(5)degrees, V = 1976(2) angstrom3, Z = 8, 2309 reflections, R = 0.045; 5, monoclinic C2/c, a = 11.099(2) angstrom, b = 19.106(2) angstrom, c = 12.558(2) angstrom, beta = 104.10(1)degrees, V = 2582.8(5) angstrom3, Z = 8, 2113 reflections, R = 0.052. - M MAEKAWA; M MUNAKATA; T KURODASOWA; Y NOZAKAJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 603 (4) 603 - 607 0300-9246 1994/02 [Refereed]
Novel di- and tetra-copper(I) complexes of pyridazine (pydz) have been prepared and determined crystallographically. The yellow crystals of the dicopper(I) complex, [Cu2(pydz)3(MeCN)2] [PF6]2, 1 are monoclinic, space group C2/c, with a = 21.720(6), b = 8.803(8), c = 15.778(6) angstrom, beta = 114.33(2)degrees, Z = 4, R = 0.056 and R' = 0.072. Two copper atoms are triply bridged by three pydz ligands to give a binuclear structure, in which the Cu ... Cu separation is 3.065(2) angstrom. Each Cu atom is co-ordinated by three N atoms of three pydz molecules and one N atom of a MeCN molecule, providing a distorted tetrahedral environment. The orange crystals of the tetracopper(I) complex, [Cu4(pydz)6][ClO4]4.2MeCO 2 are monoclinic, space group P2(1)/a, with a = 16.368(2), b = 13.860(2), c = 10.542(2) angstrom, beta = 102.25(1)degrees, Z = 2, R = 0.050 and R' = 0.058. Two Cu atoms are bridged by four N atoms of two pydz molecules to form a six-membered N2Cu2N2 framework. Furthermore, two parallel NCuN2 frameworks are linked by two different pydz molecules to give a tetranuclear structure. Four Cu atoms are coplanar and each Cu atom is in a trigonal-square environment. The shortest Cu ... Cu separations are 3.096(1) and 3.264(1) angstrom. If in the preparation of 2 ethylene or CO atmospheres are employed instead of Ar, copper(I) pydz adducts with C2H4 or CO are obtained which have been characterized by IR and H-1 NMR spectroscopy. The former shows nu(c=c) of C2H4 at 1541 cm-1; the latter shows nu(co) at 2108 cm-1. - Masahiko Maekawa; Megumu Munakata; Takayoshi Kuroda-Sowa; Youichi NozakaJournal of the Chemical Society, Dalton Transactions (4) 603 - 607 1472-7773 1994 [Refereed]
Novel di- and tetra-copper(I) complexes of pyridazine (pydz) have been prepared and determined crystallographically. The yellow crystals of the dicopper(I) complex, [Cu2(pydz)3(MeCN)2][PF6]2 1 are monoclinic, space group C2/c, with a = 21.720(6), b = 8.803(8), c = 15.778(6) Å, β = 114.33(2)°, Z = 4, R = 0.056 and R′ = 0.072. Two copper atoms are triply bridged by three pydz ligands to give a binuclear structure, in which the Cu ⋯ Cu separation is 3.065(2) Å. Each Cu atom is co-ordinated by three N atoms of three pydz molecules and one N atom of a MeCN molecule, providing a distorted tetrahedral environment. The orange crystals of the tetracopper(I) complex, [Cu4(pydz)6] [ClO4]4·2Me2CO 2 are monoclinic, space group P21/a, with a = 16.368(2), b = 13.860(2), c = 10.542(2) Å, β = 102.25(1)°, Z = 2, R = 0.050 and R′ = 0.058. Two Cu atoms are bridged by four N atoms of two pydz molecules to form a six-membered N2Cu2N2 framework. Furthermore, two parallel N2Cu2N2 frameworks are linked by two different pydz molecules to give a tetranuclear structure. Four Cu atoms are coplanar and each Cu atom is in a trigonal-square environment. The shortest Cu ⋯ Cu separations are 3.096(1) and 3.264(1) Å. If in the preparation of 2 ethylene or CO atmospheres are employed instead of Ar, copper(I) pydz adducts with C2H4 or CO are obtained which have been characterized by IR and 1H NMR spectroscopy. The former shows vC=C of C2H4 at 1541 cm-1 the latter shows νco at 2108 cm-1. - Megumu Munakata; Takayoshi Kuroda-Sowa; Masahiko Maekawa; Akihiro Honda; Susumu KitagawaJournal of the Chemical Society, Dalton Transactions (19) 2771 - 2775 1472-7773 1994 [Refereed]
Three copper(I) complexes with phenazine (phz), [{Cu2(μ-X)2(μ-phz)}∞] (X = I 1, Br 2 or Cl 3) were synthesized and their molecular structures and packing determined by single-crystal X-ray diffraction methods. The copper atoms of the Cu2I2 rhomboid in 1 are bridged by phz molecules to give an infinite linear chain and the phz molecules overlap between the infinite chains with an interplanar spacing of 3.46 Å. Compounds 2 and 3 have two-dimensional sheets of hanging phz molecules between polymeric stair frameworks of CuBr and CuCl, respectively. The interplanar spacings of adjacent phz molecules for 2 and 3 are 3.40 and 3.36 Å, respectively. All three complexes exhibit an absorption band at about 710 nm characteristic of copper(I) co-ordination polymers with phz. - M MAEKAWA; S KITAGAWA; Y NOZAKA; M MUNAKATA; T KURODASOWAANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 9 (6) 887 - 888 0910-6340 1993/12 [Refereed]
- M MAEKAWA; M MUNAKATA; T KURODA; Y NOZAKAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 208 (2) 243 - 244 0020-1693 1993/06 [Refereed]
A novel trinuclear nickel(II) complex, [Ni3(3,5-Me2pz)4(acac)2] (3,5-Me2pz = 3,5-dimethylpyrazolate, acac = acetylacetone), has been prepared and characterized crystallographically. The terminal and center nickel atoms are bridged by two 3,5-Me2pz, providing a trinuclear structure. The geometry of each nickel atom is square planar (SqPl) and these planes provide the zigzag mode. This is the first crystal structure of a trinuclear nickel(II) complex having a (SqPl)-(SqPl)-(SqPl) coordination arrangement. The Ni(l) ... Ni(2) separation is 3.1972(5) angstrom and the Ni(II) complex has no attractive Ni(II)... Ni(II) interaction. The averaged Ni-N distance of 3,5-Me2Pz and Ni-O distance of acac are 1.876 and 1.850 angstrom, respectively. - M MUNAKATA; S KITAGAWA; N UJIMARU; M NAKAMURA; M MAEKAWA; H MATSUDAINORGANIC CHEMISTRY AMER CHEMICAL SOC 32 (6) 826 - 832 0020-1669 1993/03 [Refereed]
Three copper(I) and two silver(I) complexes with phenazine (phz), [Cu2(phz)3(MeOH)2](phz)(PF6)2 (1), [Cu(phz)2(H2O)]ClO4(2), [Cu(phz)2(NO3)] (3), {[Ag(phz)]ClO4}infinity (4), and [Ag2(phz)(NO3)2]infinity (5), were synthesized, and their molecular structures and packings were determined by using single-crystal X-ray diffraction methods. 1 is composed of infinite stacks of alternating metal-free phz molecules and the dicopper complex cations [Cu2(PhZ)3(MeOH)2]2+ and gives a CT band from the latter to the former at 710 nm indicative of a donor-acceptor complex. One phz in 2 and an opposite phz in another molecule alternatively stacked to give infinite columns. The copper of 3 is coordinated to NO3- and phz in a tetrahedral geometry. The molecular packing of 4 is composed of infinite linear chains of -Ag-phz-Ag-phz- along the a axis and a pi-pi interaction of the phz molecules between the chains along the c axis. The 3D complex 5 is made of a 2D framework of six-membered rings of silvers, a weak Ag-O bonding, and a pi-pi interaction of phz molecules between the 2D sheets. Solvent and counteranion as well as metal ion have been shown to play an important role in the molecular packing of metal complexes with phz because they are coordinated to metal ion to change the complex structure. Crystal data: 1, triclinic P1BAR-, alpha = 13.008(2) angstrom, b = 13.694(2) angstrom, c = 7.789(1) angstrom, a = 102.50(1)-degrees, beta = 105.02(1)-degrees, gamma = 72.81 (1)-degrees, V - 1256.4(3) angstrom3, Z = 2, 3568 reflections, R = 0.069; 2, triclinic P1BAR, a = 10.811(4) angstrom, b = 12.576(3) angstrom, c = 8.992(1) angstrom, alpha = 105.20(1)-degrees, beta = 92.59(2)-degrees, gamma = 110.90(5)-degrees, V = 1089.0(5) angstrom3, Z = 2, 3579 reflections, R = 0.045; 3, monoclinic P2(1)/n, a = 10.686(2) angstrom, b = 26.937(1) angstrom, c = 7.219(2) angstrom, beta = 102.18(1)-degrees, V = 2031(1) angstrom3, Z = 4, 2256 reflections, R = 0.035; 4, triclinic P1BAR, a = 7.2044(6) angstrom, b = 12.943(2) angstrom, c = 7.138(2) angstrom, a = 98.64(2)-degrees, beta = 98.70(1)-degrees, gamma = 89.92-degrees, V = 650.3(2) angstrom3, Z = 2, 2275 reflections, R = 0.034; 5, monoclinic P2(1)/n, a = 5.007(3) angstrom, b = 19.454(2) angstrom, c = 7.248(6) angstrom, beta = 102.18(1)-degrees, V = 685.0(7) angstrom3, Z = 4, 2256 reflections, R = 0.035. - M MAEKAWA; S KITAGAWA; T TANIMURA; M MUNAKATA; T YONEZAWAANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 8 (6) 899 - 900 0910-6340 1992/12 [Refereed]
- M MUNAKATA; S KITAGAWA; KAWADA, I; M MAEKAWA; H SHIMONOJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ROYAL SOC CHEMISTRY 2225 (14) 2225 - 2230 0300-9246 1992/07 [Refereed]
Ternary copper(i) complexes with alkynes and 1,10-phenanthroline (phen) have been prepared and characterized by their formation constants, IR spectra, H-1 and C-13 NMR spectra, The structures of three complexes, [Cu(phen)(HC=CR)]ClO4 (R = H 1, Ph 2 or CO2Et 3) have been determined using single-crystal X-ray methods. Each copper atom in all three complexes is co-ordinated to two nitrogen atoms of phen and an alkyne molecule in a trigonal-planar arrangement. The alkyne is sideways bonded onto the copper atom. The C=C bond distances of 1.190(7) (1), 1.218(13) (2) and 1.193(10) angstrom (3) are slightly longer than those of the free alkynes and indicate that pi-back donation from copper to the alkyne is weak. The reduction of the C=C stretching frequency for metal-alkyne complexes is correlated to the acetylenic bend-back angles and the lengthening of the C=C distance of the alkyne upon co-ordination. The copper-carbon and -nitrogen distances for 1 and 2 are essentially the same as those for the corresponding olefin complexes. - Megumu Munakata; Susumu Kitagawa; Ichiro Kawada; Masahiko Maekawa; Hisao ShimonoJournal of the Chemical Society, Dalton Transactions (14) 2225 - 2230 1472-7773 1992 [Refereed]
Ternary copper(I) complexes with alkynes and 1,10-phenanthroline (phen) have been prepared and characterized by their formation constants, IR spectra, 1H and 13C NMR spectra. The structures of three complexes, [Cu(phen)(HC≡CR)]ClO4 (R = H 1, Ph 2 or CO2Et 3) have been determined using single-crystal X-ray methods. Each copper atom in all three complexes is co-ordinated to two nitrogen atoms of phen and an alkyne molecule in a trigonal-planar arrangement. The alkyne is sideways bonded onto the copper atom. The C≡C bond distances of 1.190(7) (1), 1.218(13) (2) and 1.193(10) Å (3) are slightly longer than those of the free alkynes and indicate that π back donation from copper to the alkyne is weak. The reduction of the C≡C stretching frequency for metal-alkyne complexes is correlated to the acetylenic bend-back angles and the lenghthening of the C≡C distance of the alkyne upon co-ordination. The copper-carbon and -nitrogen distances for 1 and 2 are essentially the same as those for the corresponding olefin complexes. - M MAEKAWA; M MUNAKATA; S KITAGAWA; M NAKAMURAANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 7 (5) 827 - 828 0910-6340 1991/10 [Refereed]
- M MAEKAWA; M MUNAKATA; S KITAGAWA; T YONEZAWABULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 64 (7) 2286 - 2288 0009-2673 1991/07 [Refereed]
The dicopper(I) complex with 2-(diphenylphosphino)pyridine (Ph2Ppy), [Cu2(mu-Ph2Ppy)2(CH3CN)2](PF6)2 has been prepared. The crystal structure has been determined crystallographically: Space group P1BAR, a = 10.807(6), b = 11.756(8), c = 8.606(7) angstrom, alpha = 90.36(6), beta = 95.98(5), gamma = 92.90(5)-degrees, Z = 1; R = 0.067. The two copper atoms are bridged by two Ph2Ppy molecules in a head-to-tail arrangement, resulting in a rare staggered conformation of the eight-membered ring Cu2P2-N2C2, whose factor is concerned with the coordination numbers of the central metal atoms. H-1 NMR studies show that the ligand of a CH3CN in the titled compound undergoes dissociation in acetone solution. - M MAEKAWA; M MUNAKATA; S KITAGAWA; M NAKAMURAANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEM 7 (3) 521 - 522 0910-6340 1991/06 [Refereed]
- M MUNAKATA; M MAEKAWA; S KITAGAWA; M ADACHI; H MASUDAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 167 (2) 181 - 188 0020-1693 1990/01 [Refereed]
- M MUNAKATA; M MAEKAWA; S KITAGAWA; S MATSUYAMA; H MASUDAINORGANIC CHEMISTRY AMER CHEMICAL SOC 28 (23) 4300 - 4302 0020-1669 1989/11 [Refereed]
- M MAEKAWA; S KITAGAWA; M MUNAKATA; H MASUDAINORGANIC CHEMISTRY AMER CHEMICAL SOC 28 (10) 1904 - 1909 0020-1669 1989/05 [Refereed]
- M MAEKAWA; S KITAGAWA; M MUNAKATANIPPON KAGAKU KAISHI CHEMICAL SOC JAPAN (4) 438 - 444 0369-4577 1988/04 [Refereed]
- S KITAGAWA; M MUNAKATA; M TSURUMI; M MAEKAWAINORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 121 (2) 113 - 117 0020-1693 1986/11 [Refereed]
Books etc
- 錯体化合物事典前川雅彦 (ContributorP2, P4, P5, P12, P19, P26, P29, P32, P447)朝倉書店 2019/09 9784254141054
- 錯体化学会選書４「多核種の溶液および固体ＮＭＲ」北川 進; 水野元博; 前川雅彦 (Joint work)三共出版株式会社 2008/10 9784782705681
- Construction of the molecular assemblies of copper(I) and silver(I) complexes with phenazine and control of their propertiesNew Functionality Materials, Volume C Synthetic Process and Control of Fructinality Materials, Elsevier Science Publisers 1993
- Construction of the molecular assemblies of copper(I) and silver(I) complexes with phenazine and control of their propertiesNew Functionality Materials, Volume C Synthetic Process and Control of Fructinality Materials elsevier Science Publisers 1993
Conference Activities & Talks
- Syntheses and crystal structures of novel Cu(I)-C2H4 coordination polymers bridged by 2,2':4',4''-terpyridine [Not invited]Sho Yoshimura; Masahiko Maekawa; Kunihisa Sugimoto; Takayoshi Kuroda-SowaThe 104th CSJ Annual Meeting (2024) 2024/03
- 4,4':2',2'':4'',4'''-クォーターピリジンを配位子とする多核Cu(I)-エチレン錯体の合成および構造 [Not invited]吉村 祥; 前川雅彦; 杉本 邦久; 大久保 貴志; 黒田 孝義錯体化学会第 73 回討論会 水戸市民会館 (茨城県水戸市) 錯体化学会
- 2,6-ジ(ピリミジン-4-イル)ピリジンを橋かけ配位子とする新規なAg(I)-配位高分子のアニオン選択的な自己集積化 [Not invited]田中佑汰; 前川雅彦; 杉本邦久; 大久保貴志; 黒田孝義錯体化学第72回討論会(2022)
- 2，2'-ビピリジン関連配位⼦に架橋された⼤環状四核Ir(III)-ヒドリド錯体の合成，構造および性質 [Not invited]寺田光太; 前川雅彦; 大久保貴志; 黒田孝義錯体化学会第71回討論会（2021）
- ピリミジニル基を有する多座窒素配位子を用いた新規な多核Ag(I)錯体の合成と構造 [Not invited]田中佑汰; 前川雅彦; 大久保貴志; 黒田孝義日本化学会第101春季年会(2021)
- 4,4’:2’,2’’:4’’,4’’’-クォータピリジンに架橋された多核Ir(III)ヒドリド錯体の合成，構造および性質寺田光太;前川雅彦;大久保貴志;黒田孝義日本化学会第100春季年会(2020) 東京理科大学野田キャンパス
- Cu(I) metallomacrocycle and coordination polymers with 2,2';5',4''-terpyridine directed by anions and solvents [Not invited]T. Hayashi; M. Maekawa; T. Okubo; T.Kuroda-SowaThe 7th Asian Conference on Coordination Chemistry (ACCC7 2019) 2019/10 Kuala Lumpur, Malaysia
- 新規な多核Cu(I)-エチレン錯体の対アニオンによる構造制御 [Not invited]林 輝昌; 前川 雅彦; 大久保 貴志; 黒田 孝義錯体化学会第69回討論会 2019/09
- Structural controls and properties of novel polynuclear Cu(I)-C2H4 complexes directed by counter anions [Not invited]T. Hayashi; M. Maekawa; T. Okubo; T. Kuroda-Sowa日本化学会第99春季年会(2019) 2019/03
- 多座窒素配位子を有する多核Ir(III)ヒドリド錯体の合成とC-Cl結合およびC-H結合の活性化 [Not invited]多座窒素配位子を有する多核Ir(III)ヒドリド錯体の合成とC; Cl結合およびC; H結合の活性化第68回錯体化学討論会 2018/07
- Terpyridine類縁配位子を用いた新規なCu(I)ーエチレン配位高分子の合成および構造 [Not invited]薮田真冬; 前川雅彦; 大久保貴志; 黒田孝義第68回錯体化学討論会 2018/07
- アニオンおよび溶媒支配による新規なCu(I)配位高分子の構造制御 [Not invited]林 輝昌; 前川雅彦; 大久保貴志; 黒田孝義第68回錯体化学討論会 2018/07
- Heterometallic Ag(I)-Ir(III) hydride coordination polymers bridged by Ir(III) metalloligands [Not invited]M. Maekawa; Y. Kubo; T. Okubo; T. Kuroda-SowaThe 43th International Conference on Coordination Chemistry (ICCC 2018) 2018/07
- Syntheses, crystal structures and properties of novel heterometallic polynuclear {Cu(I), Ag(I)}-Ir(III) complexes conducted by Ir(III) hydride metalloligands [Not invited]S. Oda; M. Maekawa; T. Okubo; T. Kuroda-Sowa日本化学会第98春季年会(2018) 2018/03
- Syntheses, structures and properties of novel Cu(I) coordination polymers with multidentate nitrogen ligands [Not invited]T. Hayashi; M. Maekawa; T. Okubo; T. Kuroda-Sowa日本化学会第98春季年会(2018) 2018/03
- Syntheses, structures and properties of novel polynuclear Cu(I) ethylene complexes with the related terpyridine ligands [Not invited]M. Yabuta; M. Maekawa; T. Okubo; T. Kuroda-Sowa日本化学会第98春季年会(2018) 2018/03
- Terpyridine関連配位子を用いた新規な多核Cu(I)錯体の合成，構造および性質 [Not invited]藪田真冬; 前川雅彦; 大久保貴志; 黒田孝義第67回錯体化学討論会 2017/09
- Ir(III)ヒドリド錯体を用いた混合金属多核錯体の合成，構造および性質 [Not invited]小田翔基; 前川雅彦; 大久保貴志; 黒田孝義第67回錯体化学討論会 2017/09
- Heterometallic Ag(I)−Ir(III) hydride coordination polymers bridged by Ir(III) metalloligands [Not invited]M. Maekawa; Y. Kubo; T. Okubo; T. Kuroda-Sowa; M. MunakataThe 6th Asian Conference on Coordination Chemistry (ACCC 2017) 2017/07
- Syntheses, structures and properties of heterometallic coordinationpolymers bridged by Ir(III) hydride metalloligands [Not invited]ODA, Shoki; MAEKAWA, Masahiko; OKUBO, Takashi; KURODA-SOWA; Takayoshi日本化学会第97春季年会(2017) 2017/03
- Syntheses and structures of novel polynuclear Cu(I) complexes withthe related terpyridine ligands [Not invited]YABUTA, Mafuyu; MAEKAWA, Masahiko; OKUBO, Takashi; KURODA-SOWA; Takayoshi日本化学会第97春季年会(2017) 2017/03
- Diverse copper(I) ethylene complexes with related 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine ligands [Not invited]Masahiko Maekawa; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataThe 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem2015) 2015/12
- Structural Controls of Cu(I)-C2H4 Coordination Polymers with 4,4’-Bipyrimidine Directed by Anions and Solvents [Not invited]Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu kitagawa4th International Conference on Metal-Organic Frameworks and Open Framework Compounds (MOF2014) 2014/09
- Structurally Diverse Copper(I) Ethylene Adducts with Related 3,6-BIS(2-PYRIDYL)-1,2,4,5-Tetrazine Ligands [Not invited]M. Maekawa; K. Sugimoto; T. Okubo; T. Kuroda-Sowa; M. Munakata; S. KitagawaThe 41th International Conference on Coordination Chemistry (ICCC41) 2014/07
- 新規なヘテロ金属Ag(I)-Ir(III)ヒドリド配位高分子の合成および構造 [Not invited]前川 雅彦; 久保 有希実; 大久保 貴志; 黒田 孝義; 宗像 惠第63回錯体化学討論会 2013/11 那覇 （琉球大学千原キャンパス） 第63回錯体化学討論会
3種の2,2'-ビピリジン類縁配位子(L)を用いて、配位不飽和なIr(III)-ヒドリド錯体[Ir(H)2(PPh3)2(L)]BF4を合成し、さらにCF3COOAgと反応させることにより、3種の新規なヘテロ金属Ag(I)-Ir(III)ヒドリド配位高分子を合成し、そのX線構造および性質を明らかにした。 - 多座窒素配位子を有する新規なCu(I)-エチレン錯体の合成,構造および性質 [Not invited]前川 雅彦; 南野 愛; 大久保 貴志; 黒田 孝義; 宗像 惠第６２回錯体化学討論会 2012/09 富山（富山大学五福キャンパス） 第６２回錯体化学討論会
C2H4雰囲気下，アセトン溶媒中，[Cu(MeCN)4]BF4と4,6-ビス(2-ピリジル)-ピリミジン (bppym)を反応させたところ，[Cu2(bppym)(C2H4)2](BF4)2?Me_2CO (1)が得られた。同様に[Cu(C2H4)n]ClO4とbppymを反応させたところ，[Cu2(bppym)(C2H4)2](ClO4)2?Me2CO (2)が得られた。またC2H4雰囲気下，メタノール溶媒中，[Cu(MeCN)4]BF4と4,6-ビス(2-ピリジル)-ピラジン (bppz)を反応させたところ，[Cu2(bppz)(C2H4)2](BF4)2?MeOH (3)が得られた。Ｘ線構造解析の結果，錯体1, 2および3はいずれも新規な二核Cu(I)-エチレン錯体であることが明らかとなった。 - Structural controls of Cu(I) C2H4 coordination polymers of 4,4’-bipyrimidine [Not invited]前川 雅彦; 大久保 貴志; 黒田 孝義; 宗像 惠The 40th International Conference on Coordination Chemistry (ICCC40) 2012/09 Valencia, Spain The 40th International Conference on Coordination Chemistry (ICCC40)
- Novel mono- and dinuclear Iridium(III) hydride complexes of 2,2’-bipyrimidine [Not invited]前川 雅彦; 久保 有希実; 大久保 貴志; 黒田 孝義; 宗像 惠The 40th International Conference on Coordination Chemistry (ICCC40) 2012/09 Valencia, Spain The 40th International Conference on Coordination Chemistry (ICCC40)
- Ir(III)ヒドリド錯体を連結した新規な一次元Ir(III)-Ag(I)配位高分子の合成および構造 [Not invited]前川 雅彦; 久保 有希実; 大久保 貴志; 黒田 孝義; 宗像 惠第６２回錯体化学討論会 2012/09 富山（富山大学五福キャンパス） 第６２回錯体化学討論会
[Ir(H)2(PPh3)2(Me2CO)2]BF4と4,4'-ビキナゾリン(biqz)を用いて、錯体配位子として配位不飽和なIr(III)-ヒドリド錯体[Ir(H)2(PPh3)2(biqz)]BF4を合成し、さらにCF3COOAgと反応させることにより、新規な一次元Ag(I)-Ir(III)-biqz混合金属配位高分子を合成し、そのX線構造および性質を明らかにした。 - First Cu(I) coordination polymers of 4,4’-biquinazoline and the C2H4 adduct [Not invited]前川 雅彦; 南野 愛; 大久保 貴志; 黒田 孝義; 宗像 惠The 40th International Conference on Coordination Chemistry (ICCC40) 2012/09 Valencia, Spain The 40th International Conference on Coordination Chemistry (ICCC40)
- 多座窒素配位子を用いた新規なCu(I)-エチレン錯体の合成，構造および性質 [Not invited]前川 雅彦; 南野 愛; 大久保 貴志; 黒田 孝義; 宗像 惠日本化学会第92春季年会 2012/03 慶應大学日吉キャンパス(横浜) 日本化学会第92春季年会
C2H4雰囲気下，アセトン溶媒中，[Cu(MeCN)4]BF4と4,6-ビス(2-ピリジル)-ピリミジン (bppym)を反応させたところ，[Cu2(bppym)(C2H4)2](BF4)2?Me2CO (1)が得られた。同様に[Cu(C2H4)n]ClO4とbppymを反応させたところ，[Cu2(bppym)(C2H4)2](ClO4)2?Me2CO (2)が得られた。Ｘ線構造解析の結果，錯体1および2はいずれも新規な二核Cu(I)-エチレン錯体であることが明らかとなった。 - 多座窒素配位子を有する新規なIr(III)ヒドリド錯体の合成，構造および性質 [Not invited]前川 雅彦; 久保 有希実; 大久保 貴志; 黒田 孝義; 宗像 惠日本化学会第92春季年会 2012/03 慶應大学日吉キャンパス(横浜) 日本化学会第92春季年会
Ar雰囲気下，CHCl3溶液中，[Ir(H)2(PPh3)2(Me2CO)2]X(X=BF4, PF6)と様々なビピリミジン系配位子を反応させ，5種の新規なIr(III)ヒドリド錯体を単離することに成功し，その構造ならびに性質をX線構造解析，IR, TG-DTA, 固体UV-VIS, 1H NMR法より特徴付けた。例えば，2,2'-ビピリミジン (bpym)を用いた場合，合成溶媒選択的に単核Irヒドリド錯体[Ir(H)2(PPh3)2(bpym)]BF4および二核Irヒドリド錯体[Ir2(H)4(PPh3)4(bpym)](BF4)2が生成することが明らかとなった。 - 3,6-ビス(2-ピリジル)-1,2,4,5-テトラジンを配位子とする様々なCu(I)-エチレン錯体の合成および構造 [Not invited]前川 雅彦; 宮崎 武志; 大久保 貴志; 黒田 孝義; 宗像 惠日本化学会第92春季年会 2012/03 慶應大学日吉キャンパス(横浜) 日本化学会第92春季年会
C2H4雰囲気下，Me2CO中，Cu(ClO4)2，金属銅および3,6-ビス(2-ピリジル)-1,2,4,5-テトラジン(bptz)を反応させると，3種の新規なCu(I)-bptz/C2H4錯体および4核Cu(I)-bptz錯体が生成することを見出し，その構造および性質を明らかにした。特にテトラジン環がアニオンラジカル化した{[Cu2(bptz)(C2H4)2]ClO4}2ならびにテトラジン環が大きく歪んだ[Cu2(bptz)(C2H4)2](ClO4)2は興味が持たれる。 - ビピリミジン系多座窒素配位子を有する新規なイリジウム(III)ヒドリド錯体の合成と構造化学的特徴付け [Not invited]前川 雅彦; 久保 有希実; 大久保 貴志; 宗像 惠; 黒田 孝義第６１回錯体化学討論会 2011/09 岡山（岡山理科大学） 第６１回錯体化学討論会
Ar下、CHCl3中、[Ir(H)2(PPh3)2(Me2CO)2]BF4と4-(2-ピリジル)ピリミジン(pprd)を反応させ、新規な単核錯体[Ir(H)2(pprd)(PPh3)2]BF4を合成した。同様に2,2'-ビピリミジン(bpym)を反応させると、単核錯体[Ir(H)2(bpym)(PPh3)2]BF4および二核錯体[Ir2(H)4(bpym)(PPh3)4](BF4)2が生成することを見出した。いずれの錯体も溶液内において環電流効果に基づく特徴的な磁気異方性シフトが観測された。 - アニオンラジカルを配位子とする始めてのCu(I)-エチレン錯体の合成、構造およびキャタクタリゼーション [Not invited]前川 雅彦; 宮崎 武志; 大久保 貴志; 宗像 惠; 黒田 孝義第６１回錯体化学討論会 2011/09 岡山（岡山理科大学） 第６１回錯体化学討論会
C2H4下、Me2CO中、Cu(ClO4)2、金属Cuおよび3,6-ビス(2-ピリジル)-1,2,4,5-テトラジン(bptz)を反応させると、アニオンラジカルを配位子とする始めての二核Cu(I)-C2H4錯体{[Cu2(bptz)(C2H4)2]ClO4}2が生成することを見出し、そのX線構造および性質を明らかにした。あわせてbtpzが極めて珍しいcis形構造を取った二核錯体[Cu2(bptz)(C2H4)2](ClO4)2が生成することを見出した。 - アニオンおよび溶媒に導かれた4,4'-ビピリミジン類を配位子とする新規なCu(I)配位高分子の自己組織化 [Not invited]前川 雅彦; 南野 愛; 大久保 貴志; 宗像 惠; 黒田 孝義第６１回錯体化学討論会 2011/09 岡山（岡山理科大学） 第６１回錯体化学討論会
C2H4雰囲気下、MeOH中、[Cu(CH3CN)4]X (X=BF4, PF6)と4,4'-ビキナゾリン(biqz)を反応させると、biqzのキレート部位と橋かけ部位がCu(I)イオンに配位し、Cu2C6N6骨格からなる14員環構造が繋げられた新規なCu(I)ポリマー錯体{[Cu4(biqz)2(CH3CN)4(MeOH)4(BF4)4}n (1)および{[Cu4(biqz)2(CH3CN)8](PF6)4}n(2)が自己組織化されることを見出した。同様に、Me2CO中において[Cu(C2H4)n]ClO4とbiqzを反応させると、錯体1および2とは異なり、アニオンおよび溶媒選択的に、一次元ジグザグ鎖構造を有するCu(I)エチレン付加体{[Cu2(biqz)(C2H4)2](ClO4)2}n(3)が自己組織化されることを見出した。 - ビピリミジン系配位子により構築された新規なCu(I)配位高分子の合成、構造および性質 [Not invited]前川 雅彦; 南野 愛; 大久保 貴志; 黒田 孝義; 宗像 惠日本化学会第91春季年会(2011) 2011/03 神奈川大学横浜キャンパス 日本化学会第91春季年会(2011)
C2H4雰囲気下、メタノール中、[Cu(CH3CN)4]X (X=BF4, PF6)と4,4'-ビキナゾリン(biqz)を反応させたところ、{[Cu4(biqz)2(CH3CN)4(MeOH)4](BF4)4}n (1)および{[Cu4(biqz)2(CH3CN)8](PF6)4}n (2)が得られた。Ｘ線構造解析の結果、錯体1および2はいずれもbiqzのキレート部位と橋架け部位がCu(I)イオンに配位し、Cu2C6N6骨格からなる14員環構造が繋げられた新規なCu(I)ポリマー錯体であることがわかった。 - ビピリミジン系架橋配位子を用いた新規なIr(III)ヒドリド錯体の合成および構造 [Not invited]前川 雅彦; 久保 有希実; 大久保 貴志; 黒田 孝義; 宗像 惠日本化学会第91春季年会(2011) 2011/03 神奈川大学横浜キャンパス 日本化学会第91春季年会(2011)
Ar雰囲気下、CHCl3中、[Ir(H)2(PPh3)2(Me2CO)2]X (X=BF4, PF6)と4-(2-ピリジル)ピリミジン(pprd)および4,4’-ビキナゾリン(biqz)を反応させたところ、[Ir(H)2(PPh3)2(pprd)]BF4 (1)および[Ir(H)2(PPh3)2(biqz)]PF6 (2)が得られた。Ｘ線構造解析の結果、錯体1および2はIr原子にヒドリド、PPh3および窒素配位子が配位した単核錯体であることがわかった。溶液中において環電流効果に伴う特徴的な1H NMRシフトを観測した。 - テトラジンアニオンラジカルを有する新規なCu(I)-エチレン錯体の合成および構造 [Not invited]前川 雅彦; 宮崎 武志; 大久保 貴志; 黒田 孝義; 宗像 惠日本化学会第91春季年会(2011) 2011/03 神奈川大学横浜キャンパス 日本化学会第91春季年会(2011)
C2H4雰囲気下、Me2CO中、Cu(ClO4)2、金属銅および3,6-ビス(2-ピリジル)-1,2,4,5-テトラジン(bptz)を反応させることにより、テトラジンアニオンラジカルを有する二核Cu(I)-エチレン錯体が生成することを見出し、その構造および性質を明らかにした。あわせて、ラジカル化していないbptzが配位した2種類の二核Cu(I)-エチレン錯体が生成することを見出した。 - Novel Cu(I) metallamacrocycles toward structurally and functionally new inorganic anion receptors [Not invited]前川 雅彦; 大久保 貴志; 黒田 孝義; 宗像 惠; 京都大学大学院工学研究科The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010) 2010/12 Honolulu, Hawaii, USA The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
- 平面性Schiff塩基配位子を有するFe錯体の合成・構造とSCO挙動 [Not invited]木村 佳樹; 川崎 惇; 大久保 貴志; 前川 雅彦; 黒田 孝義第６０回錯体化学討論会 2010/09 大阪 第６０回錯体化学討論会
- テトラジンアニオンラジカルを有する新規なCu(I)-エチレン錯体の合成と構造 [Not invited]前川 雅彦; 宮崎武志; 大久保 貴志; 黒田 孝義; 宗像 惠第60回錯体化学討論会 2010/09 大阪 （大阪国際交流センター） 第60回錯体化学討論会
エチレン雰囲気下、Me2CO中、Cu(ClO4)2、金属銅および3,6-ビス(2-ピリジル)-1,2,4,5-テトラジン(bptz)を反応させたところ、テトラジンアニオンラジカルを有する二核Cu(I)- -bptz/C2H4錯体が生成することを見出し、その構造および性質を明らかにした。あせてシス形配置を有する二核Cu(I)-bptz/C2H4錯体の単離・構造解析も明らかにした。 - チオシアン酸鉄と架橋配位子bpbによって構築されたフレームワーク構造を有する錯体の構造と物性 [Not invited]増田 隆之; 鈴木 詩織; 大久保 貴志; 前川 雅彦; 黒田 孝義第６０回錯体化学討論会 2010/09 大阪 第６０回錯体化学討論会
- クロラニル酸を架橋基とした新規な一次元鎖鉄錯体の合成と磁気的性質 [Not invited]諸富 匠; 前川 雅彦; 大久保 貴志; 黒田 孝義第６０回錯体化学討論会 2010/09 大阪 第６０回錯体化学討論会
- CN架橋基を有するCoシッフ塩基錯体の合成と構造 [Not invited]川崎 惇; 大久保 貴志; 前川 雅彦; 黒田 孝義第６０回錯体化学討論会 2010/09 大阪 第６０回錯体化学討論会
- 平面性コバルト(II)Salphen系錯体の積層構造と物性 [Not invited]川崎 惇; 大久保 貴志; 前川 雅彦; 黒田 孝義日本化学会第90春季年会 2010/03 大阪 日本化学会第90春季年会
- Synthesis and structures of novel Cu(I) ethylene complexes with a tetrazine anion radical ring [Not invited]前川 雅彦; 宮崎 武志; 大久保 貴志; 黒田 孝義; 宗像 惠日本化学会第90回春季年会 2010/03 東大阪（近畿大学本部キャンパス） 日本化学会第90回春季年会
C2H4雰囲気下、アセトン中、Cu(ClO4)2、金属銅および3,6-ビス(2-ピリジル)-1,2,4,5-テトラジン (bptz)を反応させたところ、2種類の針状結晶{[Cu2(bptz)(C2H4)2]ClO4}2 (1)および板状結晶[Cu2(bptz)(C2H4)2](ClO4)2 (2)が得られた。Ｘ線構造解析の結果、bptzが還元されてテトラジンアニオンラジカルを生成し、錯体１はアニオンラジカルを配位子とする始めての二核Cu(I)-エチレン錯体である。 - チオシアン酸コバルトとbpb架橋配位子により構築された3次元相互貫入フレームワーク錯体の構造とゲスト分子吸脱着特性 [Not invited]増田 隆之; 大島 有紀子; 富永 登志; 大久保 貴志; 前川 雅彦; 黒田 孝義日本化学会第90春季年会 2010/03 大阪 日本化学会第90春季年会
- カルボキシル基を有するFe(II)SCO錯体における水素結合の効果 [Not invited]木村 佳樹; 大久保 貴志; 前川 雅彦; 黒田 孝義日本化学会第90春季年会 2010/03 大阪 日本化学会第90春季年会
- Synthesis of Cu(I) and Ag(I) Metallamacrocycles as Structurally and Functionally New Inorganic Anion Receptors [Not invited]前川 雅彦; 大久保 貴志; 黒田 孝義; 宗像 惠; 北川 進The second Asian Conference on Coordination Chemistry (2nd ACCC) 2009/11 Nanjing, China The second Asian Conference on Coordination Chemistry (2nd ACCC)
- Novel Cu(I) Ethylene Complexes Three?Dimensionally Self?Assembled by an Intermolecular π?π Stacking Interaction and a C?H???N Contact [Not invited]前川 雅彦; 富永 登志; 大久保 貴志; 黒田 孝義; 宗像 惠The second Asian Conference on Coordination Chemistry (2nd ACCC) 2009/11 Nanjing, China The second Asian Conference on Coordination Chemistry (2nd ACCC)
- 架橋能を有するterpy系Co(II)及びCu(II)錯体による配位高分子の合成と物性 [Not invited]泉 貴文; 富永 登志; 前川 雅彦; 大久保 貴志; 黒田 孝義第５９回錯体化学討論会 2009/09 長崎 第５９回錯体化学討論会
- ビスカテコール配位子からなるCo(II)三核錯体の合成と性質 [Not invited]末永 勇作; 前川 雅彦; 峯松 敏江; 藤島 康紘; 冨永 登志; 中口 祐樹第59回錯体化学討論会 2009/09 長崎 第59回錯体化学討論会
ビスカテコールと酢酸コバルトから、Ⅱ価のコバルト三核錯体の結晶構造解析に成功した。コバルトはN3O3の六配位で、光学活性な三角構造を形成していた。 - S字型架橋配位子を用いた多核鉄錯体の合成 [Not invited]諸富 匠; 大久保 貴志; 前川 雅彦; 黒田 孝義第５９回錯体化学討論会 2009/09 長崎 第５９回錯体化学討論会
- Salphen系配位子を用いた平面性コバルト(II)錯体の構造と物性 [Not invited]川崎 惇; 前川 雅彦; 大久保 貴志; 黒田 孝義第５９回錯体化学討論会 2009/09 長崎 第５９回錯体化学討論会
- N4O2型配位環境を有する一次元鎖Fe(II)スピンクロスオーバー錯体の合成と構造 [Not invited]清水 俊行; 富永 登志; 鍋井 淳宏; 前川 雅彦; 大久保 貴志; 黒田 孝義第５９回錯体化学討論会 2009/09 長崎 第５９回錯体化学討論会
- N2O型Schiff塩基配位子による鉄錯体の合成と物性 [Not invited]木村 佳樹; 前川 雅彦; 大久保 貴志; 黒田 孝義第５９回錯体化学討論会 2009/09 長崎 第５９回錯体化学討論会
- 4,4'-ビピリミジン類を配位子とする新規なCu(I)配位高分子の合成と構造 [Not invited]前川 雅彦; 富永 登志; 大久保 貴志; 黒田 孝義; 宗像 惠; 杉本 邦久; 北川 進第59回錯体化学討論会 2009/09 長崎（長崎大学文京キャンパス） 第59回錯体化学討論会
Ar/C2H4雰囲気下、MeOH中、[Cu(CH3CN)4]BF4と4,4'-ビピリミジン (bpm)を反応させたところ、そのゲージ内にガラス管由来のSiF6アニオンを捕捉した3次元Cu(I)-bpm配位高分子が自己集積化した。またC2H4雰囲気下、同様の反応を試みたところ、その空孔内にBF4アニオンを捕捉したメタラマクロサイクルが連結された2次元Cu(I)-bpm-C2H4付加体が生成した。 - 強磁性的相互作用を示すbis-Schiff塩基配位子を有 した新規Fe(II)錯体の合成及び構造 [Not invited]清水 俊行; 鍋井 淳宏; 前川 雅彦; 大久保 貴志; 黒田 孝義日本化学会第８９春季年会 2009/03 船橋 日本化学会第８９春季年会
- カルボキシル基を有するN2O型Schiff Base配位子によるFe錯体の合成とその多核化 [Not invited]木村 佳樹; 玉浦 裕貴; 大久保 貴志; 前川 雅彦; 黒田 孝義日本化学会第８９春季年会 2009/03 船橋 日本化学会第８９春季年会
- Self-assemblies of novel Cu(I) metallamacrocyclic carbonyl adducts by anion templation [Not invited]前川 雅彦; 富永 登志; 鍋井 淳宏; 大久保 貴志; 黒田 孝義; 宗像 惠; 北川 進日本化学会第８９春季年会 2009/03 船橋 日本化学会第８９春季年会
CO雰囲気下、[Cu(CH3CN)4]BF4と6,6'-ジメチル-4,4'-ビピリミジン(Me2bpm)を反応させた場合、四核Cu(I)メタラマクロサイクリックCO付加体[Cu4(Me2bpm)4(CO)4](BF4)4が、一方[Cu(CH3CN)4]PF6とMe2bpmを反応させた場合、メタラカリックス[3]アレン型の三核Cu(I)-CO付加体が連結された２次元Cu(I)配位高分子{ { [Cu3(Me2bpm)3(CO)3](PF6)3}[Cu(CH3CN)]BF4}がアニオン選択的に自己集積化されることを見出した。 - bis-Schiff塩基配位子を有する一次元鎖Fe錯体の構造と磁気特性 [Not invited]鍋井 淳宏; 大久保 貴志; 前川 雅彦; 宗像 惠; 黒田 孝義日本化学会第８９春季年会 2009/03 船橋 日本化学会第８９春季年会
- 7,7,8,8-tetracyanoquinodimethane (TCNQ) 由来のイソシアニド配位を有するシッフ塩基コバルト錯体の合成 [Not invited]川崎 惇; Yu Zhong; 鍋井 淳宏; 大久保 貴志; 前川 雅彦; 黒田 孝義日本化学会第８９春季年会 2009/03 船橋 日本化学会第８９春季年会
- Self-assemblies of novel Cu(I) metallamacrocyclic ethylene adducts by 4,4'-bipyrimidine derivatives [Not invited]前川 雅彦; 富永 登志; 鍋井 淳宏; 大久保 貴志; 黒田 孝義; 宗像 惠; 北川 進日本化学会第８９春季年会 2009/03 船橋 日本化学会第８９春季年会
C2H4雰囲気下、[Cu(CH3CN)4]BF4と6,6'-ジメチル-4,4'-ビピリミジン(Me2bpm)を反応させた場合、三核Cu(I)メタラマクロサイクリック-エチレン付加体が、[Cu(CH3CN)]+に繋げられ、その空孔内にBF4-アニオンを捕捉した二次元Cu(I)配位高分子 {[Cu4(Me2bpm)3(C2H4)3(CH3CN)](BF4)4}nが自己集積化した。また[Cu(CH3CN)4]BF4と6,6'-ジフェニル-4,4'-ビピリミジン(Ph2bpm)を反応させた場合、単核Cu(I)-エチレン錯体[Cu(Ph2bpm)(C2H4)]BF4が生成した。 - 架橋能を有するコバルトSCO 錯体によるCu(I)配位高分子の合成と物性 [Not invited]泉 貴文; 鍋井 淳宏; 前川 雅彦; 大久保 貴志; 黒田 孝義第５８回錯体化学討論会 2008/09 金沢 第５８回錯体化学討論会
- 新規なCu(I)メタラマクロサイクリックエチレン付加体の合成および構造 [Not invited]前川 雅彦; 富永登志; 鍋井淳宏; 大久保 貴志; 黒田 孝義; 宗像 惠; 北川 進第58回錯体化学討論会 2008/09 金沢 （金沢大学角間キャンパス） 第58回錯体化学討論会
[Cu(CH3CN)4]BF4と4,4'-ビピリミジン(bpm)をエチレン下反応させ空孔内にBF4アニオンを捕捉したメタラカリックスアレンが繋がった２次元Cu(I)-bpm-エチレン付加体の構築に成功した。本研究ではさらに6,6'-ジフェニル-4,4'-ビピリミジン(Ph2bpm)を用い、同様に合成を行ない黄色針状結晶を得た。IR測定などからCu(I)-Ph2bpm-C2H4錯体の生成を確認した。 - qsal 誘導体を用いた多核FeSCO 錯体の合成と物性 [Not invited]玉浦 裕貴; 鍋井 淳宏; 富永 登志; 前川 雅彦; 大久保 貴志; 黒田 孝義第５８回錯体化学討論会 2008/09 金沢 第５８回錯体化学討論会
- Bis-Schiff 塩基配位子を用いたFe(III)錯体と架橋配位子との一次元鎖錯体の磁性および構造におよぼすアニオン効果 [Not invited]鍋井 淳宏; 大久保 貴志; 前川 雅彦; 黒田 孝義第５８回錯体化学討論会 2008/09 金沢 第５８回錯体化学討論会
- Bis-Schiff 塩基配位子と架橋配位子からなる一次元鎖Fe(II)スピンクロスオーバー錯体の合成と物性 [Not invited]清水 俊行; 鍋井 淳宏; 大久保 貴志; 前川 雅彦; 黒田 孝義第５８回錯体化学討論会 2008/09 金沢 第５８回錯体化学討論会
- Self-assemblies of novel Cu(I) and Ag(I) coordination polymers by anion templation [Not invited]前川 雅彦; 富永登志; 鍋井淳宏; 黒田 孝義; 宗像 惠; 大久保 貴志; 北川 進日本化学会第88春季年会 2008/03 日本化学会 日本化学会第88春季年会
アニオンテンプレート法を用いて4-(2-ピリジル)ピリミジン(pprd)および4,4'-ビピリミジン(bpm)を配位子とする新規な銅(I)および銀(I)配位高分子を自己集積化させることを試み、特にエチレン雰囲気下、[Cu(CH3CN)]BF4とbpmを反応さた場合、空孔内にBF4-アニオンを捕捉したC2H4の脚を有するメタラカリックス[3]アレンエチレ付加体が２次元シート構造状に繋がった興味深い{ { [Cu3(pprd)3(C2H4)3](BF4)3}[Cu(CH3CN)]BF4}が自己集積化することを見出した。 - bis-Schiff塩基配位子を有するFe錯体の構造とスピンクロスオーバー挙動 [Not invited]鍋井 淳宏; 大久保 貴志; 前川 雅彦; 宗像 惠; 黒田 孝義日本化学会第８８春季年会 2008/03 東京 日本化学会第８８春季年会
- bis-Schiff塩基配位子を有するFeおよびCo錯体の構造とスピンクロスオーバー挙動 [Not invited]鍋井 淳宏; 大久保 貴志; 前川 雅彦; 宗像 惠; 黒田 孝義第５７回錯体化学討論会 2007/09 名古屋 第５７回錯体化学討論会
- 平面性Schiff-base 配位子を有する新規Co(II)一次元錯体の構造及び磁気特性 [Not invited]黒田 孝義; 宗像 惠; 前川 雅彦; 鍋井 淳宏日本化学会第８７春季年会 2007/03 吹田 日本化学会第８７春季年会
- The Redox Behavior of Binuclear Metal Complexes with Bis(catecholate) Ligand [Not invited]末永 勇作; 前川 雅彦; 黒田 孝義; 宗像 惠; 梅畑優貴子日本化学会第８７春季年会 2007/03 大阪（関西大学） 日本化学会第８７春季年会
酸化還元活性なカテコール部位を２つもつビスカテコールを配位子としたCo(III)二核錯体を合成し、NMR、元素分析により同定した。また、温度可変NMR、UV、CVから二核錯体の性質を明らかにした。末端のN-N配位子に2,2'-bipyridine(bpy), 2,2'-dipyridylamine(dpa)を使用するとdpa の強い配位子場の影響で、ビスカテコール部分が容易に化学酸化できることを見出した。 - 急峻なスピン転移をもつ鉄(II)スピンクロスオーバー錯体の協同現象に対する異種金属のドーピング効果 [Not invited]黒田 孝義; 宗像 惠; 前川 雅彦; 久米 啓晶第５６回錯体化学討論会 2006/09 広島 第５６回錯体化学討論会
- 平面性Mn(III)錯体の水素結合二量体で観測される単一分子磁石的挙動 [Not invited]黒田 孝義; 宗像 惠; 前川 雅彦; 鍋井 淳宏第５６回錯体化学討論会 2006/09 広島 第５６回錯体化学討論会
- Syntheses and Properties of Binuclear Metal Complexes with Conjugated Bis(catecholate) Ligand. [Not invited]末永 勇作; 前川 雅彦; 黒田 孝義; 宗像 惠; 平野泰広第５６回錯体化学討論会 2006/09 広島（広島大学） 第５６回錯体化学討論会
三重結合でカテコールを連結した新規ビスカテコールを合成した。このCo(III)二核錯体を合成し、NMR、元素分析により同定した。さらに、温度可変NMR、UV、CVにより、二核錯体の性質を明らかにした。 - Self-assembly of Cu(I) and Ag(I) metallocycles by anion templation [Not invited]前川 雅彦; 黒田 孝義; 宗像 惠; 北川 進第５６回錯体化学討論会 2006/09 第５６回錯体化学討論会（広島市、広島大学東千田キャンパス） 第５６回錯体化学討論会
アニオンテンプレート法を用いて、エチレン雰囲気下、4-(2-ピリジル)ピリミジンを配位子とする3核、4核、6核Cu(I)メタラサイクリック錯体、およびサンドイッチ型構造を有する4核Ag(I)錯体を対アニオン選択的に自己集積化し、その結晶構造および溶液内構造を明らかにした。 - Mn(III)錯体の水素結合二量体の単一分子磁石挙動 [Not invited]黒田 孝義; 宗像 惠; 前川 雅彦; 鍋井 淳宏２００６分子構造総合討論会 2006/09 静岡 ２００６分子構造総合討論会
- 鉄(II)スピンクロスオーバー錯体の協同現象に対する異種金属のドーピング効果 [Not invited]久米啓晶; 黒田 孝義; 宗像 惠; 前川 雅彦日本化学会第８６春季年会 2006/03 船橋 日本化学会第８６春季年会
- 平面性Mn(III)錯体の強磁性2量体で観測される単一分子磁石的挙動 [Not invited]鍋井淳宏; 黒田 孝義; 宗像 惠; 前川 雅彦日本化学会第８６春季年会 2006/03 船橋 日本化学会第８６春季年会
- Structures and Properties of Silver(I) Coordination Polymer with Benzylthioether Ligand [Not invited]末永 勇作; 前川 雅彦; 黒田 孝義; 宗像 惠; 江島和也日本化学会第86春季年会 2006/03 千葉（日本大学） 日本化学会第86春季年会
ベンジルチオエーテル基を含む三脚型配位子を合成し、そのAg(I)配位高分子の光誘導機能を明らかにした。 - Unique Ag(I) metallomacrocycles encapsulating a XF62- anion (X=Si, Ge and Sn) in the sandwich structure [Not invited]前川 雅彦; 黒田 孝義; 宗像 惠; 北川 進日本化学会第８６春季年会 2006/03 日本化学会（船橋市、日本大学理工学部船橋キャンパス） 日本化学会第８６春季年会
２つの平面四角形４核銀(I)メタロマクロサイクリック内にXF62-アニオンを選択的に取り込んだサンドイッチ構造を有する３つの銀(I)メタロマクロサイクリック{[Ag4(pprd)4]2(XF6)}(BF4)6?8MeNO2 (pprd=4-(2-ピリジル)ピリミジン; X=Si, Ge, Sn)を合成し、その固体および溶液内構造を明らかにした。これらは二価アニオンをメタロマクロサイクリック内に取り込んだ始めての例である。 - 2-Dimensional Silver(I) Coordination Polymer with Twisted Naphthalene Rings [Not invited]末永 勇作; 前川 雅彦; 黒田 孝義; 宗像 惠環太平洋国際化学会議 2005/12 アメリカ、ハワイ 環太平洋国際化学会議
ナフタレン環の8つの水素原子をチオフェニルエーテル基を含む嵩高い置換基で置き換えた配位子を用いて銀(I)金属錯体ポリマーを合成した。単結晶X線構造解析の結果から、ナフタレン環が約30-35°ねじれた状態で、錯体骨格内に取り込まれていることを明らかにした。新規な４つの化合物のうち、圧力によって可逆的に変色する化合物を見出した。 - Syntheses and structural characterization of novel mono- and dinuclear iridium hydrido complexes with polydentate nitrogen ligands [Not invited]前川 雅彦; 黒田 孝義; 宗像 惠The 2005 International Chemical Congress of Pacific Basin Societies (Pacifichem2005) 2005/12 ホノルル, ハワイ州, アメリカ The 2005 International Chemical Congress of Pacific Basin Societies (Pacifichem2005)
- Two structural isomers of Mn12-benzoate induced by coexistence of one or two napy molecules [Not invited]鍋井淳宏; 黒田 孝義; 宗像 惠; 前川 雅彦The 2005 International Chemical Congress of Pacific Basin Societies 2005/12 ホノルル（米国） The 2005 International Chemical Congress of Pacific Basin Societies
- Effect of diphenylphosphate (dpp) substitution on the structure and magnetic properties of Mn12 SMMs [Not invited]黒田 孝義; 宗像 惠; 前川 雅彦; Bian Guo Quin; 波多野雅紀; 小中尚The 2005 International Chemical Congress of Pacific Basin Societies 2005/12 ホノルル（米国） The 2005 International Chemical Congress of Pacific Basin Societies
- Abrupt spin transition and LIESST phenomena observed in a Fe(II) complex with a N4O2 donor set [Not invited]黒田 孝義; 宗像 惠; 前川 雅彦; 先崎由蘭; 杉本邦久; 速水真也; 前田米蔵The 2005 International Chemical Congress of Pacific Basin Societies 2005/12 ホノルル（米国） The 2005 International Chemical Congress of Pacific Basin Societies
- π系の拡がった平面性Schiff base配位子を用いた新規Mn(III)錯体の構造と磁性 [Not invited]鍋井淳宏; 黒田 孝義; 宗像 惠; 前川 雅彦２００５分子構造総合討論会 2005/10 東京 ２００５分子構造総合討論会
- 拡張π系シッフ塩基配位子を有する鉄(II)錯体の構造と光誘起スピン転移 [Not invited]黒田 孝義; 宗像 惠; 前川 雅彦; 久米啓晶; 速水真也; 前田米蔵第５５回錯体化学討論会 2005/09 新潟 第５５回錯体化学討論会
- 拡がったπ系を有する新規鉄(II)錯体の合成とそのスピン転移 [Not invited]久米啓晶; 黒田 孝義; 宗像 惠; 前川 雅彦第５５回錯体化学討論会 2005/09 新潟 第５５回錯体化学討論会
- 平面性Schiff base配位子を用いた新規Mn(III)錯体の構造とその磁性 [Not invited]日比野一幸; 黒田 孝義; 宗像 惠; 前川 雅彦第５５回錯体化学討論会 2005/09 新潟 第５５回錯体化学討論会
- ヒドロキシピリジン誘導体で部分置換した新規Mn12核錯体の構造 [Not invited]鍋井淳宏; 黒田 孝義; 宗像 惠; 前川 雅彦第５５回錯体化学討論会 2005/09 新潟 第５５回錯体化学討論会
- カリックス様Cu(I)エチレンおよび一酸化炭素メタラサイクリック錯体の合成と構造 [Not invited]前川 雅彦; 小中 尚; 黒田 孝義; 宗像 惠; 北川 進第55回錯体化学討論会 2005/09 新潟（朱鷺メッセ） 第55回錯体化学討論会
- Syntheses and Properties of Co(III) Dinuclear Complexes with π Conjugated Biscatecholate Ligands [Not invited]末永 勇作; 前川 雅彦; 黒田 孝義; 宗像 惠; Cortl; G. Pierpont第55回錯体化学討論会 2005/09 新潟、朱鷺メッセ 第55回錯体化学討論会
分子内にカテコール部位を2つ有するπ共役系配位子を合成し、そのCo二核錯体を合成した。NMR、UVスペクトルからキャラクタリぜーションを行い、Coは三価に酸化されており、配位子の両末端に八面体構造のCoが配位結合されていることを明らかにした。温度可変NMR測定から、酸化還元活性なビスカテコール分子の1つのシグナルが可逆的にシフトする挙動を観測した。 - １、８－ナフチリジンの共存により誘起された安息香酸架橋Mn12核錯体の構造異性体 [Not invited]鍋井 淳宏; 黒田 孝義; 前川 雅彦; 宗像 惠日本化学会第８５春季年会 2005/03 神奈川大学（横浜） 日本化学会第８５春季年会
- Syntheses and structures of rhodium and iridium complexes with polycyclic aromatic hydrocarbon ligands [Not invited]前川 雅彦; 萱沼 陽二郎; 鍋井 淳宏; 黒田 孝義; 末永 勇作; 宗像 惠日本化学会第85春季年会 2005/03 横浜（神奈川大学） 日本化学会第85春季年会
多環式芳香族化合物(PAHs)を配位子とするダブルデッカー構造を有する４つのロジウムおよびイリジウム錯体[M(Cp*)(η6-PAHs)](BF4)2 (M=Rh, Ir; PAHs=ピレン, トリフェニレン,フェナントレン)を合成し、その固体および溶液内構造をＸ線構造解析、1Dおよび2D NMRより明らかにした。３つのIr錯体はいずれも配位シフトに加え環電流効果に伴う特異な1H および 13C NMRスペクトルを与えることを見出した。 - Mnganese(II) naphthalocyaninateの磁気特性 [Not invited]日比野 一幸; 黒田 孝義; 前川 雅彦; 宗像 惠日本化学会第８５春季年会 2005/03 神奈川大学（横浜） 日本化学会第８５春季年会
- 窒素系架橋配位子で部分置換した新規Mn12核錯体の合成と単一分子磁性 [Not invited]鍋井 淳宏; 黒田 孝義; 前川 雅彦; 宗像 惠２００４分子構造総合討論会 2004/10 広島大学（広島） ２００４分子構造総合討論会
- A Novel Mn12 Single-Molecule Magnet [Mn12O12(OAc)12(dpp)4] [Not invited]黒田 孝義; Bian Guo-Qing; 小中 尚; 波多野 雅紀; 前川 雅彦; 宗像 惠; 宮坂 等; 山下IX th International Conference on Molecule-based Magnets 2004/10 Tsukuba, Japan IX th International Conference on Molecule-based Magnets
- 配位不飽和なMn(III)を有するMn12核錯体の構造及びその誘導体の合成 [Not invited]波多野 雅紀; 黒田 孝義; Bian Guo-Qing; 小中 尚; 前川 雅彦; 宗像 惠; 宮坂 等; 山下第５４回錯体化学討論会 2004/09 熊本大学（熊本） 第５４回錯体化学討論会
- 窒素系架橋基で部分置換した新規Mn12核錯体の合成および磁性 [Not invited]鍋井 淳宏; 黒田 孝義; 前川 雅彦; 宗像 惠第５４回錯体化学討論会 2004/09 熊本大学（熊本） 第５４回錯体化学討論会
- Syntheses and structures of rhodium and iridium complexes with polycyclic aromatic hydrocarbon ligands [Not invited]前川 雅彦; 萱沼 陽二郎; 鍋井 淳宏; 黒田 孝義; 宗像 惠第54回錯体化学討論会 2004/09 熊本（熊本大） 第54回錯体化学討論会
ピレン(pyr)およびトリフェニレン(triph)を配位子とする新規ロジウムおよびイリジウム錯体、[M(Cp*)(η6-pyr)](BF4)2 (M=Rh, Ir)および[M(Cp*)(η6-triph)](BF4)2 (M=Rh, Ir)を合成し、その構造および性質を明らかにした。 - かさ高い架橋基を有するMn(III)二核錯体の構造とその磁性 [Not invited]上島 弘義; 黒田 孝義; 前川 雅彦; 宗像 惠第５４回錯体化学討論会 2004/09 熊本大学（熊本） 第５４回錯体化学討論会
- Syntheses and crystal structures of novel rhodium and iridium complexes with [2.2]paracyclophane [Not invited]前川 雅彦; 黒田 孝義; 末永 勇作; 宗像 惠The 36th International Conference on Coordination Chemistry 2004/07 メリダ市、メキシコ The 36th International Conference on Coordination Chemistry
[2.2]パラシクロファン (pcp)を配位子とする新規な９つのロジウムおよびイリジウム錯体 [Rh(η6-pcp)(C2H4)2]BF4、 [M(η6-pcp)(diene)]X (M=Rh and Ir; diene=1,5-シクロオクタジエン (cod)および 2,5-ノルボナジエン (nbd); X=BF4 and ClO4) and [M2(η:η6-pcp)(diene)2]X2を合成し、その固体および溶液内構造を明らかにした。 - A Novel Mn12 Single-Molecule Magnet [Mn12O12(OAc)12(dpp)4] [Not invited]黒田 孝義; Bian, G. Q; 小中 尚; 波多野 雅紀; 前川 雅彦; 宗像 惠36th International Conference on Coodination Chemistry 2004/07 Merida, Mexico 36th International Conference on Coodination Chemistry
- 拡がったπ系を有するSchiff base配位子を用いた新規鉄(II)スピンクロスオーバー錯体の合成と構造および磁性 [Not invited]黒田 孝義; 先崎 由蘭; 木下 同; 前川 雅彦; 宗像 惠; 杉本 邦久; 前田 米蔵日本化学会第８４春季年会 2004/03 関西学院大学（西宮） 日本化学会第８４春季年会
- ヒドロキシピリジンで架橋された新規Mn12核錯体の合成とその単一分子磁性 [Not invited]鍋井 淳宏; 黒田 孝義; 前川 雅彦; 宗像 惠日本化学会第８４春季年会 2004/03 関西学院大学（西宮） 日本化学会第８４春季年会
- Structure and Function of Silver Ⅰ Coordination Polymer with Aromatic Compounds [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 山崎裕二; 前川 雅彦第53 回錯体化学討論会（山形） 2003/09 第53 回錯体化学討論会（山形）
空孔内にゲスト分子としてphenanthlene を有する［2.2］paracyclophane のAg Ⅰ錯体高分子の合成に成功し、その結晶構造及びゲスト分子の可逆的吸着／脱着機能を明らかにした。 - Synthesis, Structure and Property of Porous Copper Ⅰ Complexes [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 伊藤富樹; 前川 雅彦第53 回錯体化学討論会（山形） 2003/09 第53 回錯体化学討論会（山形）
空孔を有する銅Ⅰ錯体の合成に成功した。この空孔にはメチルテトラヒドロフランが取り込まれており、可逆的に吸着／脱着することを明らかにした。 - Synthesis and magnetic property of Mn12 Single-Molecule Magnets with phosphinate bridge [Not invited]黒田 孝義; 宗像 惠; 波多野雅紀; 前川 雅彦第53 回錯体化学討論会（山形） 2003/09 第53 回錯体化学討論会（山形）
Mn12 核錯体をホスフィン酸で化学修飾を行ない、得られた化合物が単一分子磁性を示すことを明らかにした。 - Synthesis and magnetic property of Mn Ⅲ -phthalocyanate and its derivatives [Not invited]黒田 孝義; 宗像 惠; 上島弘義; 前川 雅彦第53 回錯体化学討論会（山形） 2003/09 第53 回錯体化学討論会（山形）
Mn- フタロシアニン錯体およびその誘導体を合成し、それらの極低温での磁性を調べた結果、反強磁性相互作用を有することがわかった。 - Structure and Photochromism of Silver Ⅰ Complexes with Diarylethene Derivative having Two Pyridyl Groups [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 郡島望; 前川 雅彦第53 回錯体化学討論会（山形） 2003/09 第53 回錯体化学討論会（山形）
ピリジル基を有するジアリールエテン誘導体BM-2-PTP を合成し、これを有する三種類のAg Ⅰ錯体の単結晶合成に成功した。その結晶構造及びフォトクロミック挙動を明らかにした。 - Syntheses, Structures and Photochromic Behaviors of Silver Ⅰ Coordination Polymers with Ring-closed Diarylethene [Not invited]宗像 惠; 黒田 孝義; 小中尚; 前川 雅彦第53 回錯体化学討論会（山形） 2003/09 第53 回錯体化学討論会（山形）
ジアリールエテン誘導体cis-dbe の閉環体を配位子とする新規Ag Ⅰ錯体の合成に成功した。cis-dbe のAg への配位様式の違いによってフォトクロミズムの反応速度が異なることを見出した。 - Synthesis and magnetic property of a novel Mn12 complex partially substituted by 2.aminopyridine [Not invited]黒田 孝義; 宗像 惠; 鍋井淳宏; 前川 雅彦第53 回錯体化学討論会（山形） 2003/09 第53 回錯体化学討論会（山形）
2. アミノピリジンで部分置換した新規Mn12 核錯体を合成し、その磁性測定から、単一分子磁石としての性質を有することを明らかにした。 - Synthesis and magnetic property of a novel Mn4 complex with coordination of 1,10-phenanthroline [Not invited]黒田 孝義; 宗像 惠; 鍋井淳宏; 前川 雅彦分子構造総合討論会（京都） 2003/09 分子構造総合討論会（京都）
1-10 フェナントロリン配位を有する新規Mn4 核錯体を合成しその構造と磁性を明らかにした。 - Synthesis and Structure of Porous Two-Dimensional CopperⅠComplexes with Dithiaparacyclophane [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 伊藤富樹; 前川 雅彦第83回春季年会（東京） 2003/03 第83回春季年会（東京）
空孔を有する二次元銅Ⅰ ジチアパラシクロファン錯体の合成に成功した。この空孔にはTHF及びアセトニトリルが取り込まれており、可逆的に吸着／脱着することを明らかにした。 - Mn12 Single.Molecule Magnets With Extended π.Conjugated Carboxylate Bridges [Not invited]黒田 孝義; 宗像 惠; 野上忠豊; 前川 雅彦; 山下正廣; 杉本邦久ナノ錯体国際会議（岡崎） 2003/03 ナノ錯体国際会議（岡崎）
拡がったπ系を有するカルボン酸を用いて新規Mn12核錯体を合成しそれらの単一分子磁性を調べた。 - Structural characterization of novel iridium complexes with polydentate nitrogen ligands in solution and in the solid state [Not invited]前川 雅彦; 黒田 孝義; 末永 勇作; 宗像 惠日本化学会第83春季年会（東京） 2003/03 日本化学会第83春季年会（東京）
2,3,5,6.テトラキス（2.ピリジル）.ピラジンを始めとする3種の多座窒素配位子を用いて5種の新規な単核および二核イリジウムヒドリド錯体を合成し、その溶液内および固体構造を単結晶X線構造解析、二次元NMR法、UV.VIS法などより特徴づけた。特にこれらの化合物は溶液内において隣の配位子からの環電流効果によると考えられる普通でない化学シフトを与えるを始めて見出した。 - Synthesis of Photochromic Dinuclear RhodiumⅡComplexes with Bisthienyl Maleimide. [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 稲葉季暁; 前川 雅彦第83回春季年会（東京） 2003/03 第83回春季年会（東京）
フォトクロミズムを有する2,3.ビス（2,4,5.トリメチル.3.チエニル）マレイミドのRhⅡ錯体の合成に成功し、単結晶X線構造解析により構造を明らかにし、フォトクロミズムと構造の関係を検討した。 - Structure and properties of silverⅠcoordination polymer with thiophenyl substituted aromatic compound [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦; 立花和徳; 小野昇; 谷弘幸 由徳大介日本化学会第83春季年会（東京） 2003/03 日本化学会第83春季年会（東京）
ナフタレン環の特定の位置にチオフェニル基を導入した有機配位子を合成した。その銀Ⅰ錯体の構造を単結晶X線構造解析により、明らかにした。 - Sythesis and Magnetic Property of a Novel Mn12 Complex brigded by Methylenediphosphonic acid. [Not invited]黒田 孝義; 宗像 惠; 波多野雅紀; 前川 雅彦日本化学会第83春季年会（東京） 2003/03 日本化学会第83春季年会（東京）
Mn12acとMethylenediphosphonic acid（mdpa）を反応させることにより、アセテートが一部mdpaに置換されたMn12mdpaを得た。この錯体の交流磁化率測定の結果、単一分子磁石の性質を有していることがわかった。 - Structures and Magnetic properties of a neutral and anionic Mn12 complexes bridged by 2.thiophenecarboxylic acid [Not invited]黒田 孝義; 宗像 惠; 野上忠豊; 小中尚; 前川 雅彦日本化学会第83春季年会（東京） 2003/03 日本化学会第83春季年会（東京）
2.チオフェンカルボン酸 を用いて Mn12 核錯体およびそのアニオンを合成し、それらの構造および物性を調べた。磁化率測定の結果、これらの錯体がいずれも単一分子磁石の性質を有していることがわかった。 - Novel Mn12 Single-Molecule Magnets With Methanesulfonate or Diphenyl-phosphate Bridges [Not invited]黒田 孝義; 宗像 惠; 福田智司; 飯田哲二; 前川 雅彦; 山下正廣; 宮第７回分子磁性国際会議（ICMM2002） （バレンシア） 2002/10 第７回分子磁性国際会議（ICMM2002） （バレンシア）
メタンスルホン酸及びジフェニルフォスフェートで架橋された二種の新規なMn12核錯体を合成し、それらの構造解析を行った。交流及び直流磁化の測定からこれらがいずれも単一分子磁石であることを明らかにした。（英文） - Structure and photo-induced property of Silver(I) coordination polymer with benzyl groups [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦第52回錯体化学討論会（東京） 2002/10 第52回錯体化学討論会（東京）
ベンゼン環の6つの水素原子を複数のベンジルチオエーテル基で置換した化合物を合成し、その銀Ⅰ錯体ポリマーの構造と性質について発表した。1,3,5?位のトリ置換体を用いると銀Ⅰ錯体ポリマーを形成することで、初めて光によるクロミック現象をしめすことが明らかになった。 - Structures and magnetic properties of nobel Mn12 single-molecule magnets with oxo bridges [Not invited]黒田 孝義; 宗像 惠; 飯田哲二; 小寺武裕; 前川 雅彦; 山下正廣; 宮分子構造総合討論会（神戸） 2002/10 分子構造総合討論会（神戸）
メタンスルホン酸及びジフェニルホスフェートで架橋された新規なMn12核錯体を合成し、その構造解析を行った。交流・直流磁化及び磁気ヒステリシスの測定からこの化合物が単一分子磁石であることを明らかにした。 - Syntheses of silverⅠcoordination polymer with 1,4,5,8?tetrathioether group substituted naphthalene ligand [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦; 立花和徳第52回錯体化学討論会（東京） 2002/10 第52回錯体化学討論会（東京）
ナフタレン環のすべての水素原子をチオフェニル基で置換した化合物は熱や圧力によって変色現象を示す、いわゆるクロミズムを発現する化合物であることから、ナフタレン環に位置選択的にチオフェニル基を導入した化合物を合成し、その性質および、金属錯体の性質について発表した。 - Synthesis and Structure of Porous CopperⅠComplexes with Dithi-aparacyclophane [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 伊藤富樹; 前川 雅彦第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
ヨウ化銅Ⅰと2,11?ジチアパラシクロファンを用いて空孔を有するCuⅠ錯体の合成に成功した。この空孔にはTHF及びアセトニトリルが取り込まれたポリマー構造であることを明らかにした。 - Structures and magnetic properties of nobel Mn12 single-molecule magnets with oxo bridges [Not invited]黒田 孝義; 宗像 惠; 飯田哲二; 小寺武裕; 前川 雅彦; 山下正廣; 宮第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
メタンスルホン酸で架橋された新規なMn12核錯体を合成し、その構造解析を行った。交流及び直流磁化及び磁気ヒステリシスの測定からこの化合物が単一分子磁石であることを明らかにした。 - Structures and magnetic properties of Mn12 single-molecule magnets with extended π?conjugated carboxylic acids [Not invited]黒田 孝義; 宗像 惠; 野上豊忠; 前川 雅彦第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
ナフタレンなどの拡張π系を有するカルボン酸で置換したMn12核錯体を合成し、それらの構造と磁性を明かにした。分子間のπ・π相互作用は存在するが単一分子磁性には影響を及ぼさないことが分かった。 - Syntheses and magnetic properties of iron complexes with extended π?conjugated Schiff-base ligands [Not invited]黒田 孝義; 宗像 惠; 先崎由蘭; 前川 雅彦第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
ナフタレン骨格を有するSchiff塩基を配位子とする鉄Ⅱ錯体の合成を行い、新規な2核錯体の生成を単結晶X線構造解析で明かにした。この化合物は220Kでスピンクロスオーバーを示した。 - Syntheses, structures and reactivity of novel iridiumⅢhydrido complexes with multidentate nitrogen ligands [Not invited]前川 雅彦; 友松大輔; 黒田 孝義; 宗像 惠第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
2, 4, 6?トリス（2?ピリジル）?1, 3, 5?トリアジン（tptz）を用いて単核および二核IrⅢヒドリド錯体、｛[Ir（H）2（PPh3）2（tptz）]PF6?, [Ir2（H）4（PPh3）4（tptz）]（PF6）2・2H2O?｝を合成し、溶液内および固体構造を単結晶X線構造解析法および二次元NMR法より詳細に検討した。 - Synthesis, crystal structure, and magnetic property of a novel Mn12 single-molecule magnet with diphenylphosphate bridges [Not invited]黒田 孝義; 宗像 惠; 福田智司; 三好真介; 前川 雅彦; 山下正廣; 宮第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
ジフェニルフォスフェートで架橋された新規なMn12核錯体を合成し、その構造解析を行った。交流及び直流磁化及び磁気ヒステリシスの測定からこの化合物が単一分子磁石であることを明らかにした。 - Synthesis of Photochromic Metal Complex with 1,2?Bis[4?methyl?2?（2?pyridyl）?5?thiazolyl]perfluorocyclopentene [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 小寺武裕; 前川 雅彦第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
AgⅠ錯体の合成に成功した。得られた錯体の構造をX線構造解析により明らかにした。構造は標記配位子に2つのAgが配位した二核構造を形成し、光照射によりフォトクロミズムを示すことを明らかにした。 - Syntheses and magnetic properties of Mn12 single-molecule magnets with Schiff-base ligands [Not invited]黒田 孝義; 宗像 惠; 成相伸明; 前川 雅彦第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
Schiff塩基を含むカルボン酸を架橋配位子とする新規なMn12核錯体を合成し、その磁性を調べた。いくつかの錯体は単一分子磁石としての特性を示した。 - Structures and Photochromism of cis?1,2?Dicyano?1,2?bis（2,4,5?trimethyl?3?thienyl）ethene?Diruthenium（Ⅱ,Ⅲ）Complex [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 石原弘道; 前川 雅彦第52回錯体化学討論会（東京） 2002/09 第52回錯体化学討論会（東京）
[Ru2（O2CC2H5）]（BF4）に表記配位子の閉環体を用いて新規混合原子価二核Ru（Ⅱ、Ⅲ）錯体の合成に成功した。この錯体は、521mmと405mmの光照射によりフォトクロミズムを示すことを見出した。 - Synthesis and structure of novel rhodium and iridium complex with [2. 2] paracyclophane [Not invited]前川 雅彦; 黒田 孝義; 宗像 惠第49回有機金属討論会（神戸） 2002/09 第49回有機金属討論会（神戸）
[2. 2]パラシクロファン（pcp）を用い、新規な11種のロジウムおよびイリジウム錯体｛[M（pcp）（diene）2]＋，[M2（pcp）（diene）2]2＋，[M（pcp）（Cp＊）]2＋（M＝Rh and Ir；diene＝1, 5?cyclooctadiene，nbd＝2, 5?norbonadiene）｝を系統的に合成し、そのX線結晶構造および性質を明らかにした。 - Syntheses and crystal structures of mononuclear [2. 2] paracyclophane com-plexes of rhodium and iridium supported by the pentamethylcyclopentadienyl ligand [M（η6?pcp）（η6?C5Me5）] （BF4）2 （M＝Rh and Ir） [Not invited]前川 雅彦; 黒田 孝義; 末永 勇作; 宗像 惠The 35th International Conference on Coordination Chemistry（ドイツ） 2002/07 The 35th International Conference on Coordination Chemistry（ドイツ）
支持配位子としてペンタメチルシクロペンタジエニルアニオン（Cp＊）を用いて、 [2. 2]パラシクロファン（pcp）の単核RhⅢおよびIrⅢ錯体[M（η6?pcp）（η6?C5Me5）]（BF4）2 （M＝Rh ? and Ir ?）を合成し、そのX線結晶構造を始めて明らかにした。 - Crstal structure and photo?induced property of one, two?dimensional silverⅠcomplexes with poly（benzylsulfanyl）benzene [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦; 杉本威史XXXVth. International Conference on Coordination Chemistry（ドイツ） 2002/07 XXXVth. International Conference on Coordination Chemistry（ドイツ）
ベンゼン環の6つの水素原子を複数のベンジルチオエーテル基で置換した化合物を合成し、その銀Ⅰ錯体ポリマーの構造と性質について発表した。（英文） - A NOVEL Mn12 SINGLE-MOLECULE MAGNET WITH DIPHENYL-PHOSPHATE BRIDGES [Not invited]黒田 孝義; 宗像 惠; 福田智司; 三好真介; 前川 雅彦; 山下正廣; 宮第35回配位化学国際会議（ICCC35） （ハイデルベルグ） 2002/07 第35回配位化学国際会議（ICCC35） （ハイデルベルグ）
4つのジフェニルフォスフェートで架橋された新規なMn12核錯体を合成し、その構造解析を行った。交流及び直流磁化の測定からこの化合物が単一分子磁石であることを明らかにした。（英文） - Solvent-dependent formation of di- and trinuclear rhodium and iridium complexes bridged by N, N donor ligands [Not invited]前川 雅彦; 森田智典; 于暁燕; 張浩徹; 北日本化学会第 81 春季年会 （東京） 2002/03 日本化学会第 81 春季年会 （東京）
ピラジンを始めとする 3 種の窒素橋かけ配位子とロジウムおよびイリジウムヒドリド錯体 [M（H）2（PPh3）2（solvent）2]＋ （M＝Rh, Ir） を種々の溶液中で反応させ、 溶媒選択的に 6 種の二核、 三核ロジウムおよびイリジウム錯体が生成することを見いだし、 これら生成物を X 線構造解析、 IR、 NMR、 UV VIS 法などより特徴づけた。 - The magnetic property of Fe-complexes coordinated by Schiff base ligand with extended π system [Not invited]黒田 孝義; 宗像 惠; 先崎由蘭; 前川 雅彦日本化学会第 81 春季年会 （東京） 2002/03 日本化学会第 81 春季年会 （東京）
拡がったπ系を有するシッフ塩基を用いて新規 FeおよびFe錯体を合成した。 いずれも 200 K から 300 K でスピンクロスオーバー現象が見られた。 - Magnetic property of Mn12 complexes bridged by carboxylates with extended π conjugated system [Not invited]黒田 孝義; 宗像 惠; 野上忠豊; 前川 雅彦日本化学会第 81 春季年会 （東京） 2002/03 日本化学会第 81 春季年会 （東京）
π共役系の配位子として 2 ナフタレンカルボン酸を用いて Mn12 核錯体を合成し、 その物性を調べた。 磁化率測定の結果、 この錯体が単一分子磁石の性質を有していることがわかった。 - Structure and thermal transition behavior of tiophenyl substituted aromatic compound [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦; 植田篤斉日本化学会第 81 春季年会 （東京） 2002/03 日本化学会第 81 春季年会 （東京）
ナフタレン環のすべての水素原子をチオフェニル基で置換した化合物は熱や圧力によって変色現象を示す、 いわゆるクロミズムを発現する化合物であるが、 黄色体と赤色体の単結晶 X 線構造解析からそれぞれの構造を明らかにし、 さらに熱測定による転移現象を解析し、 発表した。 - Synthesis of Photochromic Molybdenum Complexes with Bis （thienyl） maleimide [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 小寺武裕; 前川 雅彦日本化学会第 81 回春季年会 （東京） 2002/03 日本化学会第 81 回春季年会 （東京）
フォトクロミズムを有する 2, 3 bis （2, 4, 5 trimethyl 3 thienyl） maleimide （open bttm） 及び closed bttm を用いて 2 種の一次元 Mo錯体ポリマー [Mo2（open bttm）（CF3COO）4]、 [Mo2（closed bttm）（CF3COO）4] の合成に成功した。 - Structure and properties of copper complex with thiophenylether substituted aromatic ligands [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦; 植田篤斉日本化学会第 81 春季年会 （東京） 2002/03 日本化学会第 81 春季年会 （東京）
ナフタレン環のすべての水素原子をチオフェニル基で置換した化合物の変色現象を粉末 X 線、 熱測定、 固体反射スペクトルから明らかにしたうえで、 その銅錯体を合成し、 性質について発表した。 - Structure and Magnetic Property of Novel Mn12 Nuclear Complex Partially Substituted by Diphenylphosphate [Not invited]黒田 孝義; 宗像 惠; 福田智司; 飯田哲二; 三好真介; 前川 雅彦日本化学会第 81 春季年会 （東京） 2002/03 日本化学会第 81 春季年会 （東京）
Mn12 安息香酸錯体に対して 4 等量の Diphenylphosphate を反応させる事により、 4 つの安息香酸がジフェニルホスフェートで置換した新規な Mn12 核錯体が得られた。 交流磁化率測定の結果、 この錯体が単一分子磁石の性質を有していることがわかった。 - Structuers and Physical Properties of Copper Iodine Mixed-metal Complex Polymers Bridged by Dithiocarbamate Complex [Not invited]黒田 孝義; 宗像 惠; 糸井裕人; 三好真介; 前川 雅彦日本化学会第 81 春季年会 （東京） 2002/03 日本化学会第 81 春季年会 （東京）
金属ジチオカルバマト錯体とヨウ化銅の反応により、 新規混合金属錯体ポリマーの合成に成功した。 これらはヨウ化銅の一次元鎖がジチオカルバマト錯体によって架橋された二次元、 または三次元構造であった。 - Structure and Photochromism Dimolybdenum Complex and Dirhodium Complexes with cis 1, 2 Dicyano 1, 2 Bis （2, 4, 5 Trimethyl 3 Thienyl） Ethene [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 石原弘道; 前川 雅彦日本化学会第 81 回春季年会 （東京） 2002/03 日本化学会第 81 回春季年会 （東京）
cis 1, 2 dicyano 1, 2 bis （2, 4, 5 trimethyl 3 thienyl） ethene の開環体 cis dbe を用いてフォトクロミズムを有する一次元二核 Rh錯体 [Rh2（CF3COO）4（cis dbe）] （benzene） の合成に成功した。 また閉環体 closed dbe の一次元二核 Rh錯体 [Rh2（CF3COO）4（closed dbe）] （p xylene） も合成した。 - Efects of Metal Complexes and Antimicrobial Conpounds on Longevity of Cut-Gerbera Flowers [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 海老原正也; 前川 雅彦日本化学会第 81 回春季年会 （東京） 2002/03 日本化学会第 81 回春季年会 （東京）
我々は、 カーネーションの切り花に Ag錯体を与えると、 花持ちが約 2 倍長くなることを見出している。 今回、 ガーベラの切り花に種々の Ag錯体を与え、 花持ちに及ぼす効果を検討した。 - Syntheses of metal complexes with star-burst molecule consisting of π electron system [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦; 松岡康一2002/03分子が三方向に伸張した 4 種のスターバースト型の分子を合成し、 その構造を明らかにした。 また、 熱測定から相変化について考察した。 さらに、 銀錯体の合成を行ない、 構造と性質について発表した。
- Search for Ethylene Binding Protein as a Marker of Ag Ions [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 大段友紀子; 前川 雅彦日本化学会第 81 回春季年会 （東京） 2002/03 日本化学会第 81 回春季年会 （東京）
[Ag（S2O3）2]3 － を吸収させたモヤシの子葉を種々の処理の後、 Agイオンの存在量を ICP AES により測定した。 また、 さらにガスクロマトグラフィーによりエチレン吸収量を求め、 エチレン受容体の探索を行った。 - Synthesis and structure of novel rhodium and iridium complex with [2.2] paracyclophane [Not invited]前川 雅彦; 橋本 直樹; 黒田 孝義; 末永 勇作; 宗像 惠第 51 回錯体化学討論会 （島根） 2001/09 第 51 回錯体化学討論会 （島根）
［2.2］ パラシクロファン （pcp） を用い、 新規な二核 Rh 錯体 ［Rh2 （nbd） 2 （pcp）］ （BF4） 2 を合成した。 錯体 1 は Rh が pcp のベンゼン環の両側に η6 配位した二核構造を形成している。 また錯体 1 の反応溶液の 1HNMR 測定を行ったところ反応溶液中では二核錯体と共に単核錯体 ［Rh （nbd） （pcp）］ BF4 が生成していることを見出した。 - Physical propertis of Mn12 complexes with basic carboxylic bridges [Not invited]黒田 孝義; 宗像 惠; 野上忠豊; 前川 雅彦第 51 回錯体化学討論会 （松江） 2001/09 第 51 回錯体化学討論会 （松江）
塩基性度の高いカルボン酸で置換した Mn12 核錯体を合成しその置換基の種類と構造・磁性の相関を調べた。 その結果、 カルボン酸の塩基性度は Mn12 核錯体の磁性に顕著な影響を及ぼさないことを明らかにした。 - Syntheses and structures of novel iridium complexes bridged by multidentate nitrogen ligands [Not invited]前川 雅彦; 森田智典; 宗像 惠; 北川進第 51 回錯体化学討論会 （島根） 2001/09 第 51 回錯体化学討論会 （島根）
テトラ 2 ピリジニルピラジン （tpypz） および 4′,4′′′′ （1， 4 フェニレン） ビス （2， 2′:6′,2′′ ターピリジン） （pbtpy） を用いて二核 Ir ヒドリド錯体 ［Ir2 （H） 4 （PPh3） 4 （tpypz）］ （BF4） 2 および ［Ir2 （H） 4 （PPh3） 4 （pbtpy）］ （BF4） 2 を合成し、 その構造および性質を明らかにした。 - The Synthesis of 1 D Cu/Au Mixed Metal Complex Polymer [Not invited]宗像 惠; 黒田 孝義; 米本涼恵; 前川 雅彦第 51 回錯体化学討論会 （松江） 2001/09 第 51 回錯体化学討論会 （松江）
1, 4, 8, 11 tetraazacyclotetradecane （cyclam） の銅 錯体 [Cu （cyclam） ] （ClO4） 2 を合成し、 これと K [Au （CN） 2] を用いて Cu および Au が CN 基で架橋された一次元混合金属錯体 [Cu （cyclam） Au2 （CN） 4] の構築に成功した。 - Synthesis and structure of silver coordination polymer with thiobenzylether group substituted aromatic compounds [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦; 杉本威史第 51 回錯体化学討論会 （松江） 2001/09 第 51 回錯体化学討論会 （松江）
ベンゼン環に複数のベンジルチオエーテル基をもつ化合物には光照射によって黄色から赤色に変わるクロミック現象を示すものが知られている。 本研究では金属錯体を合成し、 その構造と性質を明らかにすることを目的にした。 銀錯体では銀には硫黄原子が配位しており、 全体として一次元鎖構造を形成していた。 クロミック現象を有する金属錯体ポリマーを見出した。 - Synthesis and properties of copper coordination polymer with thiophenylether group substituted aromatic compounds [Not invited]末永 勇作; 黒田 孝義; 宗像 惠; 前川 雅彦; 二宮康彰; 植田篤斉第 51 回錯体化学討論会 （松江） 2001/09 第 51 回錯体化学討論会 （松江）
側鎖にかさ高い置換基をもつナフタレンを配位子に銅錯体ポリマーを合成し、 単結晶 X 線構造解析を行なった。 その結果、 銅と塩素原子からなる五角形三核ユニットと配位子が交互に連結された一次元構造を形成していることが明らかになった。 ナフタレン骨格は約 31°ねじれており、 先に合成した銀錯体と比較検討した結果を報告した。 - Synthesis of Silver π Complexes with Diphenyl Derivatives [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 中川久雄; 前川 雅彦第 51 回錯体化学討論会 （松江） 2001/09 第 51 回錯体化学討論会 （松江）
1, 8 diphenyl 1, 3, 5, 7 octatetraene （dpot） と 4, 4 diethoxydiphenyl （dedp） の Agπ錯体 {[Ag2 （dpot） （ClO4） 2], [Ag （dedp） （CF3SO3)]} を合成し、 前者は metallocyclophane 構造を有する極めて興味ある化合物であることを明らかにした。 - Syntheses and Structures of Cu Complex Polymers Bridged by Dithiolato Complexes [Not invited]黒田 孝義; 宗像 惠; 奥谷貴志; 糸井裕人; 三好真介; 前川 雅彦第 51 回錯体化学討論会 （松江） 2001/09 第 51 回錯体化学討論会 （松江）
ジメチルジチオカルバマト錯体 [M （Me2dtc） 2] （M = Ni, Pd） とヨウ化銅の反応により、 二次元シート構造を有する新規錯体ポリマー [M （Me2dtc） 2Cu4I4] の合成に成功した。 - Structure and Photochromism of cis 1, 2 Dicyano 1, 2 bis （2, 4, 5 trimethyl 3 thienyl） ethene Dinuclear Molybdenum Complexes [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 石原弘道; 前川 雅彦第 51 回錯体化学討論会 （松江） 2001/09 第 51 回錯体化学討論会 （松江）
cis 1, 2 dicyano 1, 2 bis （2, 4, 5 trimethyl 3 thienyl） ethene の閉環体 closed-dbe を用いたフォトクロミック一次元二核 Mo 錯体 [{Mo2 （CF3COO） 4} 2 （closed-dbe） 2] の合成に成功した。 開環体 cis dbe の二核 Mo 錯体 [Mo2 （CF3COO） 4 （cis dbe） ] （benzene） も合成した。 - Syntheses and structures of novel iridium complexes with terphenyl [Not invited]前川 雅彦; 黒田 孝義; 宗像 惠; 三浦裕介第 51 回錯体化学討論会 （島根） 2001/09 第 51 回錯体化学討論会 （島根）
ρ Terphenyl （terph） を用いて新規な Ir 錯体 ｛［Ir （η6 terph） （cod） 2］ （BF4） 2｝ 3 を合成し、 その X 線構造および性質を明らかにした。 錯体 1 は単位格子中に異なる 3 分子の ［Ir （η6 terph） （cod） 2］ （BF4） 2 を含み、 いずれも terph の 3 つのベンゼン環の両側のベンゼン環の上下より Ir が η6 配位した二核錯体であることを明らかにした。 - Synthesis of Silver Complex Derived from 2, 3 Bis （2, 4, 5 trimethyl 3 thienyl） maleic anhydride [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 豊島康孝; 前川 雅彦第 51 回錯体化学討論会 （松江） 2001/09 第 51 回錯体化学討論会 （松江）
フォトクロミズムを有する 2, 3 bis （2, 4, 5 trimethyl 3 thienyl） maleic anhydride （bma） を用いて、 一次元構造を有する Ag 錯体 [Ag2 （closed-bma） （CF3COO） 2]n の合成に成功した。 この錯体は 550 nm の光照射で閉環体から開環体へ変化することを見出した。 - Synthesis and structure of metal coordination polymer with trinaphthene derivatives [Not invited]末永 勇作; 黒田 孝義; 宗像恵; 前川 雅彦; 杉本威史日本化学会第 79 春季年会 (神戸) 2001/03 日本化学会第 79 春季年会 (神戸)
1, 4 ジチイン環骨格を有する芳香族化合物を合成し､ その金属錯体ポリマーの構造と性質について発表した｡ - Triple-decker, Spiral and Herringbone Silver ■ Complexes of Benzopyrene and the Derivatives [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 仲劍初; 前川 雅彦日本化学会 第 79 回春季年会 (神戸) 2001/03 日本化学会 第 79 回春季年会 (神戸)
ベンゾピレン及びその誘導体を用いて新規骨格を有する三層構造､ らせん構造およびヘリボーン構造の Ag ■ 錯体を構築し､ その物性､ 特に電気伝導性とπ-π stack との関係を検討した｡ - Synthesis of Photochromic Silver ■ Complexes with Bisthienylmaleic Anhydride [Not invited]宗像 惠; 黒田 孝義; 豊島康孝; 前川 雅彦日本化学会 第 79 回春季年会 (神戸) 2001/03 日本化学会 第 79 回春季年会 (神戸)
2, 3 bis (2, 4, 5 trimethyl 3 thienyl) maleic anhydride (bma) を用いてフォトクロミズムを有するAg(I)錯体 [Ag4(bma)(CF3COO)4] の合成に成功した｡ 405nmの光照射を行うと黄色の開環体から赤色の閉環体への変化し､ 546nmの光照射で元の開環体に戻った｡ - Synthesis and Structure of Three Dimensional Silver ■ p Complexes with Biphenylene [Not invited]宗像 惠; 黒田 孝義; 中川久雄; 前川 雅彦日本化学会 第 79 回春季年会 (神戸) 2001/03 日本化学会 第 79 回春季年会 (神戸)
従来合成困難と考えられていた biphenylene (bph) の Ag ■ π錯体 [Ag(dph)(ClO4)] の合成に成功した｡ Ag はそれぞれ η2 様式で bph の 2 分子及び 2 つの ClO－4 の酸素原子が配位した4面体構造をとっており､ これを基本単位とした新規 3 次元ネットワーク構造が構築できた｡ - Effect of Silver■ Complexes on Ethylene-Promoted Flower Blooming and Longevity ■ : Ethylene Activity Inhibition [Not invited]宗像 惠; 黒田 孝義; 末永 勇作; 米本涼恵; 井野一朗; 生地伸光; 久保麻威工; 前川 雅彦日本化学会 第 79 回春季年会 (神戸) 2001/03 日本化学会 第 79 回春季年会 (神戸)
つぼみのバラの切り花に各種銀(I)錯体を吸収させた後､ 外部から20 ppm エチレンを与え､ 開花及び花持ちに及ぼす効果を検討した｡ カーネーションと同様にバラでも [Ag(CN)2]－及び [Ag(S2O3)2]3－ はエチレン活性阻害作用を示し､ 花持ちが長くなることを見出した｡ - Optical and magnetic properties of a charge-transfer complex between a Mn12 single-molecule magnet and a TTF derivative [Not invited]黒田 孝義; 宗像 惠; 杉本恵子; 前川 雅彦; David N. Hendrickson日本化学会 第 79 春季年会 (神戸) 2001/03 日本化学会 第 79 春季年会 (神戸)
Mn12 核錯体と TTF 誘導体との電荷移動錯体を合成した｡ 結晶は暗黒赤色で 520 nm 付近に強い吸収を示し､ また磁化率測定の結果からこの結晶も単一分子磁石としての性質を持っていると考えられる｡ - Syntheses and structures of rhodium and iridium paracyclophane complexes with Cp＊ as a support ligand [Not invited]前川 雅彦; 橋本 直樹; 佐藤徹馬; 黒田 孝義; 末永 勇作; 宗像 惠日本化学会第 79 春季年会 (神戸) 2001/03 日本化学会第 79 春季年会 (神戸)
パラシクロファン (pcp) 錯体 [RhCp＊(pcp)](BF4)2 ■ および [Ir2(Cp＊)2(pcp)](BF4)4 ■ を合成し､ その構造および性質を調べた｡ 錯体 1 は X 線構造解析より pcp のベンゼン環の片側にのみ Rh が配位した単核構造を錯体 2 は 1H NMR および IR より pcp のベンゼン環の両側に Ir が配位した二核構造を形成していることが示された｡ - Syntheses and structures of di and trinuclear iridium complexes bridged by 4, 4′ bipyridine analogues [Not invited]前川 雅彦; 森田智典; 宗像 惠; 北川進日本化学会第 79 春季年会 (神戸) 2001/03 日本化学会第 79 春季年会 (神戸)
橋かけ配位子としてビピリジン類縁化合物である長いスペーサー部分を有する 4, 4′ トリメチレンピリジン (tmdp) を用い､ 新規三核イリジウム錯体 [Ir3(H)6(PPh3)6(tmdp)3](PF6)3 ■ を合成し､ その構造および性質を明らかにした｡ 錯体 1 の構造は 3 つのイリジウム原子が 3 つの tmdp により架橋され Ir3 コアを有する三核錯体を形成しており､ Ir3 コアの中心には対アニオンである PF6 が取り込まれている｡ - Synthesis and structure of metal coordination polymer with piezochromism [Not invited]末永 勇作; 黒田 孝義; 宗像恵; 前川 雅彦; 小島憲道; 松下科研費特定領域研究 (A) ｢集積型金属錯体｣ 第 2 回錯体化学若手研究者講演会 (札幌) 2001/02 科研費特定領域研究 (A) ｢集積型金属錯体｣ 第 2 回錯体化学若手研究者講演会 (札幌)
圧力によって色の変化する有機化合物は数多く知られているが､ 本講演では銀(I)錯体ポリマーが高圧下で可逆的に色が変化することを構造との関係で発表した｡
MISC
- Valence tautomeric behavior of tri-nuclear mixed-valence CoIII/CoII complex containing 2,3,6,7,10,11-hexahydroxytriphenylene (H6L)Y. Suenaga; M. Inomata; S. Yabumoto; R. Yamaguchi; T. Okubo; M. Maekawa; T. Kuroda-Sowa 近畿大学理工学研究所研究報告 30- 1 -10 2018
- K. Tanshima; H. Anma; T. Okubo; M. Maekawa; T. Kuroda-Sowa Annual reports by Research Institute for Science and Technology 29- (29) 11 -16 2017/02
- 谷嶋晃樹; 野田祐輔; 中山将伸; 杉本邦久; 大久保貴志; 前川雅彦; 黒田孝義 錯体化学会討論会講演要旨集 66th- 2016
- K. Himoto; T. Okubo; M. Maekawa; T. Kuroda-Sowa 近畿大学理工学総合研究所研究報告 27- (27) 43 -47 2015/02
- Y. Nakahashi; S. Suzuki; Y. Ota; T. Okubo; M. Maekawa; T. Kuroda-Sow 近畿大学理工学総合研究所研究報告 27- (27) 35 -41 2015/02
- Suenaga Yusaku; Ueda Shyogo; Umehata Yukiko; Maekawa Masahiko 近畿大学理工学総合研究所研究報告 27- (27) 25 -34 2015/02
- Yu Zhong; Kuroda-Sowa Takayoshi; Okamoto Akihiro; Nabei Atsuhiro; Okubo Takashi; Maekawa Masahiko Science and technology 25- (25) 11 -19 2013/02
- OKUBO Takashi; TANAKA Naoya; MAEKAWA Masahiko; KURODA-SOWA Takayoshi Science and technology 24- (24) 53 -57 2012/02
- KIM Ho Kyung; INUZUKA Yoshie; OKUBO Takashi; MAEKAWA Masahiko; KURODA-SOWA Takayoshi Science and technology 23- (23) 19 -22 2011/02
- Suenaga Yusaku; Hirano Yasuhiro; Umehata Yukiko; Kamei Kuniaki; Maekawa Masahiko Science and technology 23- (23) 23 -33 2011/02
- 山野 江梨奈; 藤野 治; 前川 雅彦 Science and technology 22- (22) 27 -33 2010/02
- 富永 登志; 前川 雅彦; 大久保 貴志; 黒田 孝義; 宗像 惠 Science and technology 22- (22) 35 -40 2010/02
- Suenaga Yusaku; Umehata Yukiko; Minematsu Toshie; Maekawa Masahiko Science and technology 21- (21) 35 -43 2009/02
- 有田 伸也; 藤野 治; 前川 雅彦 Science and technology 21- (21) 53 -58 2009/02
- Fujino Osamu; Orimi Kazuhiro; Maekawa Masahiko Science and technology 20- 17 -20 2008/02
- Fujino Osamu; Maekawa Masahiko; Kawahigashi Tatsuo; Minami Takeshi; Nakaguchi Yuzuru; Yamazaki Hideo Science and technology 18- 29 -33 2006/02
- 2-D silver(I) coordination polymer with octakis(benzylsulfanyl)naphthalene and twisted naphthalene structure近畿大学理工学総合研究所研究報告 18- 47 2006
- Maekawa Masahiko; Suenaga Yusaku; Kuroda-Sowa Takayoshi; Munakata Megumu; Konaka Hisashi Science and technology 16- 21 -24 2004/02
- Suenaga Yusaku; Konaka Hisashi; Sugimoto Takeshi; Miyako Emi; Kuroda-Sowa Takayoshi; Maekawa Masahiko; Munakata Megumu Science and technology 15- 25 -33 2003/02
- Maekawa Masahiko; Suenaga Yusaku; Kuroda-Sowa Takayoshi; Munakata Megumu Science and technology 15- 47 -55 2003/02
- 前川 雅彦; 末永 勇作 理工学総合研究所研究報告 (15) 77 -84 2003/02
- Suenaga Yusaku; Sugimoto Takeshi; Katoh Kazuo; Higashino Kenji; Murakami Tomomi; Shimamaru Yusuke; Kuroda-Sowa Takayoshi; Maekawa Masahiko; Munakata Megumu Science and technology 14- 25 -33 2002/02
- Crystal structure of 9,10-bis(phenylethynyl)anthracene近畿大学理工学総合研究所研究報告, 12, 27-30- 2000
- Crystal structure of 3, 6-bis (dimethylamino) acridine hydroperchloride (acridine orange・ HCIO4)近畿大学理工学総合研究所研究報告, 11, 29-32.- 1999
- Maekawa Masahiko; Munakata Megumu; Kuroda-Sowa Takayoshi; Suenaga Yusaku Science and technology 10- 49 -54 1998/02
- Maekawa Masahiko; Munakata Megumu; Kuroda-Sowa Takayoshi; Suenaga Yusaku Science and technology 9- 45 -51 1997/03
- Munakata Megumu; Maekawa Masahiko; Kuroda-Sowa Takayoshi Journal of the Faculty of Science and Technology, Kinki University 31- 17 -23 1995/10
- Munakata Megumu; Kuroda-Sowa Takayosi; Maekawa Masahiko Journal of the Faculty of Science and Technology, Kinki University 30- 55 -61 1994/10
- ビニルフェロセンが配位した新規銅(I)錯体の合成、構造および性質近畿大学理工学部研究報告 29, 31- 1993
- 109Ag核磁気共鳴スペクトルに及ぼす溶媒の効果近畿大学環境科学研究所研究報告 20, 247- 1992
- 2,6-ジアミノピリジンを有する銀(I)二核錯体の合成と構造近畿大学環境科学研究所研究報告 20, 295- 1992
- Munakata Megumu; Kitagawa Susumu; Maekawa Masahiko Report of the Environmental Science Research Institute, Kinki University 19- 247 -250 1991/10
- NMR法による遷移金属の状態分析近畿大学環境科学研究所研究報告 18, 317- 1990
- Maekawa Masahiko; Kitagawa Susumu; Munakata Megumu Journal of the Faculty of Science and Technology, Kinki University 25- 103 -108 1989/09
- 2,2'-ビキノンの銅(I)錯体の合成とサーモクロミズム近畿大学理工学部研究報告 25, 81- 1989
- Munakata Megumu; Maekawa Masahiko; Kitagawa Susumu Journal of the Faculty of Science and Technology, Kinki University 24- 57 -62 1988/09
- Kitagawa Susumu; Maekawa MasahikoMunakata Megumu Journal of the Faculty of Science and Technology, Kinki University 24- 63 -67 1988/09
- 前川 雅彦; 北川 進; 宗像 恵 日本化学会誌 1988- (4) p438 -444 1988/04
Research Grants & Projects
- ヘテロ金属メタラマクロサイクリック・配位高分子の構築と機能Japan Society for the Promotion of Science：Grant-in-Aid for Scientific Research (C)Date (from‐to) : 2014/04 -2017/03Author : MAEKAWA Masahiko
- 高度に自己組織化されたメタラマクロサイクリックの精密合成と機能Japan Society for the Promotion of Science：Grant-in-Aid for Scientific Research (C)Date (from‐to) : 2011/04 -2014/03Author : MAEKAWA Masahiko
- Japan Society for the Promotion of Science：Grants-in-Aid for Scientific ResearchDate (from‐to) : 2008/04 -2010Author : MAEKAWA MasahikoThe C2H4 adducts of novel 13 Cu(I) coordination polymers and metallamacrocycles were self-assembled by the combinations of parent Cu(I) complexes with different counter anions and three 4,4'-bipyrimidine derivatives. The roles of counter anions and reaction solvents were systematically proved in the formation processes. These new compounds are expected to become as a potential anion receptor. In addition, thermally stable polynuclear Cu(I) ethylene adducts are useful to construct the chemical adsorption and the catalytic reaction sites.
- Japan Society for the Promotion of Science：Grants-in-Aid for Scientific ResearchDate (from‐to) : 2002 -2003Author : MAEKAWA MasahikoWe systematically prepared nine[2.2]paracyclophane complexes of Rh and Ir,[Rh(η^6-pcp)(C_2H_4)_2]BF_4・thf 1・thf (pcp=[2.2]paracyclophane),[Rh(η^6-pcp)(diene)]BF_4 (diene=1,5-cyclooctadiene (cod) 2・CH_2Cl_2;2,5-norbornadiene (nbd) 3),[Rh2(η^6,η^6-pcp)(diene)_2](BF_4)_2 (diene=cod 4;nbd 5),[Ir(η^6-pcp)(cod)]X (X=BF_4 6a;ClO_4 6b・CH_2Cl_2) and [Ir2(η^6,η^6-pcp)(cod)_2]X_2 (X=BF_4 7a;ClO_4 7b), seven structures of which were crystallographically characterized. In complexes 1・thf,2・CH_2Cl_2,3 and 6b・CH_2Cl_2, each of the Rh or Ir atoms are η^6-bonded to the upper side of the two decks in the pep ligand to afford a mononuclear structure. The average interannular distances between the two decks are 3.03(1・thf),3.01 (2・CH_2Cl_2),3.04 (3)and 3.01 Å(6b・CH2Cl2), respectively. In complexes 4,5 and 7b, two Rh or Ir atoms are η^6-coordinated to the upper and lower decks in the pep ligand to provide a dinuclear structure. The average interannular distances between the two decks are 3.04(4),3.05(5)and 3.05 Å (7b),respectively. On complexes 1・thf-7b, the average interannular distances of 3.01 to 3.05 Å between the two decks were found to be shorter than that(3.09 Å) of the metal-free pep ligand, suggesting that the repulsive π-interaction between the two decks is reduced by the coordination of the metal fragment with the diene ligand to the pep ligand. In addition, the relationships between the intramolecular distances and the configuration of the two ethylenic bridges were quite obvious. If the interannular distance was shorter than 3.05 Å, the configuration of the two ethylenic bridges was more likely a twisted cross type, and if the interannular distance was shorter than 3.01 Å, the configuration was more likely a parallel type, accompanying with the structure conversion of the two ethylenic bridges and the slide of the two decks. Novel two indium terphenyl complexes were also prepared and their structures were characterized crystallographically. The reaction of [Ir(cod)_2]BF_4 with p-terphenyl(p-tp) in CH_2Cl_2 to afford dinuclear Ir(I) complex {[Ir_2(p-tp)(cod)_2](BF_4)_2・2CH_2Cl_2}_3(8・2CH_2Cl_2), whereas the reaction of the intermediate [Ir(η5-C_5Me_5)(M_2CO)_3]^<3+> in Me_2CO with m-terphenyl(m-tp) to provide mononuclear Ir(III) complex [Ir(m-tp)(η^5-C_5Me_5)](BF_4)_2 (9).In complex 8・2CH_2Cl_2 two Ir atoms are η^6-coordinated to both sides of terminal benzene rings from the upper and lower sides in the p-tp ligand, while one Ir atom is η^6-coordinated to one side of the terminal benzene ring in the m-tp ligand in complex 9.Each crystal structure described the first coordination mode found in metal complexes with the m-and p-tp ligands.
- 日本学術振興会：科学研究費助成事業Date (from‐to) : 1997 -1998Author : 前川 雅彦金属イオン(Cu(I),Ag(I),Rh(I))と2種のロッド型有機系配位子(1,4-ビス(4-ピリジル)ブタジィン (4-pbd)ならびに1,4-ビス(4′-ピリジルエチニル)ベンゼン(2-pbd))を用いて新規な金属錯体ポリマーを系統的に合成し、その分子構造を明らかにした。 (1) 4-bpbを用いたCu(I)ならびにAg(I)金属錯体ポリマーの構築と分子構造 [Cu(CH_3CN)_4]PF_6,AgCF_3SO_3ならびAgClO_4と4-pbdを反応させ、{[Cu_2(4-pbd)_3(CH_3CN)_2](PF_6)_2}_n(1), {[Ag(4-pbd)](CF_3SO_3)}_n。(2),{[Ag(4-pbd)](ClO_4)}_n(3)の単離・構造決定を行なった。錯体1はCu原子が4-pbdの両端のピリジン環のN原子に順次橋かけされジグザグ型のはしご型一次元無限鎖構造を形成し、この一次元無限鎖がさらにお互い絡みあい、interwoven二次元シート構造を形成している。また錯体2および3はAg原子が4-pbdの両端のピリジン環のN原子により順次橋かけされ、直線型一次元無限鎖構造を形成している。 (2) 2-bpbを用いたCu(I)ならびにAg(I)金属錯体ポリマーの構築と分子構造 [CU(CH_3CN)_4]PF_6ならびにAgCF_3SO_3と2-pbdを用いて金属錯体ポリマーの合成を試み、{[CU(2-pbd)]BF_4}_n(4)および{[Ag(2-pbd)CF_3SO_3]}_n(5)の単離・構造決定を行なった。錯体4はCu原子が2-pbdのピリジン環の両端のN原子により順次橋かけされ3次元ネットワーク構造を形成しており、また錯体5は各々のAgが2-bpdの両端のピリジン環のN原子により順次橋かけされ螺旋状に1次元鎖構造を形成し、さらにこの1次元鎖がCF_3SO_3により橋かけされて2次元シート構造を形成している。 (3) 4-pbdを用いたRh(I)錯体金属のポリマーの構築と分子構造 [Rh(cod)_2]X(cod=1,5-シクロオクタジエン;X=BF_4,PF_6)を用いて金属錯体ポリマーの合成を試み、{[RF(4-pbd)X}_n(X=BF_4(6);PF_6(7))の単離・構造決定を行なった。錯体6および7はRh原子が4-pbdの両端のピリジン環のN原子に順次橋かけされジグザグ型の一次元無限鎖構造を形成している。
- 日本学術振興会：科学研究費助成事業Date (from‐to) : 1994 -1994Author : 前川 雅彦金属イオンを含む分子集合体は電気伝導性化合物に代表されるように多種多様な立体構造と酸化状態を取ることが可能であり、単核には見られなかった新規な物性や機能を発現することから興味が持たれる。このような機能性分子集合体を構築するためには単核および二核錯体ユニットを橋かけ配位子やspacerを用いて秩序正しくつないだり積み重ねたりすることが必要不可欠である。本研究では二核Pd(I)錯体を橋かけ配位子を用いてつないだ一次元鎖状多核Pd錯体の構築を試み、その系統的合成法を確立する共に、その構造および性質を明らかにした。 具体的には二核Pd(I)錯体[Pd_2(dppm)_2]^<2+>(1)(dppm=1,1′-ビス(ジフェニル)フォスフィノメタン)をprecursor錯体とし、橋かけ配位子である1,4-ジイソシアノベンゼンや4,4′-ビフェニルジカルボニルなどを反応させ一次元鎖状Pd錯体の構築を行ない、これらの構造をNMR、IR、元素分析などから明らかにした。またこれらの詳細な構造を明らかにするため単結晶化を行ない、現在単結晶X線構造解析を行なっているところである。さらにこれら一次元鎖状Pd錯体に機能を付与させるため部分酸化やオレフィン類などとの反応も行ない、その物理化学的性質も明らかにした。 今後、SやP原子を含む種々の橋かけ配位子を用いて、新規な多核Pd錯体の合成を試み、その構造および性質を明らかにして行く予定である。
- 日本学術振興会：科学研究費助成事業Date (from‐to) : 1994 -1994Author : 宗像 惠; 前川 雅彦(1)エチレン受容体とAg^+イオンとの特異的結合.Ag^+イオンによるエチレン活性阻害作用の研究から、エチレン受容体のAg^+結合サイトには少なくともSが1コあることを提案した。今回はさらにAg^+イオン以外のCu^+,Au^+,Tl^+,Cd^<2+>,Hg^<2+>,Pd^<2+>のCl^-,CN^-,S_2O_3^<2->,thioglucoseなどの錯体について、カ-ネーションの花持ちに及ぼす影響を検討した。Pd(II)錯体およびTl(I)錯体がわずか1〜2日ではあるが花持ちをよくする、つまりエチレン作用を阻害することを見い出した。Pd^2やTl^+に共通する性質はイオンの大きさ、電荷、電子配置ではなく、ソフトなイオンであるということである。これは我々が提案しているAg-binding siteがSを含むソフトな環境にあることを支持するものである。 (2)エチレン受容体の分離.昨年はAg^+イオンをマーカーにした新規なエチレン受容体分離法について検討したが、いくつかの重要な問題点が残されていた。特にICP-MAS法で、カラム分離した画分に含まれる極微量のAg^+(ppbオーダー)を精度良く検出するには、多くの前処理の検討が必要であったが、今回マトリックアスを透析で除去することで精度良く測定できることを明らかにした。またエチレン受容体の分離には白色燈下で育てたもやしの新芽より、暗室で育てたもやしの新芽の方が適していることがわかった。暗室内で育てたもやし新芽の抽出相をCM-Sephadexカラムで分離した結果、Ag^+イオンは100〜109mlの画分のみに検出され、この部分に受容体が存在する可能性があることを示した点で注目される。
- Japan Society for the Promotion of Science：Grants-in-Aid for Scientific ResearchDate (from‐to) : 1993 -1994Author : KITAGAWA Susumu; DEGUCHI Kenzou; FUJITO Teruaki; MAEKAWA Masahiko; MUNAKATA Megumu; KAWATA SatoshiThere are many useful nuclei in low resonance frequency region. However, few studies of their solid state NMR spectra have been reported because of their low sensitivity. In order to overcome the difficulties in measurements of high resolution solid state MAS NMR spectra, We have prepared a high sensitive probe for nuclei having low resonance frequency (low-gamma) and half-integer spin. Especially, Ag-109 NMR probe is useful for material science of silver compounds. The important points to prepare the probe are as follows. (1) According to Hartman-Hahn condition, the CP time is much longer than that in usual C-13 experiments, 50-100 ms. In addition to this, the applied field is much stronger than that of C-13 case. Thus, the probe should work against high power for long time. (2) To fill larger amount of sample in a bullet sample tube, the coil diameter is enlarged. (3) The probe circuits are improved in response to the above conditions. On these basis we have prepared a probe and succeeded in measuring Ag-109 spectra of various silver compounds with high sensitivity. The CPMAS conditions was checked by using [Ag(2,9-phenanthroline)2]PF6. The plots of signal intensity vs. contact time were obtained for practical use. The maximum intensity was obtained at a contact time, t=50 ms. The spectra were measured for various Ag compounds from mononuclear to coordination polymers. We found that[Ag(dihydroxybenzoquinone dianion)]n is the best compound to obtain a strong signal within a short time due to its shortest distance of 109Ag...1H.In addition to the know-how for the measurements we have completed chemical shifts scheme depending on donor atoms of ligands. The shift ranges from 0 ppm to 1000 ppm. the origin of the chemical shift was also discussed by using linear type silver compounds of pyridine derivatives. The shift trend shows that sigma-andpi-mechanism are competing.
- Japan Society for the Promotion of Science：Grants-in-Aid for Scientific ResearchDate (from‐to) : 1993 -1994Author : YOSHIDA Zenichi; MAEKAWA Masahiko; TAKEKUMA Shinichi; MATSUBARA YoshioImportant results obtained in this research are as follows : 1.The bicapped C_<60> with gamma-cyclodextrin found to behave as a chemical nitrogenase which fixes nitrogen to produce NH_3. 2.Synthesis of 1,3-dipheny1-2-pyrazoline ring fused C_<60>, interesting system from biological and materials view points, was achieved. 3.Of 10pi aromatic system, 3,5-guaiazulenequinone and [5] radialene substituted with 1,3-dithiol groups were synthisized. Some biological property for the former, and electrochemical and physical propaties for the latter were elucidated. 4.Indolone, new 8pi aromatic pigment was discovered to exist as chromoprotein in a mushroom. It plays a very important role in protein photosynthesis.
- 日本学術振興会：科学研究費助成事業Date (from‐to) : 1993 -1993Author : 宗像 恵; 前川 雅彦(1)エチレン受容体とAg^+イオンとの特異的結合の解明. 銀イオンとエチレン受容体との特異的結合を明らかにするため、カ-ネ-ションの老化促進における銀錯体イオン活性阻害作用を詳細に検討した。ジエチレントリアミン、トリエチレンテトラミン、エチレンジアミン四酢酸などAg錯体はエチレン活性をほとんど阻害しなかった。一方、Ag(CN)^-_2,Ag(S_2O_3)^<3->_2,Ag(thioglucose)^-_2,Ag(penicillamine)^<3->_2は大きなエチレン活性阻害効果を示した。前者の錯体ではAg^+イオンと配位子との結合は弱く、細胞壁や細胞膜中の官能基、特にメルカプト基によってAg^+イオンが引き抜かれるため、細胞膜を通過できないと考えられる。一方Ag^+イオンと強く結合している後者の錯体ではAg^+は細胞膜内の官能基と結合できないので、受容体まで近づくことができると考えられる。一方、ジメルカプトマレオニトリル、ジメルカプトコハク酸、ヘキサシクロテトロコサン[24]S_6(OH)_3などのAg錯体はほとんどエチレン阻害作用を示さなかった。これらの錯体ではAg^+と配位子との結合が余りにも強いため、エチレン受容体といえどもAg^+を引き抜くことができなかったものと考えられる。つまり、含S配位子と比較した場合、単のAg^+結合サイトにはSが2コ又は3コあるものと考えられる。 エチレン受容体の分離. 大豆及びもやしの新芽に銀イオンを吸収させ、この銀イオンをマ-カ-にした新規なエチレン受容体分離法を開拓した。もやしの新芽を用い、この方法に従って得られた抽出相をCM-Sephadexカラムで分離した。銀イオンは0〜120mlまでの有色部分と240ml以降の無色部分に検出された。今後の課題はこれら銀イオンが検出された部分のどの部分に受容体があるかを特定することである。
- Japan Society for the Promotion of Science：Grants-in-Aid for Scientific ResearchDate (from‐to) : 1992 -1993Author : MUNAKATA Megumu; MAEKAWA Masahiko; KITAGAWA Susumu(1) Novel molecular assemblies of Cu (I) complexes with phenazine (phz), [(Cu_2(mu-X)_2(mu-phz)]_* (X=Cl, 1 ; X=Br, 2 and X=1, 3) were synthesized. 1 and 2 have two-dimensional sheets hanging phz molecules between polymeric stair frames of CuCl and CuBr, respectively, and indicate absorption band characteristic of copper(I) coordination polymer with phz at about 710nm. (2) Metal-phz complexes with infinite stack columns were constracted for the first time. [Cu_2(phz)_3(MeOH)_2](phz)(PF_6)_2 is infinite stacks of alternating metal-free and coordinating phz molecules. The huge poynuclear complex [Ag_2(phz)(NO_3)_2]_* is made of two-dimensional framework of six-membered rings of silvers and pi-pi interaction of phz molecules between the two-dimensional sheets. (3) We succeeded in bulding Cu(I)-2,1,3-benzothiadiazole(btd) complexes with praphite structure. {[Cu_2(btd)_3(ClO_4)](ClO_6)_2thf}_* is a 2D structure composed of six-membered rings of coppers interconnected by six btds, [Cu_6(btd)_6]^<6+>. The 2D sheet composed of the six-membered rings is still maintained in {[Cu_6(btd)_4(HPO_3F)_4]^<2+>}_* although HPO_3F anions take part in the interconnecting as well as btd molecules. The Cu framework of the six-membered rings of coppers interconnected by btd and NO_3 in the 2D complex [Cu(btd)(NO_3)]_* to give a chair form which makes it possible to stack btd molecules within and between the 2D sheets and forms a layred structure similar to that of graphite.
- 日本学術振興会：科学研究費助成事業Date (from‐to) : 1992 -1992Author : 宗像 惠; 前川 雅彦; 北川 進本研究ではtetrakis-(methylthio)tetrathiafulvalene(tmt-TTF)を用いることにより金属としてハロゲン化銅(I)の分子集合体を構築し、さよにヨウ素で部分酸化し高伝導性機能を付与することを目的とした。 (1)[(CuI)2(tmt-TTF)]_∞:Cuが2つのIとtmt-TTFの2つのSで架橋された一次元無限鎖構造である。Cu-S距離は2.38Aである。隣接無限鎖間の最近接S…S間距離は3.75Aであり、これはSのvan der Waals半径(3.60A)よりも若干長いが伝導経路となる可能性がある。なおtmt-TTF間のstackingは存在しない。[(CuI)_2(tmt-TTF)]_∞の固体状態での電子スペクトルは510nm付近にCuIからtmt-TTFへのCTbandを与えた。[(CuI)2(tmt-TTF)]_∞をヨウ素でドーピングした黒色粉末{[(CuI)2(tmt-TTF)]Ix}_∞の固体状態での電子スペクトルは450nmから700nmの間に幅広い吸収を与えた。この化合物のlogσ(電気伝導度)は室温で-1.7Scm^<-1>であり、これは半導体電気伝導度範囲にある。ヨウ素ドープによりドナー分子のtmt-TTFが部分酸化され、このような高い伝導性を示したと考えられる。 (2)[(CuBr)2(tmt-TTF)]_∞:Cuがtmt-TTFとBrで架橋された無限鎖構造をとっている。またCu-Cu間を1つのBrが架橋している。注目されることはCuとBrがらせん構造を形成していることである。さらにtmt-TTFがこの骨格間を架橋した二次元ネットワーク構造をとっている。 以上、ハロゲン化銅(I)を用いて分子集合体を構築するのにtmt-TTFは極めて有効な配位子であることが示された。ここで合成した [(CuI)_2(tmt-TTF)]_∞と[(CuBr)2(tmt-TTF)]_∞はTTF系配位子が直接金属に配位した初めての例である。TTF系配位子は容易に部分酸化できるため、その錯体に電気伝導性機能が付与できるという長所を有する。
- 日本学術振興会：科学研究費助成事業Date (from‐to) : 1991 -1991Author : 宗像 恵; 前川 雅彦; 北川 進2,1,3ーベンゾチアジアゾ-ル(btd)を用いて一次元および二次元ネットワ-ク構造を有するCu(I)およびAg(I)錯体ポリマ-の合成に成功した。 (1)[Cu_2(btd)_2(CIO_4)]CIO_4.Cuにbtdのみで架橋された二次元ネットワ-クを有する錯体ポリマ-を合成することが出来た。対アニンのCIO_4^-は配位したものと配位しないものが1:1で存在しており、それに応じて4配位と3配位Cuが1:1で存在している。この二次元構造はほぼ同一平面上に存在する六員環Cu骨格を単位として構成されている。 (2)[Cu(btd)(HPO_3F)].btdとさらにHPO_3F^-の二つがCuに架橋した二次元ネットワ-ク構造を有する錯体ポリマ-が合成できた。この二次元構造も六員環Cu骨格を単位として構成されている。btd架橋とHPO_3F^-の結合距離が少し異なるため六員環Cu骨格は同一平面になく僅かに厚みを有している。 (3)[Ag(btd)(CIO_4)].Ag(I)のbtd錯体ではどのような構造をとるか興味がもたれる。Agにそれぞれ別のbtdのNが配位した一次元錯体ポリマ-であり、CIO_4^-がAgに弱く配位しているためNーAgーN角は166.6(4)°,144.3(4)°と大きく折れ曲がっている。ポリマ-鎖のbtdの間にπーπ相互作用(CーC=3.35A^^°)が存在する。しかし六員環Ag骨格を有する[Cu_2(btd)_2(CIO_4)]CIO_4しは全く異なる構造をとることがわかった。 以上述べたようにbtdはCu(I)及びAg(I)錯体ポリマ-を構築する上で極めて有用な配位子であり、金属及びアニオンによて、構造制御できることを初めて明らかにした。これら錯体ポリマ-では420〜500nmに強度の大きい吸収が観測された。適当な酸化剤を用いて部分酸化することができれば、伝導性が飛躍的に増大することが期待される。