![](https://www.kindai.ac.jp/data/images/professor/2743.jpg)
杉本 邦久(スギモト クニヒサ)
理工学部 理学科 | 教授 |
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■研究者基本情報
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研究キーワード
- X線構造解析 共結晶体 精密構造解析 放射光X線 分子性結晶 単結晶構造解析 電子密度解析
現在の研究分野(キーワード)
■経歴
経歴
- 2022年04月 - 現在 特定国立研究開発法人理化学研究所客員研究員
- 2022年04月 - 現在 京都大学高等研究員客員教授
- 2022年04月 - 現在 近畿大学理工学部教授
- 2021年04月 - 2022年03月 神戸大学大学院理学研究科 化学専攻客員教授
- 2019年04月 - 2022年03月 東北大学金属材料研究所客員教授
- 2019年01月 - 2022年03月 京都大学高等研究院特定准教授
- 2018年11月 - 2022年03月 公益財団法人高輝度光科学研究センターチームリーダー・主幹研究員
- 2014年05月 - 2021年03月 神戸大学客員准教授
- 2018年08月 - 2018年12月 京都大学客員准教授
- 2018年04月 - 2018年10月 公益財団法人高輝度光科学研究センター主幹研究員
- 2008年04月 - 2018年03月 公益財団法人高輝度光科学研究センター研究員
- 2008年04月 - 2016年03月 理化学研究所客員研究員
- 2000年04月 - 2008年03月 株式会社リガク研究員
- 2005年04月 - 2007年03月 マックスプランク固体物理学研究所客員研究員
委員歴
- 2024年04月 - 2026年03月 SPring-8ユーザー協同体(SPRUC) 行事委員長
- 2024年04月 - 2026年03月 日本結晶学会 庶務幹事
- 2022年04月 - 2026年03月 SPring-8ユーザー協同体(SPRUC) 行事幹事
- 2022年04月 - 2024年03月 日本結晶学会 編集副委員長
- 2022年04月 - 2024年03月 日本結晶学会 広報委員長
- 2016年04月 - 2024年03月 日本結晶学会 編集委員
- 2014年04月 - 2024年03月 日本結晶学会 広報委員
- 2018年04月 - 2022年03月 日本結晶学会 編集委員幹事
- 2018年09月 - 2020年08月 日本学術会議 化学委員会 企画分科会 情報科学との融合による新化学創成小委員会委員
- 2018年04月 - 2020年03月 日本結晶学会 広報委員長
- 2012年04月 - 2014年03月 日本結晶学会 編集委員
■研究活動情報
受賞
論文
- Yuki Sano; Ryojun Toyoda; Koki Chida; Takeharu Yoshii; Hirotomo Nishihara; Yuta Nishina; Daisuke Asanoma; Shinya Takaishi; Kunihisa Sugimoto; Ryota SakamotoACS Applied Materials & Interfaces 2024年08月
- Ryota Inoue; Ryo Sumitani; Hisashi Honda; Daisuke Kuwahara; Zi Lang Goo; Kunihisa Sugimoto; Tomoyuki MochidaInorganic Chemistry 63 31 14770 - 14778 2024年07月
- Shogo Kawaguchi; Shintaro Kobayashi; Hiroki Yamada; Hirotaka Ashitani; Michitaka Takemoto; Yasuhiko Imai; Takaki Hatsui; Kunihisa Sugimoto; Osami SakataJournal of Synchrotron Radiation 31 4 955 - 967 2024年06月The demand for powder X-ray diffraction analysis continues to increase in a variety of scientific fields, as the excellent beam quality of high-brightness synchrotron light sources enables the acquisition of high-quality measurement data with high intensity and angular resolution. Synchrotron powder diffraction has enabled the rapid measurement of many samples and various in situ/operando experiments in nonambient sample environments. To meet the demands for even higher throughput measurements using high-energy X-rays at SPring-8, a high-throughput and high-resolution powder diffraction system has been developed. This system is combined with six sets of two-dimensional (2D) CdTe detectors for high-energy X-rays, and various automation systems, including a system for automatic switching among large sample environmental equipment, have been developed in the third experimental hutch of the insertion device beamline BL13XU at SPring-8. In this diffractometer system, high-brilliance and high-energy X-rays ranging from 16 to 72 keV are available. The powder diffraction data measured under ambient and various nonambient conditions can be analysed using Rietveld refinement and the pair distribution function. Using the 2D CdTe detectors with variable sample-to-detector distance, three types of scan modes have been established: standard, single-step and high-resolution. A major feature is the ability to measure a whole powder pattern with millisecond resolution. Equally important, this system can measure powder diffraction data with high Q exceeding 30 Å−1 within several tens of seconds. This capability is expected to contribute significantly to new research avenues using machine learning and artificial intelligence by utilizing the large amount of data obtained from high-throughput measurements.
- Nobuhiro Sato; Ryojun Toyoda; Tetsu Sato; Zi Lang Goo; Shinya Takaishi; Koki Chida; Takeharu Yoshii; Hirotomo Nishihara; Kunihisa Sugimoto; Ryota SakamotoPrecision Chemistry 2024年06月
- Yoshitaka Tamura; Megumi Okazaki; Hiroto Ueki; Kenta Aihara; Tomoki Kanazawa; Dongxiao Fan; Rie Haruki; Akihide Iwase; Shunsuke Nozawa; Fumitaka Ishiwari; Kunihisa Sugimoto; Akinori Saeki; Kazuhiko MaedaChemSusChem 2024年05月Abstract The development of a highly active photocatalyst for visible‐light water splitting requires a high‐quality semiconductor material and a cocatalyst, which promote both the migration of photogenerated charge carriers and surface redox reactions. In this work, a cocatalyst was loaded onto an oxyfluoride photocatalyst, Pb2Ti2O5.4F1.2, to improve the water oxidation activity. Among the metal oxides examined as cocatalysts, RuO2 was found to be the most suitable, and the O2 evolution activity depended on the preparation conditions for Ru/Pb2Ti2O5.4F1.2. The highest activity was obtained with RuCl3‐impregnated Pb2Ti2O5.4F1.2 heated under a flow of H2 at 523 K. The H2‐treated Ru/Pb2Ti2O5.4F1.2 showed an O2 evolution rate an order of magnitude higher than those for the analogues without the H2 treatment (e. g., RuO2/Pb2Ti2O5.4F1.2). Physicochemical analyses by X‐ray absorption fine‐structure spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and time‐resolved microwave conductivity measurements indicated that the optimized photocatalyst contained partially reduced RuO2 species with a particle size of ~5 nm. These partially reduced species effectively trapped the photogenerated charge carriers and promoted the oxidation of water into O2. The optimized Ru/Pb2Ti2O5.4F1.2 could function as an O2‐evolving photocatalyst in Z‐scheme overall water splitting, in combination with an Ru‐loaded, Rh‐doped SrTiO3 photocatalyst.
- Emina Yamada; Hirotoshi Sakamoto; Hirosuke Matsui; Tomoya Uruga; Kunihisa Sugimoto; Minh-Quyet Ha; Hieu-Chi Dam; Ryotaro Matsuda; Mizuki TadaJournal of the American Chemical Society 2024年04月
- Emina Yamada; Hirotoshi Sakamoto; Hirosuke Matsui; Tomoya Uruga; Kunihisa Sugimoto; Minh-Quyet Ha; Hieu-Chi Dam; Ryotaro Matsuda; Mizuki Tada2023年12月
- Shunsuke Kitou; Masaki Gen; Yuiga Nakamura; Kunihisa Sugimoto; Yusuke Tokunaga; Shintaro Ishiwata; and Taka‐hisa ArimaAdvanced Science 2023年08月Abstract An anomalously high valence state sometimes shows up in transition‐metal oxide compounds. In such systems, holes tend to occupy mainly the ligand p orbitals, giving rise to interesting physical properties such as superconductivity in cuprates and rich magnetic phases in ferrates. However, no one has ever observed the distribution of ligand holes in real space. Here, a successful observation of the spatial distribution of valence electrons in cubic perovskite SrFeO3 by high‐energy X‐ray diffraction experiments and precise electron density analysis using a core differential Fourier synthesis method is reported. A real‐space picture of ligand holes formed by the orbital hybridization of Fe 3d and O 2p is revealed. The anomalous valence state in Fe is attributed to the considerable contribution of the ligand hole, which is related to the metallic nature and the absence of Jahn‐Teller distortions in this system.
- Shunsuke Kitou; Yoshio Kaneko; Yuiga Nakamura; Kunihisa Sugimoto; Yusuke Nomura; Ryotaro Arita; Yoshinori Tokura; Hiroshi Sawa; Taka-hisa ArimaPhysical Review B 108 2 2023年07月
- Tatsuo Gejo; Yuka Tanaka; Takuya Sakano; Satoshi Takeuchi; Osamu Takahashi; Hitoshi Osawa; Kunihisa Sugimoto; Kenji Tamasaku; Masaki OuraJournal of Physics B: Atomic, Molecular and Optical Physics 56 6 065002 - 065002 2023年03月Abstract The multi-ionization processes of Kr and Xe in the K-edge photon energy region were investigated using short-pulse x-rays and time-of-flight apparatus. The generation of Kr13+ ions in this photon energy region was observed for the first time. The distribution characteristics observed in the experiment, such as the production of Kr13+ ions, high production ratios of Kr4+, Kr5+, and Kr6+ ions, and the existence of a small peak for Kr8+, were quantitatively reproduced by the Monte Carlo simulation for the charge distribution of Kr ions following 1s of inner shell ionization. The highly charged ions were suppressed in the experiments compared with those in the simulation, probably owing to the inhibition of certain Coster-Kronig processes in the highly charged ions, which were not considered for analysis. The charge distribution of Xe ions following 1s of inner shell ionization was also investigated. A similar charge distribution was observed when the photon energy was located between the K and L edges. This is because the Xe 1s hole state mainly undergoes ultrafast relaxation to the 2p hole state owing to the strong dipole transition moment between the 1s and 2p states.
- Takaki Uchiyama; Hidenori Goto; Eri Uesugi; Akihisa Takai; Lei Zhi; Akari Miura; Shino Hamao; Ritsuko Eguchi; Hiromi Ota; Kunihisa Sugimoto; Akihiko Fujiwara; Fumihiko Matsui; Koji Kimura; Kouichi Hayashi; Teppei Ueno; Kaya Kobayashi; Jun Akimitsu; Yoshihiro KubozonoScientific Reports 13 1 2023年01月Abstract Doping a typical topological insulator, Bi2Se3, with Ag impurity causes a semiconductor–metal (S-M) transition at 35 K. To deepen the understanding of this phenomenon, structural and transport properties of Ag-doped Bi2Se3 were studied. Single-crystal X-ray diffraction (SC-XRD) showed no structural transitions but slight shrinkage of the lattice, indicating no structural origin of the transition. To better understand electronic properties of Ag-doped Bi2Se3, extended analyses of Hall effect and electric-field effect were carried out. Hall effect measurements revealed that the reduction of resistance was accompanied by increases in not only carrier density but carrier mobility. The field-effect mobility is different for positive and negative gate voltages, indicating that the EF is located at around the bottom of the bulk conduction band (BCB) and that the carrier mobility in the bulk is larger than that at the bottom surface at all temperatures. The pinning of the EF at the BCB is found to be a key issue to induce the S-M transition, because the transition can be caused by depinning of the EF or the crossover between the bulk and the top surface transport.
- Pingping Huang; Yukihiro Yoshida; Tokutaro Komatsu; Yuiga Nakamura; Kunihisa Sugimoto; Hiroshi KitagawaInorganic Chemistry 2023年01月
- Sofie Stampe Leiszner; Khetpakorn Chakarawet; Jeffrey R. Long; Eiji Nishibori; Kunihisa Sugimoto; James A. Platts; Jacob OvergaardInorganic Chemistry 2023年01月
- Masahiko Maekawa; Terumasa Hayashi; Kunihisa Sugimoto; Takashi Okubo; T. Kuroda-SowaDalton Transactions 2023年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...
- Wataru Kosaka; Honoka Nemoto; Kohei Nagano; Shogo Kawaguchi; Kunihisa Sugimoto; Hitoshi MiyasakaChemical Science 14 4 791 - 800 2023年The magnetic phase change triggered by structural modifications involving gas adsorption was realized for the first time in a layered metal–organic framework, where the inter-layer magnetic interaction was related to the inter-layer distance.
- Yongbing Shen; Mengxing Cui; Shinya Takaishi; Hideyuki Kawasoko; Kunihisa Sugimoto; Takao Tsumuraya; Akihiro Otsuka; Eunsang Kwon; Takefumi Yoshida; Norihisa Hoshino; Kazuhiko Kawachi; Yasuhiko Kasama; Tomoyuki Akutagawa; Tomoteru Fukumura; Masahiro YamashitaNature Communications 13 1 495 - 495 2022年12月Abstract Lithium-ion-encapsulated fullerenes (Li+@C60) are 3D superatoms with rich oxidative states. Here we show a conductive and magnetically frustrated metal–fullerene-bonded framework {[Cu4(Li@C60)(L)(py)4](NTf2)(hexane)}n (1) (L = 1,2,4,5-tetrakis(methanesulfonamido)benzene, py = pyridine, NTf2− = bis(trifluoromethane)sulfonamide anion) prepared from redox-active dinuclear metal complex Cu2(L)(py)4 and lithium-ion-encapsulated fullerene salt (Li+@C60)(NTf2−). Electron donor Cu2(L)(py)2 bonds to acceptor Li+@C60 via eight Cu‒C bonds. Cu–C bond formation stems from spontaneous charge transfer (CT) between Cu2(L)(py)4 and (Li+@C60)(NTf2−) by removing the two-terminal py molecules, yielding triplet ground state [Cu2(L)(py)2]+(Li+@C60•−), evidenced by absorption and electron paramagnetic resonance (EPR) spectra, magnetic properties and quantum chemical calculations. Moreover, Li+@C60•− radicals (S = ½) and Cu2+ ions (S = ½) interact antiferromagnetically in triangular spin lattices in the absence of long-range magnetic ordering to 1.8 K. The low-temperature heat capacity indicated that compound 1 is a potential candidate for an S = ½ quantum spin liquid (QSL).
- S. Yamada; H. Sagayama; M. Yamazaki; H. Aoki; K. Sugimoto; T. ArimaJournal of Solid State Chemistry 315 123504 - 123504 2022年11月
- Hayato Moriyama; Kazuya Otsubo; Kunihisa Sugimoto; Shogo Kawaguchi; Hiroshi KitagawaAngewandte Chemie (International ed. in English) 2022年10月A one-dimensional (1D) halogen-bridged dinuclear-metal complex (MMX-chain) exhibits various electronic states based on a mixed-valence metal-dimer system. This report deals with the synthesis and physical properties of a new MMX-chain with a bulky pendant ligand, Pt 2 (mc c -HexCS 2 ) 4 I (mc c -HexCS 2 = trans -4-(methoxycarbonyl)cyclohexanedithiocarboxylate). The steric hindrance caused by the bulky substituent induces a strain in its 1D chain, achieving at ambient condition the first pure alternate charge-polarization (ACP) state (-Pt 2+ -Pt 3+ -I - -Pt 3+ -Pt 2+ -I - -), a kind of spin-Peierls state, as confirmed by X-ray diffraction and its conducting and magnetic properties. The strain effect is also manifested as a very large linear thermal expansion along the chain direction, which is quite different from conventional MMX-chains without a bulky ligand. The design of low-dimensional materials with ligand variations is expected to lead to the emergence of new electron-lattice coupled electronic states.
- Yanting Zhang; Shino Hamao; Hidenori Goto; Yoshihiro Kubozono; Hideki Okamoto; Kunihisa Sugimoto; Nobuhiro Yasuda; Akihiko Fujiwara; Ritsuko EguchiJOURNAL OF PHYSICAL CHEMISTRY C 2022年10月A high carrier transport capability with strong x-x interactions is expected to result from the extension of x conjugation in small molecules. This is an important factor to create promising molecules, leading to the development of high-performance and new applications in organic electronic devices. We systematically demonstrate the charge transport capability and trap density of states in dibenzo[n]phenacenes (DBnPs) (n = 5-7) with a hybrid x structure between the phenacene and acene cores. A DB6P field-effect transistor (FET) achieves a relatively high-field-effect mobility beyond 2 cm2 V-1 s-1, which indicates excellent FET performance in comparison with DB5P and DB7P. The calculated charge-transfer integrals based on the crystal structure and the distribution of the trap density of states confirm the superior transport capability and FET properties in DB6P. We demonstrate that molecules with C2h symmetry result in high crystallinity and close packing in crystals, leading to high-performance FETs.
- Jae-Kyung Han; Kunihisa Sugimoto; Megumi Kawasaki; Klaus-Dieter LissMATERIALS LETTERS 321 2022年08月This study highlights the capability of high-energy synchrotron X-rays to investigate polymorphous phase transformation upon nanostructuring and diffusion bonding of Al and Mg through high-pressure torsion. The measurements providing diffraction peak profiles at a series of local positions over the sample volume allow mapping of gradual yet significant structural changes in the Al-Mg nanocrystalline alloy. The diffraction peaks involve apparent grain refinement broadening and compositional broadening with increasing shear strain. The results reveal strain-dependent transformations between f.c.c and h.c.p. phases with a sharp dissolution at strains of-2500 and subsequent homogenization towards the formation of an Al supersaturated solid solution with the Mg concentration of-14-15 at.%.
- Mickaele Bonneau; Christophe Lavenn; Jia-Jia Zheng; Alexandre Legrand; Tomofumi Ogawa; Kunihisa Sugimoto; Francois-Xavier Coudert; Regis Reau; Shigeyoshi Sakaki; Ken-ichi Otake; Susumu KitagawaNATURE CHEMISTRY 14 7 816 - + 2022年07月The safe storage of flammable gases, such as acetylene, is essential for current industrial purposes. However, the narrow pressure (P) and temperature range required for the industrial use of pure acetylene (100 < P < 200 kPa at 298 K) and its explosive behaviour at higher pressures make its storage and release challenging. Flexible metal-organic frameworks that exhibit a gated adsorption/desorption behaviour-in which guest uptake and release occur above threshold pressures, usually accompanied by framework deformations-have shown promise as storage adsorbents. Herein, the pressures for gas uptake and release of a series of zinc-based mixed-ligand catenated metal-organic frameworks were controlled by decorating its ligands with two different functional groups and changing their ratio. This affects the deformation energy of the framework, which in turn controls the gated behaviour. The materials offer good performances for acetylene storage with a usable capacity of similar to 90 v/v (77% of the overall amount) at 298 K and under a practical pressure range (100-150 kPa).
- Sounak Sarkar; Thomas Bjorn Egede Gronbech; Aref Mamakhel; Martin Bondesgaard; Kunihisa Sugimoto; Eiji Nishibori; Bo Brummerstedt IversenANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61 22 e202202742 2022年05月Glass-forming metal-organic frameworks (MOFs) have novel applications, but the origin of their peculiar melting behavior is unclear. Here, we report synchrotron X-ray diffraction electron densities of two zeolitic imidazolate frameworks (ZIFs), the glass-forming Zn-ZIF-zni and the isostructural thermally decomposing Co-ZIF-zni. Electron density analysis shows that the Zn-N bonds are more ionic than the Co-N bonds, which have distinct covalent features. Variable-temperature Raman spectra reveal the onset of significant imidazolate bond weakening in Co-ZIF-zni above 673 K. Melting can be controlled by tuning the metal-ligand and imidazole bonding strength as shown from thermal analysis of nine solid-solution CoxZn1-x-ZIF-zni (x=0.3 to 0.003) MOFs, and a mere 4 % Co-doping into Zn-ZIF-zni results in thermal decomposition instead of melting. The present findings demonstrate the key role of the metal-ligand bonds and imidazolate bonds in controlling the delicate balance between melting and decomposition processes in this class of ZIF compounds.
- Yannik Appiarius; Philipp J. Gliese; Stephan A. W. Segler; Pascal Rusch; Jiangbin Zhang; Paul J. Gates; Rumpa Pal; Lorraine A. Malaspina; Kunihisa Sugimoto; Tim Neudecker; Nadja C. Bigall; Simon Grabowsky; Artem A. Bakulin; Anne StaubitzJOURNAL OF PHYSICAL CHEMISTRY C 126 9 4563 - 4576 2022年03月Boron-nitrogen substitutions in polycyclic aromatic hydrocarbons (PAHs) have a strong impact on the optical properties of the molecules due to a significantly more heterogeneous electron distribution. However, besides these single-molecule properties, the observed optical properties of PAHs critically depend on the degree of intermolecular interactions such as pi-pi-stacking, dipolar interactions, or the formation of dimers in the excited state. Pyrene is the most prominent example showing the latter as it exhibits a broadened and strongly bathochromically shifted emission band at high concentrations in solution compared to the respective monomers. In the solid state, the impact of intermolecular interactions is even higher as it determines the crystal packing crucially. In this work, a thiophene-flanked BN-pyrene (BNP) was synthesized and compared with its all-carbon analogue (CCP) in solution and in the solid state by means of crystallography, NMR spectroscopy, UV-vis spectroscopy, and photoluminescence (PL) spectroscopy. In solution, PL spectroscopy revealed the solvent-dependent presence of excimers of CCP at high concentrations. In contrast, no excimers were found in BNP. Clear differences were also observed in the single-crystal packing motifs. While CCP revealed overlapped pyrene planes with centroid distances in the range of classical pi-stacking interactions, the BNP scaffolds were displaced and significantly more spatially separated.
- Taishun Manjo; Shunsuke Kitou; Naoyuki Katayama; Shin Nakamura; Takuro Katsufuji; Yoichi Nii; Taka-hisa Arima; Joji Nasu; Takumi Hasegawa; Kunihisa Sugimoto; Daisuke Ishikawa; Alfred Q. R. Baron; Hiroshi SawaMATERIALS ADVANCES 3 7 3192 - 3198 2022年02月Orbital degrees of freedom appear in partially filled degenerate orbitals and are responsible for a variety of physical properties. Although many methods for directly observing orbital states in ordered states have been proposed, it is difficult to determine degenerate orbital states directly. We found that high-precision diffraction data obtained by synchrotron radiation X-rays can be used to observe only the valence electron density distribution with minimal analytical bias. The results obtained using this method clearly showed the anisotropy of the partially filled degenerate 3d orbital states in spinel vanadium oxide FeV2O4. The 3d orbital quantum state was successfully determined from this anisotropy.
- Kazuya Otsubo; Shuya Nagayama; Shogo Kawaguchi; Kunihisa Sugimoto; Hiroshi KitagawaJACS Au 2 1 109 - 115 2022年01月Metal-organic frameworks (MOFs), made from various metal nodes and organic linkers, provide diverse research platforms for proton conduction. Here, we report on the superprotonic conduction of a Pt dimer based MOF, [Pt2(MPC)4Cl2Co(DMA)(HDMA)·guest] (H2MPC, 6-mercaptopyridine-3-carboxylic acid; DMA, dimethylamine). In this framework, a protic dimethylammonium cation (HDMA+) is trapped inside a pore through hydrogen bonding with an MPC ligand. Proton conductivity and X-ray measurements revealed that trapped HDMA+ works as a preinstalled switch, where HDMA+ changes its relative position and forms an effective proton-conducting pathway upon hydration, resulting in more than 105 times higher proton conductivity in comparison to that of the dehydrated form. Moreover, the anisotropy of single-crystal proton conductivity reveals the proton-conducting direction within the crystal. The present results offer insights into functional materials having a strong coupling of molecular dynamic motion and transport properties.
- Masahiko Maekawa; Shoki Oda; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-SowaRESULTS IN CHEMISTRY 4 2022年01月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.
- Yu Kitamura; Yuiga Nakamura; Kunihisa Sugimoto; Hirofumi Yoshikawa; Daisuke TanakaChemical Communications 58 81 11426 - 11429 2022年The synthesis of lanthanide metal–organic frameworks with terephthalate (Ln-BDC-MOFs) was investigated using a data-driven approach.
- Kazuya Otsubo; Shuya Nagayama; Shogo Kawaguchi; Kunihisa Sugimoto; Hiroshi KitagawaJACS AU 2 1 109 - 115 2022年01月Metal-organic frameworks (MOFs), made from various metal nodes and organic linkers, provide diverse research platforms for proton conduction. Here, we report on the super-protonic conduction of a Pt dimer based MOF, [Pt-2(MPC)(4)Cl2Co-(DMA)(HDMA)center dot guest] (H2MPC, 6-mercaptopyridine-3-carboxylic acid; DMA, dimethylamine). In this framework, a protic dimethylammonium cation (HDMA(+)) is trapped inside a pore through hydrogen bonding with an MPC ligand. Proton conductivity and X-ray measurements revealed that trapped HDMA(+) works as a preinstalled switch, where HDMA(+) changes its relative position and forms an effective proton-conducting pathway upon hydration, resulting in more than 10(5) times higher proton conductivity in comparison to that of the dehydrated form. Moreover, the anisotropy of single-crystal proton conductivity reveals the proton-conducting direction within the crystal. The present results offer insights into functional materials having a strong coupling of molecular dynamic motion and transport properties.
- Yongbing Shen; Kunihisa Sugimoto; Satoshi Yamashita; Takefumi Yoshida; Yasuhiro Nakazawa; Brian. K. Breedlove; Haitao Zhang; Masahiro YamashitaChemical Communications 58 23 3763 - 3766 2022年We report here a structurally perfect kagomé lattice {[Cu
3 (bpy)6 ](SiF6 )3 (melamine)8 }n (1 ), where bpy is 4,4′-bipyridine and [SiF6 ]2‒ is hexafluorosilicate anion. In comparison to general 1D linear, 2D layered and 3D cubic... - Guoji Huang; Behnam Ghalei; Ali Pournaghshband Isfahani; H. Enis Karahan; Daiki Terada; Detao Qin; Conger Li; Masahiko Tsujimoto; Daisuke Yamaguchi; Kunihisa Sugimoto; Ryuji Igarashi; Bor Kae Chang; Tao Li; Masahiro Shirakawa; Easan SivaniahNATURE ENERGY 6 12 1176 - + 2021年12月Graphene oxide (GO) can form ultrapermeable and ultraselective membranes that are promising for various gas separation applications, including hydrogen purification. However, GO films lose their attractive separation properties in humid conditions. Here we show that incorporating positively charged nanodiamonds (ND(+)s) into GO nanolaminates leads to humidity-resistant, yet high-performing, membranes. While native GO membranes fail at a single run, the GO/ND+ composite retains up to roughly 90% of GO's H-2 selectivity against CO2 after several cycles under an aggressive humidity test. The addition of negatively charged ND to GO brought no such stabilization, suggesting that charge compensation acts as the main mechanism conferring humidity resistance, where ND(+)s neutralize the negative charge GO sheets. We observed a similar but inferior stabilization effect when positively charged polyhedral oligomeric silsesquioxane replaces ND+. The demonstrated material platform offers a solution for separating H-2 gas from its usually humid mixtures generated from fossil fuel sources or water splitting.Graphene oxide's permeation properties make it a promising material for purification of hydrogen, but humidity can cause deleterious swelling. Here the authors remedy this by incorporating positively charged nanodiamonds into graphene oxide membranes, stabilizing the structure and minimizing performance degradation.
- Florian Kleemiss; Pim Puylaert; Daniel Duvinage; Malte Fugel; Kunihisa Sugimoto; Jens Beckmann; Simon GrabowskyACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE CRYSTAL ENGINEERING AND MATERIALS 77 892 - 905 2021年12月Sila-ibuprofen is a new potential nonsteroidal anti-inflammatory drug which deviates from its parent ibuprofen in terms of the electrostatic potential around the carbon/silicon-switched C/Si-H group. Therefore, sila-ibuprofen is more water soluble and has a lower melting enthalpy. However, its binding and inhibition properties of cyclooxygenases appear to be very similar to regular ibuprofen. Therefore, in this study, intermolecular interactions and interaction densities of both ibuprofen and sila-ibuprofen in their biologically active forms, i.e. deprotonated and as the pure S-enantiomers are investigated. Quantum-crystallographically refined salts with argininium and 1-phenylethan-1-amoninium (PEA) counter-cations as crystalline models of the interactions with the guanidine functional group of arginine inside cyclooxygenases are presented. The similarities and differences between the polarization of ibuprofen and silaibuprofen in the crystal, enzyme, solvent and isolated environments are discussed based on quantum-chemical calculations. For the explicit crystal and enzyme environments, specifically, molecular dynamics simulations starting from the crystal models were combined with QM/MM calculations.
- Masahiko Maekawa; Mafuyu Yabuta; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-SowaInorganica Chimica Acta 528 120628 Elsevier 2021年12月 [査読有り]
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. - Kentaro Aoki; Kazuya Otsubo; Yukihiro Yoshida; Yojiro Kimura; Kunihisa Sugimoto; Hiroshi KitagawaINORGANIC CHEMISTRY 60 21 16029 - 16034 2021年11月Metal string complexes, linearly aligned transition metal arrays coordinated with the multidentate organic ligands, have gained much attention both in unique electronic/structural properties and in potential applications as conductive molecular nanowires. Here we report on a dimerized Ni-II trinuclear complex, [Ni6Cl2(dpa)(8)](I-5)(2)center dot 0.25I(2) (dpa(-) = 2,2'-dipyridylamide anion). X-ray structural analysis revealed that two trinuclear moieties are bridged by a Cl anion to form a dimerized string structure. This is the first example of two Ni string complexes that are connected. In the electronic absorption and Raman spectra, characteristic absorption bands and a vibration mode based on the dimer string structure were observed. In the solid state, dimer complexes align in one dimension in an MMMXMMMX (M = metal, X = halogen) manner, leading to the intra- and interdimer antiferromagnetic interactions.
- Kentaro Aoki; Kazuya Otsubo; Yukihiro Yoshida; Yojiro Kimura; Kunihisa Sugimoto; Hiroshi KitagawaInorganic chemistry 60 21 16029 - 16034 2021年11月Metal string complexes, linearly aligned transition metal arrays coordinated with the multidentate organic ligands, have gained much attention both in unique electronic/structural properties and in potential applications as conductive molecular nanowires. Here we report on a dimerized NiII trinuclear complex, [Ni6Cl2(dpa)8](I5)2·0.25I2 (dpa- = 2,2'-dipyridylamide anion). X-ray structural analysis revealed that two trinuclear moieties are bridged by a Cl anion to form a dimerized string structure. This is the first example of two Ni string complexes that are connected. In the electronic absorption and Raman spectra, characteristic absorption bands and a vibration mode based on the dimer string structure were observed. In the solid state, dimer complexes align in one dimension in an MMMXMMMX (M = metal, X = halogen) manner, leading to the intra- and interdimer antiferromagnetic interactions.
- Takuto Mibu; Atsushi Iba; Yusaku Suenaga; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Kunihisa SugimotoInorganica Chimica Acta 527 120538 - 120538 2021年11月Two types of mononuclear cobalt complexes with two ancillary ligands containing isoquinoline groups and 3, 5-di-tert-butylcatechol (3, 5-DBCat) were synthesized. The crystal structures and spectroscopic, electrochemical, and magnetic properties of these complexes and complexes with ancillary ligands containing multiple quinoline groups were compared to clarify the steric effect of quinoline derivatives around the cobalt center. In particular, a comparison of the crystal structures of the mononuclear cobalt complexes containing tris(2-quinolylmethyl) amine (tqa) and tris(3-isoquinolylmethyl)amine (isotqa) as ancillary ligands, each of which has three isoquino-line and three quinoline rings, showed that the isotqa complex was less congested than the tqa complex around the cobalt center. As a result, the tqa complex contains Co (II), whereas the isotqa complex has the stable Co (III) electronic state due to the stronger ligand field. In this report, the steric influence of ancillary ligand substituents on the electronic states of complexes is clarified from several perspectives such as spectroscopic, electrochemical and magnetic properties.
- Masaki Donoshita; Yukihiro Yoshida; Mikihiro Hayashi; Ryuichi Ikeda; Susumu Tanaka; Yasuhisa Yamamura; Kazuya Saito; Shogo Kawaguchi; Kunihisa Sugimoto; Hiroshi KitagawaAngewandte Chemie (International ed. in English) 60 42 22839 - 22848 2021年10月Control over the stacking patterns in 2D molecular assemblies is demonstrated using chemical modification. A target system is a hydrogen-bonded cocrystal (2:1) composed of 2-pyrrolidone (Py) and chloranilic acid (CA) (PyCA). X-ray crystallography showed that weak intersheet interactions give rise to a variety of metastable overlapping patterns comprised of the 2D assemblies mainly formed via hydrogen bonds, affording reversible and irreversible structural phase transitions. We prepared cocrystals of Py and anilic acids bearing different halogens, in which 2D assemblies isostructural with those observed in PyCA exhibit various overlapping patterns. The order of stability for each overlapping pattern estimated using calculations of the intermolecular interactions did not completely coincide with those indicated by our experimental results, which can be explained by considering the entropic effect: the molecular motion of Py as detected using nuclear quadrupole resonance spectroscopy.
- Mickaele Bonneau; Kunihisa Sugimoto; Ken‐ichi Otake; Yukiko Tsuji; Nanae Shimanaka; Christophe Lavenn; Susumu KitagawaNatural Sciences 2021年10月
- D. Bessas; H. Fukui; K. Sugimoto; K. Glazyrin; I. Sergueev; G. Levchenko; A. Dukhnenko; V. Filipov; O. Isnard; D. Ishikawa; H. Yoshikawa; O. Sakata; A. Q. R. BaronJournal of Applied Physics 2021年07月
- Yusaku Suenaga; Takuto Mibu; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Kunihisa SugimotoDALTON TRANSACTIONS 50 28 9833 - 9841 2021年07月The biscatechol, H4BP (4,4 '-bis(3-tert-butyl-1,2-catechol)) that can directly connect two redox active catechol moieties was synthesized. Also, tris(2-pyridylmethyl)amine (tpa), bis(2-pyridylmethyl)(2-quinolylmethyl)amine (bpqa), (2-pyridylmethyl)bis(2-quinolyl methyl)amine (pbqa), and tris (2-quinolylmethyl)amine (tqa) were synthesized as terminal ligands of the tetracoordinated tripod. In total, five different dinuclear Co complexes were synthesized from H4BP with various terminal ligands as follows, [Co-2(BP)(tpa)(2)](PF6)(2) (1), [Co-2(BP)(tpa)(2)](PF6)(3) (2), [Co-2(BP)(bpqa)(2)](PF6)(2) (3), [Co-2(BP)(pbqa)(2)](PF6)(2) (4), and [Co-2(BP)(tqa)(2)](PF6)(2) (5). After a one-electron oxidation reaction of complex (1), complex (2), was isolated as a mixed valence state lsCo(III)-[SQ-Cat]-lsCo(III), with an absorption intensity of about 1370 nm (intervalence charge transfer (IVCT) bands) in CH3CN solution. In addition, an investigation of the magnetic properties of the dinuclear Co complex (3) with SQUID showed that the chi T-M value gradually increased as the temperature increased from 280 to 380 K. Studies in the solid and solution states using electronic spectra, cyclic voltammetry and SQUID for the above complexes provide clear evidence for three different charge distributions: complexes (1) and (3) are Co-III-[Cat-Cat]-Co-III, complex (2) is Co-III-[Sq-Cat]-Co-III, complexes (4) and (5) are Co-II-[Sq-Sq]-Co-II. Of the five cobalt dinuclear complexes, only complex (3) shows evidence of the temperature dependence of the charge distribution, displaying a thermally induced valence tautomeric transition from the lsCo(III)-[Cat-Cat]-lsCo(III) to hsCo(II)-[Sq-Sq]-hsCo(II) in both solid and solution states. However, this valence tautomeric step is incomplete at 380 K, with the chi T-M value of hsCo(II)-[Sq-Sq]-hsCo(II). This suggests that the steric hindrance of the quinolyl rings around the Co ion produces a coordination atmosphere that is weaker than that observed with pyridyl rings, which facilitates a change in the Co-III ions to Co-II.
- Kunihisa Sugimoto; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaCRYSTAL GROWTH & DESIGN 21 7 4178 - 4183 2021年07月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.
- Lorraine A. Malaspina; Alessandro Genoni; Dylan Jayatilaka; Michael J. Turner; Kunihisa Sugimoto; Eiji Nishibori; Simon GrabowskyJOURNAL OF APPLIED CRYSTALLOGRAPHY 54 Pt 3 718 - 729 2021年06月Although hydrogen bonding is one of the most important motifs in chemistry and biology, H-atom parameters are especially problematic to refine against X-ray diffraction data. New developments in quantum crystallography offer a remedy. This article reports how hydrogen bonds are treated in three different quantum-crystallographic methods: Hirshfeld atom refinement (HAR), HAR coupled to extremely localized molecular orbitals and X-ray wavefunction refinement. Three different compound classes that form strong intra- or intermolecular hydrogen bonds are used as test cases: hydrogen maleates, the tripeptide L-alanyl-glycyl-L-alanine co-crystallized with water, and xylitol. The differences in the quantum-mechanical electron densities underlying all the used methods are analysed, as well as how these differences impact on the refinement results.
- Kenta Sasaki; Haruka Yoshino; Yuushi Shimoda; Masaki Saigo; Kiyoshi Miyata; Ken Onda; Kunihisa Sugimoto; Hitomi Yamate; Hiroki Miura; Benjamin Le Ouay; Ryo Ohtani; Masaaki OhbaInorganic chemistry 60 9 6140 - 6146 2021年05月The excited-state energy was tuned successfully by guest molecules in a cyanide-bridged luminescent coordination polymer (CP). Methanol or ethanol vapor reversibly and significantly changed the luminescent color of the CP between green and yellow (Δλem = 32 nm). These vapors did not significantly affect the environment around the luminophore in the ground state of the CP, whereas they modulated the excited states for the resulting bathochromic shift. The time-resolved photoluminescent spectra of the CP systems showed that solvent adsorption enhanced the energetic relaxation in the excited states. Furthermore, time-resolved infrared spectroscopy indicated that cyanide bridging in the CP became more flexible in the excited states than that in the ground state, highlighting the sensitivity of the excited states to external stimuli, such as the guest vapor. Overall, guest-tunable excited states will allow the more straightforward design of sensing materials by characterizing the transient excited states.
- Yuiga Nakamura; Naoyuki Shibayama; Kunihisa SugimotoChemical communications (Cambridge, England) 57 21 2685 - 2688 2021年03月We observed the crystallization dynamics of halide perovskite crystals (CH3NH3PbI3) by in situ heating wide-angle X-ray scattering measurements. As a result, we revealed that crystal growth occurs during the conversion of complexes to perovskite crystals.
- Yoshinobu Kamakura; Ryo Hamano; Yuiga Nakamura; Kunihisa Sugimoto; Hirofumi Yoshikawa; Daisuke TanakaChemistry Letters 50 5 1053 - 1056 2021年03月A novel thiolate-based Pb-metal-organic framework, [Pb-2(Hdtd)(4)center dot 2DMSO](n) (KGF-2 center dot DMSO, H(2)dtd = 6-dibutylamino-1,3,5-triazine-2,4-dithol and DMSO = dimethyl sulfoxide) was prepared. The crystal structure of KGF-2 center dot DMSO consists of a one-dimensional chain composed of Pb ions and surrounding ligands. Following removal of the guest DMSO molecules, KGF-2 was obtained as a crystalline powder, which exhibited selective water sorption properties.
- Florian Kleemiss; Erna K Wieduwilt; Emanuel Hupf; Ming W Shi; Scott G Stewart; Dylan Jayatilaka; Michael J Turner; Kunihisa Sugimoto; Eiji Nishibori; Tanja Schirmeister; Thomas C Schmidt; Bernd Engels; Simon GrabowskyChemistry (Weinheim an der Bergstrasse, Germany) 27 10 3407 - 3419 2021年02月The crystal interaction density is generally assumed to be a suitable measure of the polarization of a low-molecular weight ligand inside an enzyme, but this approximation has seldomly been tested and has never been quantified before. In this study, we compare the crystal interaction density and the interaction electrostatic potential for a model compound of loxistatin acid (E64c) with those inside cathepsin B, in solution, and in vacuum. We apply QM/MM calculations and experimental quantum crystallography to show that the crystal interaction density is indeed very similar to the enzyme interaction density. Less than 0.1 e are shifted between these two environments in total. However, this difference has non-negligible consequences for derived properties.
- Masahiko Maekawa; Kota Terada; Shoki Oda; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-SowaINORGANICA CHIMICA ACTA 514 2021年01月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.
- Yusaku Suenaga; Takuto Mibu; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-Sowa; Kunihisa SugimotoDalton Transactions 50 31 10983 - 10983 2021年
[Co2(BP)(bpqa)2](PF6)2 shows evidence of temperature dependence of the charge distribution, displaying a thermally induced valence tautomeric transition from the lsCoIII-[Cat–Cat]-lsCoIII to hsCoII-[Sq–Sq]-hsCoII in both solid and solution states.
- Hiroki Fukunaga; Wataru Kosaka; Honoka Nemoto; Kouji Taniguchi; Shogo Kawaguchi; Kunihisa Sugimoto; Hitoshi MiyasakaChemistry (Weinheim an der Bergstrasse, Germany) 26 70 16755 - 16766 2020年12月 [査読有り]
The insertion of "sandwiched spins" between magnetic layers could efficiently affect the interlayer magnetic correlations, but doing so increases the complexity in the interlayer spin alignment because of competition between the inserted spin-layer interaction JNNI and the interlayer through-space interaction JNNNI if the magnitude of JNNI is of the same order as JNNNI with reciprocal signs of the respective interactions. Herein, systematic tuning of the magnetic phase variations by JNNI and JNNNI in two kinds of metal-variable isostructural series of supramolecular pillared layer magnets [MCp*2 ][{Ru2II,II (2,3,5,6-F4 CO2 )4 }2 (TCNQ)]⋅2 DCE (M=Co, Fe, Cr; 2,3,5,6-F4 PhCO2- =2,3,5,6-tetrafluorobenzoate; TCNQ=7,7,8,8-tetracyano-p-quinodimethane; DCE=1,2-dichloroethane) and their DCE-free series, in which [MCp*2 ]+ (Cp*=η5 -C5 Me5 ) species with S=0, 1/2, and 3/2 for M=Co, Fe, Cr, respectively, are sandwiched between ferrimagnetic layers of [{Ru2 }2 (TCNQ)]- , is demonstrated. The results showed that the flexible magnetic natures of these magnets are changeable in dependence on JNNI and JNNNI , as well as on interlayer inserted spins M. - Keita Daicho; Yoshiki Ozawa; Kunihisa Sugimoto; Masaaki AbeJournal of the Chinese Chemical Society 67 12 2225 - 2232 2020年12月The crystal structure of a new pyrazine-bridged trimer of oxo-centered triruthenium-carbonyl clusters formulated as [Ru3O(EtCOO)(6)(CO)(pyrazine)](2)[Ru3O(EtCOO)(6)(CO)(mu-pyrazine)(2)] (1) has been unequivocally determined by single-crystal X-ray diffraction (SC-XRD) analysis at 100 K. A supramolecular cyclic assembly of two trimers was formed via intermolecular COMIDLINE HORIZONTAL ELLIPSISCO contacts, which is further assembled into a three-dimensional orthogonal layer-by-layer stack via hydrogen bonds.
- Mickaele Bonneau; Christophe Lavenn; Kunihisa Sugimoto; Alexandre Legrand; Tomofumi Ogawa; François-Xavier Coudert; Regis Réau; Ken-ichi Otake; Susumu Kitagawa2020年11月
Abstract Safe managing and storage of explosive gas, such as acetylene, is essential for industries. The practical pressure and temperature regime is quite narrow for acetylene, and the optimization by complete release of saturated gas remains challenging to control. Here, a novel approach to narrow the pressure range of gas introduction and release for the storage of unstable and pressure-sensitive gas substance is reported. Flexible metal–organic frameworks (MOFs) are expected to be an excellent storage adsorbent owing to their gated adsorption/desorption behavior. However, developing such a system in a practical and narrow pressure range remains difficult. Here, we demonstrate that the gate-opening and closing pressures of a solid solution type based on interpenetrated MOF-508 can be optimized by tuning the deformation energy of the framework and the energy of host–guest interactions. These energies were adjusted by changing the functional group on the MOF ligands and its ratio in the mixed-ligand system. The filling and release of acetylene in the practical pressure regions of up to 180 kPa leads to an on-demand porous material for acetylene storage with an usable volumetric capacity of 106 v/v under mild temperature (273–298 K) and pressure (70–120 kPa). - Katharina Knippen; Björn Bredenkötter; Lisa Kanschat; Maryana Kraft; Tom Vermeyen; Wouter Herrebout; Kunihisa Sugimoto; Patrick Bultinck; Dirk VolkmerDalton transactions (Cambridge, England : 2003) 49 44 15758 - 15768 2020年11月In this work, we introduce the first enantiopure bistriazolate-based metal-organic framework, CFA-18 (Coordination Framework Augsburg-18), built from the R-enantiomer of 7,7,7',7'-tetramethyl-6,6',7,7'-tetrahydro-3H,3'H-5,5'-spirobi[indeno[5,6-d]-[1,2,3]triazole] (H2-spirta). The enantiopurity and absolute configuration of the new linker were confirmed by several chiroselective methods. Reacting H2-spirta in hot N,N-dimethylformamide (DMF) with manganese(ii) chloride gave CFA-18 as colorless crystals. The crystal structure with the composition [Mn2Cl2(spirta)(DMF)2] was solved using synchrotron single-crystal X-ray diffraction. CFA-18 shows a framework topology that is closely related to previously reported metal-azolate framework (MAF) structures in which the octahedrally coordinated manganese(ii) ions are triazolate moieties, and the chloride anions form crosslinked one-dimensional helical chains, giving rise to hexagonal channels. In contrast to MAFs crystallizing in the centrosymmetric space group R3[combining macron], the handedness of the helices found in CFA-18 is strictly uniform, leading to a homochiral framework that crystallizes in the trigonal crystal system within the chiral space group P3121 (no. 152).
- Florian Kleemiss; Aileen Justies; Daniel Duvinage; Patrick Watermann; Eric Ehrke; Kunihisa Sugimoto; Malte Fugel; Lorraine A Malaspina; Anneke Dittmer; Torsten Kleemiss; Pim Puylaert; Nelly R King; Anne Staubitz; Thomas M Tzschentke; Ralf Dringen; Simon Grabowsky; Jens BeckmannJournal of medicinal chemistry 63 21 12614 - 12622 2020年11月The synthesis, characterization, biological activity, and toxicology of sila-ibuprofen, a silicon derivative of the most common nonsteroidal anti-inflammatory drug, is reported. The key improvements compared with ibuprofen are a four times higher solubility in physiological media and a lower melting enthalpy, which are attributed to the carbon-silicon switch. The improved solubility is of interest for postsurgical intravenous administration. A potential for pain relief is rationalized via inhibition experiments of cyclooxygenases I and II (COX-I and COX-II) as well as via a set of newly developed methods that combine molecular dynamics, quantum chemistry, and quantum crystallography. The binding affinity of sila-ibuprofen to COX-I and COX-II is quantified in terms of London dispersion and electrostatic interactions in the active receptor site. This study not only shows the potential of sila-ibuprofen for medicinal application but also improves our understanding of the mechanism of action of the inhibition process.
- Toshihiro Okamoto; Masato Mitani; Craig P Yu; Chikahiko Mitsui; Masakazu Yamagishi; Hiroyuki Ishii; Go Watanabe; Shohei Kumagai; Daisuke Hashizume; Shota Tanaka; Masafumi Yano; Tomokatsu Kushida; Hiroyasu Sato; Kunihisa Sugimoto; Takashi Kato; Jun TakeyaJournal of the American Chemical Society 142 35 14974 - 14984 2020年09月Toward the development of high-performance organic semiconductors (OSCs), carrier mobility is the most important requirement for next-generation OSC-based electronics. The strategy is that OSCs consisting of a highly extended π-electron core exhibit two-dimensional (2D) aggregated structures to offer effective charge transport. However, such OSCs, in general, show poor solubility in common organic solvents, resulting in limited solution processability. This is a critical trade-off between the development of OSCs with simultaneous high carrier mobility and suitable solubility. To address this issue, herein, five-membered ring-fused selenium-bridged V-shaped binaphthalene with decyl substituents (C10-DNS-VW) is developed and synthesized by an efficient method. C10-DNS-VW exhibits significantly high solubility for solution processes. Notably, C10-DNS-VW forms a one-dimensional π-stacked packing motif (1D motif) and a 2D herringbone (HB) packing motif (2D motif), depending on the crystal growth condition. On the other hand, the fabrication of thin films by means of both solution process and vacuum deposition techniques forms only the 2D HB motif. External stress tests such as heating and exposure to solvent vapor indicated that 1D and 2D motifs could be synergistically induced by the total balance of intermolecular interactions. Finally, the single-crystalline films of C10-DNS-VW by solution process exhibit carrier mobility up to 11 cm2 V-1 s-1 with suitable transistor stability under ambient conditions for more than two months, indicating that C10-DNS-VW is one of the most promising candidates for breaking the trade-off in the field of solution-processed technologies.
- Shunsuke Kitou; Taishun Manjo; Naoyuki Katayama; Tatsuya Shishidou; Taka-hisa Arima; Yasujiro Taguchi; Yoshinori Tokura; Toshikazu Nakamura; Toshihiko Yokoyama; Kunihisa Sugimoto; Hiroshi SawaPHYSICAL REVIEW RESEARCH 2 3 2020年09月The orbital degree of freedom of electrons greatly influences the physical properties of materials such as magnetic order and unconventional superconductivity. An orbital is a minimal unit of "shape," and the orbital state can be unraveled by observing the spatial anisotropic distribution of electrons. However, it is difficult to experimentally extract the orbital information in a crystal because of various technical problems. Here, the Ti-3d orbital state in perovskite-type oxides RTiO3 (R = Y, Sm, and La) is directly determined by a core differential Fourier synthesis (CDFS) method using synchrotron x-ray diffraction. The valence electron-density distribution, including information on the anisotropy and the hybridization between atomic orbitals, can be extracted from the CDFS analysis. Our study not only demonstrates the relationship between the magnetic- and orbital-ordered states called the Kugel-Khomskii model, but also provides a nontrivial picture of the orbital state reconstructed by the orbital hybridization.
- Yifan Gu; Jia-Jia Zheng; Ken-Ichi Otake; Kunihisa Sugimoto; Nobuhiko Hosono; Shigeyoshi Sakaki; Fengting Li; Susumu KitagawaAngewandte Chemie (International ed. in English) 59 36 15517 - 15521 2020年09月 [査読有り]
To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (Edef ) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control Edef to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an Edef -modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced Edef of PCP enables a selective gate-opening behavior toward CHCl3 over CH2 Cl2 by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials. - Frederik Haase; Gavin A Craig; Mickaële Bonneau; Kunihisa Sugimoto; Shuhei FurukawaJournal of the American Chemical Society 142 32 13839 - 13845 2020年08月Reticular framework materials thrive on designability, but unexpected reaction outcomes are crucial in exploring new structures and functionalities. By combining "incompatible" building blocks, we employed geometric frustration in reticular materials leading to emergent structural features. The combination of a pseudo-C5-symmetrical organic building unit based on a pyrrole core with a C4-symmetrical copper paddlewheel synthon led to three distinct frameworks by tuning the synthetic conditions. The frameworks show structural features typical for geometric frustration: self-limiting assembly, internally stressed equilibrium structures, and topological defects in the equilibrium structure, which manifested in formation of a hydrogen-bonded framework, distorted and broken secondary building units, and dangling functional groups, respectively. The influence of geometric frustration on the CO2 sorption behavior and the discovery of a new secondary building unit shows geometric frustration can serve as a strategy to obtain highly complex porous frameworks.
- Lorraine A. Malaspina; Anna A. Hoser; Alison J. Edwards; Magdalena Woinska; Michael J. Turner; Jason R. Price; Kunihisa Sugimoto; Eiji Nishibori; Hans-Beat Buergi; Dylan Jayatilaka; Simon GrabowskyCRYSTENGCOMM 22 28 4778 - 4789 2020年07月Resonance-assisted hydrogen bonds (RAHBs) are exploited in chemical synthesis or serve as models for biologically relevant proton-transfer reactions [K. T. Mahmudov and A. J. L. Pombeiro, Chem. - Eur. J., 2016, 22, 16356-16398]. Their properties depend on the position of the hydrogen atom between donor and acceptor atoms. In the intramolecular RAHB of hydrogen maleate salts, this position is strongly influenced by the counter cation and varies from highly asymmetric to perfectly symmetric. This compound class is therefore ideally suited to investigate the factors determining geometry and electron density of intramolecular RAHBs. Here, it is shown that Hirshfeld atom refinements (HARs) of X-ray diffraction data of different hydrogen maleate salts can accurately and precisely match the hydrogen atom positions obtained from neutron diffraction and are independent of the model used for the hydrogen atom displacement parameters. Thus, the simplest, i.e. isotropic, HAR model can be used to locate hydrogen atoms also in bridging positions. In contrast, the determination of electron-density parameters with X-ray constrained wavefunction (XCW) fitting requires anisotropic, highly accurate hydrogen atom displacement parameters.
- Manabu Nakaya; Wataru Kosaka; Hitoshi Miyasaka; Yuki Komatsumaru; Shogo Kawaguchi; Kunihisa Sugimoto; Yingjie Zhang; Masaaki Nakamura; Leonard F Lindoy; Shinya HayamiAngewandte Chemie (International ed. in English) 59 26 10658 - 10665 2020年06月 [査読有り]
CO2 -responsive spin-state conversion between high-spin (HS) and low-spin (LS) states at room temperature was achieved in a monomeric cobalt(II) complex. A neutral cobalt(II) complex, [CoII (COO-terpy)2 ]⋅4 H2 O (1⋅4 H2 O), stably formed cavities generated via π-π stacking motifs and hydrogen bond networks, resulting in the accommodation of four water molecules. Crystalline 1⋅4 H2 O transformed to solvent-free 1 without loss of porosity by heating to 420 K. Compound 1 exhibited a selective CO2 adsorption via a gate-open type of the structural modification. Furthermore, the HS/LS transition temperature (T1/2 ) was able to be tuned by the CO2 pressure over a wide temperature range. Unlike 1 exhibits the HS state at 290 K, the CO2 -accomodated form 1⊃CO2 (P CO 2 =110 kPa) was stabilized in the LS state at 290 K, probably caused by a chemical pressure effect by CO2 accommodation, which provides reversible spin-state conversion by introducing/evacuating CO2 gas into/from 1. - Lennard Krause; Kasper Tolborg; Thomas Bjørn Egede Grønbech; Kunihisa Sugimoto; Bo Brummerstedt Iversen; Jacob OvergaardJournal of applied crystallography 53 Pt 3 635 - 649 2020年06月Hybrid photon-counting detectors are widely established at third-generation synchrotron facilities and the specifications of the Pilatus3 X CdTe were quickly recognized as highly promising in charge-density investigations. This is mainly attributable to the detection efficiency in the high-energy X-ray regime, in combination with a dynamic range and noise level that should overcome the perpetual problem of detecting strong and weak data simultaneously. These benefits, however, come at the expense of a persistent problem for high diffracted beam flux, which is particularly problematic in single-crystal diffraction of materials with strong scattering power and sharp diffraction peaks. Here, an in-depth examination of data collected on an inorganic material, FeSb2, and an organic semiconductor, rubrene, revealed systematic differences in strong intensities for different incoming beam fluxes, and the implemented detector intensity corrections were found to be inadequate. Only significant beam attenuation for the collection of strong reflections was able to circumvent this systematic error. All data were collected on a bending-magnet beamline at a third-generation synchrotron radiation facility, so undulator and wiggler beamlines and fourth-generation synchrotrons will be even more prone to this error. On the other hand, the low background now allows for an accurate measurement of very weak intensities, and it is shown that it is possible to extract structure factors of exceptional quality using standard crystallographic software for data processing (SAINT-Plus, SADABS and SORTAV), although special attention has to be paid to the estimation of the background. This study resulted in electron-density models of substantially higher accuracy and precision compared with a previous investigation, thus for the first time fulfilling the promise of photon-counting detectors for very accurate structure factor measurements.
- Shogo Kawaguchi; Michitaka Takemoto; Hideki Tanaka; Shotaro Hiraide; Kunihisa Sugimoto; Yoshiki KubotaJournal of synchrotron radiation 27 Pt 3 616 - 624 2020年05月 [査読有り]
A gas- and vapour-pressure control system synchronized with the continuous data acquisition of millisecond high-resolution powder diffraction measurements was developed to study structural change processes in gas storage and reaction materials such as metal organic framework compounds, zeolite and layered double hydroxide. The apparatus, which can be set up on beamline BL02B2 at SPring-8, mainly comprises a pressure control system of gases and vapour, a gas cell for a capillary sample, and six one-dimensional solid-state (MYTHEN) detectors. The pressure control system can be remotely controlled via developed software connected to a diffraction measurement system and can be operated in the closed gas and vapour line system. By using the temperature-control system on the sample, high-resolution powder diffraction data can be obtained under gas and vapour pressures ranging from 1 Pa to 130 kPa in temperatures ranging from 30 to 1473 K. This system enables one to perform automatic and high-throughput in situ X-ray powder diffraction experiments even at extremely low pressures. Furthermore, this developed system is useful for studying crystal structures during the adsorption/desorption processes, as acquired by millisecond and continuous powder diffraction measurements. The acquisition of diffraction data can be synchronized with the control of the pressure with a high frame rate of up to 100 Hz. In situ and time-resolved powder diffraction measurements are demonstrated for nanoporous Cu coordination polymer in various gas and vapour atmospheres. - Tomofumi Kadoya; Shotaro Mano; Aoi Hori; Keishiro Tahara; Kunihisa Sugimoto; Kazuya Kubo; Masaaki Abe; Hiroyuki Tajima; Jun-ichi YamadaOrganic Electronics 78 105570 - 105570 2020年03月We report a crystal structure analysis of an unsymmetrical organic semiconductor 2-bromo-7-butyl[1]benzothieno [3,2-b][1]benzothiophene (Br-BTBT-C-4) and its transistor characteristics. Unlike the parent compound 2-butyl-[1]benzothieno [3,2-b][1]benzothiophene (BTBT-C-4) forming a bilayer-type structure composed of headto-head herringbone packings, Br-BTBT-C-4 forms a dense head-to-tail herringbone packing arranged so as to avoid the steric hindrance between bromine atoms. The intermolecular transfer integrals in Br-BTBT-C-4 suggest its advantage for carrier transport; however, the transistor characteristics of Br-BTBT-C-4 and BTBT-C-4 were found to be almost the same. This is because BTBT-C-4 has a higher crystallinity than Br-BTBT-C-4 in vacuum deposited thin films.
- Shinobu Aoyagi; Ayumi Aoyagi; Hitoshi Osawa; Kunihisa Sugimoto; Yuki Nakahira; Chikako Moriyoshi; Yoshihiro Kuroiwa; Makoto IwataPhysical Review B 101 6 2020年02月We report results of the time-resolved x-ray structure analysis of a relaxor ferroelectric single crystal under an alternating electric field. The time dependence of the lattice strain, atomic displacements, and ferroelectric domain volumes in a 0.955Pb(Zn1/3Nb2/3)O-3- 0.045PbTiO(3) (PZN-4.5PT) single crystal during piezoelectric lattice straining and ferroelectric domain switching is revealed. The lattice strain induced by an electric field is consistent with that expected from the piezoelectric constants. The crystal mosaicity is momentarily increased by a nucleation of nanosized ferroelectric domains when the polarization switching starts. The nucleated ferroelectric domains grow with the time constant tau = 14 mu s. An intersite displacement of the disordered Pb atoms observed in those site occupancies suggests that a rotational intersite displacement of Pb atoms is easily induced by an electric field and causes continuous rotation of the spontaneous polarization. The rotational intersite displacement of Pb atoms is essential for the large piezoelectric lattice strain and fatigue-free ferroelectric domain switching.
- Ken-Ichi Otake; Kazuya Otsubo; Tokutaro Komatsu; Shun Dekura; Jared M Taylor; Ryuichi Ikeda; Kunihisa Sugimoto; Akihiko Fujiwara; Chien-Pin Chou; Aditya Wibawa Sakti; Yoshifumi Nishimura; Hiromi Nakai; Hiroshi KitagawaNature communications 11 1 843 - 843 2020年02月 [査読有り]
Water confined within one-dimensional (1D) hydrophobic nanochannels has attracted significant interest due to its unusual structure and dynamic properties. As a representative system, water-filled carbon nanotubes (CNTs) are generally studied, but direct observation of the crystal structure and proton transport is difficult for CNTs due to their poor crystallinity and high electron conduction. Here, we report the direct observation of a unique water-cluster structure and high proton conduction realized in a metal-organic nanotube, [Pt(dach)(bpy)Br]4(SO4)4·32H2O (dach: (1R, 2R)-(-)-1,2-diaminocyclohexane; bpy: 4,4'-bipyridine). In the crystalline state, a hydrogen-bonded ice nanotube composed of water tetramers and octamers is found within the hydrophobic nanochannel. Single-crystal impedance measurements along the channel direction reveal a high proton conduction of 10-2 Scm-1. Moreover, fast proton diffusion and continuous liquid-to-solid transition are confirmed using solid-state 1H-NMR measurements. Our study provides valuable insight into the structural and dynamical properties of confined water within 1D hydrophobic nanochannels. - Dirk Schlüter; Florian Kleemiss; Malte Fugel; Enno Lork; Kunihisa Sugimoto; Simon Grabowsky; Jeffrey R Harmer; Matthias VogtChemistry (Weinheim an der Bergstrasse, Germany) 26 6 1335 - 1343 2020年01月Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2 Cl2 ] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P). This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P). Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution.
- Yoshinobu Kamakura; Pondchanok Chinapang; Shigeyuki Masaoka; Akinori Saeki; Kazuyoshi Ogasawara; Shigeto R Nishitani; Hirofumi Yoshikawa; Tetsuro Katayama; Naoto Tamai; Kunihisa Sugimoto; Daisuke TanakaJournal of the American Chemical Society 142 1 27 - 32 2020年01月Recently, metal-organic frameworks (MOFs) composed of sulfur secondary building units (sulfur-SBUs) have attracted significant attention as unique electronic materials with high conductivities and photo- and electrocatalytic properties. Herein we report the crystal structure of KGF-1, an example of a Pb-MOF composed of three-dimensionally extended sulfur-SBUs that displays molecular sieving behavior, visible-light absorption, and a semiconductor band structure and is a hydrogen-evolution photocatalyst.
- Yoshimitsu Fukuyama; Nobuhiro Yasuda; Kunihisa Sugimoto; Shigeru KimuraJournal of Synchrotron Radiation 27 Pt 1 67 - 74 2020年01月 [査読有り]
A single-beam optical-trap sample holder for X-ray diffraction measurements with synchrotron radiation has been developed. The sample holder was used to obtain an X-ray diffraction image of a single ZnO particle levitated in air, without mechanical contact, by the optical gradient force exerted by a focused laser beam. The diffraction image showed a Debye ring pattern, which was similar to a powder diffraction pattern of an assemblage of ZnO particles. While the ZnO particle is held by the optical trap in air, it rotates irregularly. Therefore, the Debye ring pattern of the ZnO particle can be clearly obtained even if the ZnO particle is a single grain. Lattice parameters and crystallite size of the single ZnO particle were determined simultaneously. The lattice parameters were determined to be a = 3.2505 ± 0.0005 Å and c = 5.207 ± 0.006 Å, which are consistent with those of the assemblage of ZnO particles. The crystallite size determined by the Scherrer method was 193.4 ± 26.2 nm. - Hiroyuki Okazaki; David Billington; Naruki Tsuji; Wakana Ueno; Yoshinori Kotani; Shogo Kawaguchi; Kunihisa Sugimoto; Kentaro Toyoki; Tomoki Fukagawa; Takeshi Nishiuchi; Kazuhiro Hono; Satoshi Hirosawa; Tetsuya NakamuraActa Materialia 181 530 - 536 2019年12月 [査読有り]
© 2019 Acta Materialia Inc. We have measured the temperature dependent XRD profiles of an isotropic Nd-Fe-B-Cu sintered magnet during the annealing process. Through Rietveld refinement, we demonstrate the changes in the volume fractions of a Nd2Fe14B main-phase and the other secondary phases as a function of increasing temperature up to 1047 °C. The secondary phases mainly include dhcp-Nd, fcc-NdOx, and hcp-Nd2O3 at room temperature and fcc-Nd at elevated temperatures. The main phase starts melting above 900 °C but remains relatively stable up to 600 °C, while the dhcp-Nd phase completely disappears at around 600 °C. Taking an advantage of the excellent quality of the XRD profiles in the powdered single crystal sample, we have also investigated the electron density distribution of main-phase by MEM/Rietveld analysis in order to elucidate the origin of the large magnetic anisotropy. The change in asymmetric part of electron density is derived by the subtraction of the electron density distributions between those recorded at -123 and -173 °C, where the spin reorientation transition at -138 °C changes the magnetic anisotropy. This change is attributed to be a difference of electron density distribution between Nd f and g sites of the Nd2Fe14B, relating to the magnetic anisotropy. - Malte Fugel; Maksym V Ponomarenko; Maxie F Hesse; Lorraine A Malaspina; Florian Kleemiss; Kunihisa Sugimoto; Alessandro Genoni; Gerd-Volker Röschenthaler; Simon GrabowskyDalton transactions (Cambridge, England : 2003) 48 43 16330 - 16339 2019年11月The N-Si interaction in two pentacoordinated silicon compounds is investigated based on a complementary bonding analysis, which consists of bonding descriptors from real space and orbital space. These are derived from X-ray wavefunction refinements of high-resolution X-ray diffraction data of single crystals and from isolated-molecule theoretical wavefunctions. The two pentacoordinated compounds only differ in one methylene group, so that the amino substituent is more flexible in one of the structures, hence probing the attractive or repulsive character of the N-Si interaction. All studies suggest weak dative interactions, which do, however, greatly influence the character of the Si-F bond: A strong N-Si interaction results in a weakened Si-F bond, which is quantified in this study experimentally and theoretically.
- Maekawa Masahiko; Hayashi Terumasa; Sugimoto Kunihisa; Okubo Takashi; Kuroda-Sowa TakayoshiINORGANICA CHIMICA ACTA 497 2019年11月 [査読有り]
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. - Zhujun Zhang; Izuru Karimata; Hiroki Nagashima; Shunsuke Muto; Koji Ohara; Kunihisa Sugimoto; Takashi TachikawaNature communications 10 1 4832 - 4832 2019年10月 [査読有り]
Hematite (α-Fe2O3) is one of the most promising candidates as a photoanode materials for solar water splitting. Owing to the difficulty in suppressing the significant charge recombination, however, the photoelectrochemical (PEC) conversion efficiency of hematite is still far below the theoretical limit. Here we report thick hematite films (∼1500 nm) constructed by highly ordered and intimately attached hematite mesocrystals (MCs) for highly efficient PEC water oxidation. Due to the formation of abundant interfacial oxygen vacancies yielding a high carrier density of ∼1020 cm-3 and the resulting extremely large proportion of depletion regions with short depletion widths (<10 nm) in hierarchical structures, charge separation and collection efficiencies could be markedly improved. Moreover, it was found that long-lived charges are generated via excitation by shorter wavelength light (below ∼500 nm), thus enabling long-range hole transfer through the MC network to drive high efficiency of light-to-energy conversion under back illumination. - Moriyama Hayato; Otsubo Kazuya; Aoki Kentaro; Maesato Mitsuhiko; Sugimoto Kunihisa; Kitagawa HiroshiCHEMISTRY LETTERS 48 9 1035 - 1037 公益社団法人 日本化学会 2019年09月 [査読有り]
A novel Pt(III)–Pt(III) neutral dimer complex, Pt2(cdtb)4I2 (cdtb: 4-cyanodithiobenzoate) was successfully synthesized by the solvothermal method. Single-crystal X-ray structure analysis clearly revealed its molecular structure, where the Pt–Pt distance was 2.582(1) Å. Characteristic vibration modes and absorption bands derived from the Pt dimer structure were clearly observed in Raman and electronic absorption spectra, respectively, and the results were supported by density functional theory calculations.
- Mikihiro Hayashi; Yuki Takahashi; Yukihiro Yoshida; Kunihisa Sugimoto; Hiroshi KitagawaJournal of the American Chemical Society 141 29 11686 - 11693 2019年07月 [査読有り]
We first demonstrate the influence of d-elements on the electronic-state alternation of molecules coupled with proton transfer in d-π hybridized electron systems. Compact and planar metal complexes with protonated 2,3-pyrazinedithiolates (L), M(HL) 2 (M = Ni, Pd, and Pt), were synthesized and subsequently determined to be assembled by hydrogen bond (H-bond) interactions between pyrazine moieties. Structural and theoretical investigations revealed that these complexes are regarded as d-π hybridized electron systems based on a M(S2C2)2 core, especially, significant d-π hybridization in the Pt(S2C2)2 core was indicated. The pH-dependent optical and electrochemical measurements revealed that the Ni complex has a higher proton-accepting character and a stronger pH dependence for redox potential compared with the Pt complex. This indicates that the Ni complex has a larger amount of π-electron density on ligands than the Pt complex because the significant d-π hybridization in the Pt complex could reduce the amount of π-electron reconstructed by attaching/detaching proton. Cyclic voltammetry of Ni and Pt complexes that form an H-bonded multimer showed a potential splitting at the first redox wave (ΔE1/2 = 0.28 V for M = Ni and 0.17 V for M = Pt) corresponding to a mixed-valence state coupled with proton transfer. The ΔE1/2 values indicate that the change in electronic states by proton transfer is remarkable in the Ni complex, but moderate in the Pt complex. These experimental results lead that the d-element substitution plays a role in controlling the degree of proton-electron coupling in d-π hybridized electron systems. - Keishiro Tahara; Yuya Ashihara; Toshiki Higashino; Yoshiki Ozawa; Tomofumi Kadoya; Kunihisa Sugimoto; Akira Ueda; Hatsumi Mori; Masaaki AbeDalton transactions (Cambridge, England : 2003) 48 21 7367 - 7377 2019年06月 [査読有り]
Benzothienobenzothiophene (BTBT) and derivatives have received increasing attention as organic field-effect transistor materials and molecular conductors. This report presents the first synthesis of metal complexes involving a BTBT moiety, which was achieved by complexation of 2,2'-bipyridyl complexes of Pt(ii) and Pd(ii) with dihydroxy-substituted BTBT (1) as a new π-extended catecholato ligand (tBu2Bpy = 4,4'-di-tert-butyl-2,2'-dipyridyl). The resulting complexes M(tBu2Bpy)(O2BTBT) (M = Pt (3Pt) and Pd (3Pd)) were characterized by UV-vis spectroscopy, density functional theory (DFT) calculations, and cyclic voltammetry. The electron donating ability of BTBT was substantially enhanced upon including two oxygen substituents followed by metal coordination. This enabled chemical oxidation of 3Pt and 3Pd with a mild chemical oxidant (ferrocenium hexafluorophosphate) and formation of the one-electron-oxidized state. While 3Pt and 3Pd exhibited an absorption band originating from a catecholate → Bpy ligand-to-ligand charge transfer transition typical of this class of catecholato complexes, the radical cations exhibited a unique π-π* intramolecular charge transfer (ICT) transition absorption in which the π and π* orbitals were the newly incorporated benzothienothiophene-based donor and semiquinonato-based acceptor, respectively. The BTBT+ skeleton was electronically divided into two sites by the present chemical modification. The ICT properties of the complexes were found to be modulated by varying the metal ions. These findings offer a new approach to molecular design for (semi)conducting materials using optical properties. - Ogata Shuhei; Komiya Hiroaki; Goto Naoto; Tanabe Ryota; Sugimoto Kunihisa; Kawaguchi Shogo; Goto Kenta; Hatanaka Miho; Ishii Ayumi; Hasegawa MikiCHEMISTRY LETTERS 48 6 593 - 596 2019年06月 [査読有り]
An acyl group derived-bipyridine ligand and Eu form 3:2 complexes. The structure and luminescence behaviour were evaluated, and we found an unexpected bi-nuclear complex system, which induces efficiently the luminescence of europium ion. This observation is discussed from experimental and theoretical viewpoints. - Malte Fugel; Lorraine A Malaspina; Rumpa Pal; Sajesh P Thomas; Ming W Shi; Mark A Spackman; Kunihisa Sugimoto; Simon GrabowskyChemistry (Weinheim an der Bergstrasse, Germany) 25 26 6523 - 6532 2019年05月 [査読有り]
There are many examples of atoms in molecules that violate Lewis' octet rule, because they have more than four electron pairs assigned to their valence. These atoms are referred to as hypervalent. However, hypervalency may be regarded as an artifact arising from Lewis' description of molecules, which is based on the assumption that electrons are localized in two-center two-electron bonds and lone pairs. In the present paper, the isoelectronic phosphate (PO43- ), sulfate (SO42- ) and perchlorate (ClO4- ) anions were examined with respect to the concept of hypervalency. Lewis formulas containing a hypervalent central atom exist for all three anions. Based on X-ray wavefunction refinements of high-resolution X-ray diffraction data of representative crystal structures (MgNH4 PO4 ⋅6 H2 O, Li2 SO4 ⋅H2 O, and KClO4 ), complementary bonding analyses were performed. In this way, experimental information from the new field of quantum crystallography validate long-known facts, or refute long-standing misunderstandings. It is shown that the P-O and S-O bonds are highly polarized covalent bonds and, thus, the increase in the valence population following three-center four-electron bonding is not sufficient to yield hypervalent phosphorus or sulfur atoms, respectively. However, for the highly covalent Cl-O bond, most bonding indicators imply a hypervalent chlorine atom. - Takeaki Iwamoto; Takashi Abe; Kunihisa Sugimoto; Daisuke Hashizume; Hiroshi Matsui; Ryohei Kishi; Masayoshi Nakano; Shintaro IshidaAngewandte Chemie (International ed. in English) 58 13 4371 - 4375 2019年03月 [査読有り]
Bicyclo[1.1.0]tetrasil-1(3)-ene 1, a tetrasilicon analogue of bicyclo[1.1.0]but-1(3)-ene that contains a formal double bond between bridgehead silicon atoms in an inverted geometry, was synthesized and isolated in the form of thermally stable orange crystals. The distance between the bridgehead Si atoms in 1 is much longer than those in typical Si=Si bonds, but still shorter than that of a previously reported pentasila[1.1.1]propellane. DFT calculations suggest that the bridgehead bond in 1 comprises a σ bond with an inverted geometry and a π bond. This notion is supported by the UV/Vis spectrum of 1, which exhibits several absorption bands in the UV/Vis region. While 1 is stable toward typical trapping agents for Si=Si double bonds, 1 reacts with carbon tetrachloride to furnish a hexachlorotetrasilane. - Kohji Tashiro; Hiroko Yamamoto; Kunihisa Sugimoto; Tomohiko Takahama; Masaya Tanaka; Masaki HasegawaMACROMOLECULES 52 5 2189 - 2202 2019年03月 [査読有り]
The topotactic polymerization reaction is a special case of more general topochemical reactions, and it is defined as the photoinduced solid-state polymerization reaction, in which the space group symmetry is kept unchanged between the initial monomer and the final polymer-crystals and the morphology or crystal shape is also mostly unchanged through this solid-state polymerization reaction. The experimental check of the topotactic reaction is made by analyzing the structure relation between the original monomer single crystal and the resultant polymer single crystal. A half century ago, the 2,5-distyrylpyrazine (DSP) monomer single crystal was discovered as the first example of the [2 + 2]-type cycloaddition topotactic polymerization reaction. However, while the crystal structure of DSP monomer single crystal was analyzed, the crystal structure analysis of the corresponding polymer species had been left pending over these several tens of years, although the unit cell parameters and space group were reported in the literature. Because of such a situation, some argument was given to the proposed reaction system. Using synchrotron X-ray diffraction data, we have succeeded to analyze the crystal structure of the DSP polymer single crystal, by which clear and straightforward evidence of the topotactic polymerization reaction was extracted through the geometrical comparison between the monomer and polymer species. - Yoji Horii; Keiichi Katoh; Kunihisa Sugimoto; Ryo Nakanishi; Brian K Breedlove; Masahiro YamashitaChemistry (Weinheim an der Bergstrasse, Germany) 25 12 3098 - 3104 2019年02月 [査読有り]
In the research field of single-molecule magnets (SMMs), lanthanoid-lanthanoid interactions, so-called f-f interactions, are known to affect the SMM properties, although their magnitudes are small. In this article, an SMM with very weak f-f interactions is reported, and the effects of the interactions on the SMM properties are discussed. X-ray structural analysis of the DyIII -CdII -phthalocyaninato sextuple-decker complex (Dy2 Cd3 ) reveals that the intramolecular Dy-Dy length in Dy2 Cd3 is more than 13 Å, which is longer than the intermolecular Dy-Dy length. Even though the two DyIII ions are far apart, intermolecular ferromagnetic dipole-dipole interactions are observed in Dy2 Cd3 . From detailed analysis of ac magnetic susceptibilities, quantum tunneling of the magnetization (QTM) in Dy2 Cd3 is partially suppressed owing to the existence of very weak Dy-Dy interactions. Our results show that even very weak Dy-Dy interactions act as a dipolar bias, suppressing QTM. - Shinobu Aoyagi; Hitoshi Osawa; Kunihisa Sugimoto; Yuki Nakahira; Chikako Moriyoshi; Yoshihiro Kuroiwa; Hiroaki TakedaACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 75 E631 - E631 2019年
- Aoyagi Shinobu; Osawa Hitoshi; Sugimoto Kunihisa; Nakahira Yuki; Moriyoshi Chikako; Kuroiwa Yoshihiro; Takeda Hiroaki; Tsurumi TakaakiJAPANESE JOURNAL OF APPLIED PHYSICS 57 11 11UB06 - 11UB06 2018年11月 [査読有り]
Rare-earth substitution effects on atomic motions in resonantly vibrating piezoelectric oscillators of langasite-type crystals, namely, La3Ga5SiO14 (LGS) and Nd3Ga5SiO14 (NGS), are revealed by time-resolved X-ray crystal structure analysis under alternating electric fields. Deformations of Ga-O-Ga and Ga-O-Ga/Si bond angles accompanying deformations of RE-O (RE: La or Nd) bond lengths found in LGS are suppressed in NGS. Alternatively, rigid GaO6 octahedra are deformed in NGS. The decreases in RE-O bond lengths and Ga-O-Ga and Ga-O-Ga/Si bond angles caused by the substitution of La by Nd would make the bond lengths and angles more difficult to deform under electric fields; hence, the piezoelectric constants of NGS are smaller than those of LGS. (C) 2018 The Japan Society of Applied Physics - Z. Xiang; Y. Kasahara; T. Asaba; B. Lawson; C. Tinsman; Lu Chen; K. Sugimoto; S. Kawaguchi; Y. Sato; G. Li; S. Yao; Y. L. Chen; F. Iga; John Singleton; Y. Matsuda; Lu LiScience 362 issue 6410 65 - 69 2018年10月 [査読有り]
In metals, orbital motions of conduction electrons on the Fermi surface are quantized in magnetic fields, which is manifested by quantum oscillations in electrical resistivity. This Landau quantization is generally absent in insulators. Here, we report a notable exception in an insulator—ytterbium dodecaboride (YbB12). The resistivity of YbB12, which is of a much larger magnitude than the resistivity in metals, exhibits distinct quantum oscillations. These unconventional oscillations arise from the insulating bulk, even though the temperature dependence of the oscillation amplitude follows the conventional Fermi liquid theory of metals with a large effective mass. Quantum oscillations in the magnetic torque are also observed, albeit with a lighter effective mass. - Kohji Tashiro; Hiroko Yamamoto; Kunihisa SugimotoPOLYMER 153 474 - 484 2018年09月 [査読有り]
The crystal structure of the orthorhombic polyoxymethylene (POM) has been refined by analyzing the synchrotron X-ray diffraction data measured for a micrometer-size single crystal of moth-type morphology. The 3-dimensional elastic and compliance constants tensors were calculated for both the trigonal and orthorhombic phases on the basis of the thus-obtained accurate structure information. The crystal structure information allowed us also to discuss the solid-state phase transition behavior from the orthorhombic to the trigonal phase occurring at around 78 degrees C. For this purpose, we have performed the temperature-dependent synchrotron X-ray scattering measurement for a tiny moth-type single crystal and revealed the geometrical relation between these two crystals. The free energy was calculated as a function of temperature for these two accurately-analyzed crystal forms using a density functional theory (DFT). The result showed that the orthorhombic phase is thermodynamically more stable than the trigonal phase in a low temperature region, and the stability was reversed at about 225 K. This temperature corresponds to the phase transition point from the orthorhombic to trigonal phase, which is however considerably lower compared with the actually-observed transition point. The large discrepancy might be ascribed to the additional contribution of the entropy term due to the structural disorder and/or the thermal motion of chains with a large amplitude, which was not taken into account in the DFT calculation. - Masaki Donoshita; Mikihiro Hayashi; Ryuichi Ikeda; Yukihiro Yoshida; Shota Morikawa; Kunihisa Sugimoto; Hiroshi KitagawaChemical communications (Cambridge, England) 54 62 8571 - 8574 2018年08月 [査読有り]
A 2 : 1 hydrogen-bonded crystal of 2-pyrrolidone and chloranilic acid shows structural phase transitions accompanied by the drastic rearrangement of hydrogen-bonded tapes. Such a phenomenon is attributed to the selective and directional character of hydrogen bonds. - Malaspina Lorraine Andrade; Thomas Sajesh P; Sugimoto Kunihisa; Grabowsky SimonACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 74 E77 - E78 2018年08月 [査読有り]
- Naruki Tsuji; Hiroyuki Okazaki; Wakana Ueno; Yoshinori Kotani; David Billington; Akira Yasui; Shogo Kawaguchi; Kunihisa Sugimoto; Kentaro Toyoki; Tomoki Fukagawa; Takeshi Nishiuchi; Yoshihiro Gohda; Satoshi Hirosawa; Kazuhiro Hono; Tetsuya NakamuraACTA MATERIALIA 154 25 - 32 2018年08月 [査読有り]
The constituent phases of a Nd14.2Fe79.4B6.3Cu0.1 sintered magnet and their crystal structures at ambient and elevated temperatures have been determined by synchrotron X-ray diffraction. At room temperature, dhcp-Nd, NdOx, hcp-Nd2O3, and Nd5Fe18B18 (Nd1.1Fe4B4) secondary phases have been identified in addition to the Nd2Fe14B main phase. The dhcp-Nd phase melts around 600 degrees C, corresponding to the eutectic temperature for the ternary Nd2Fe14B, Nd and Nd5Fe18B18 system. Below 600 degrees C, the variation of the lattice constants of the dhcp-Nd phase with temperature is strongly influenced by an internal stress from the spontaneous magnetostriction of the Nd2Fe14B phase. The difference of the lattice constants of the dhcp-Nd phase compared to those of pristine Nd metal is also significant, which is possibly associated with the inclusion of interstitial oxygen atoms at the 4f Wyckoff positions in the dhcp-Nd crystal. The validity of this scenario is confirmed by first-principles calculations of the equilibrium lattice constants of three-, four-, and nine-unit-cell supercells, in which different numbers of oxygen atoms quasi randomly occupy some of the unoccupied 4f-sites. (C) 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. - Kentaro Aoki; Kazuya Otsubo; Garry S Hanan; Kunihisa Sugimoto; Hiroshi KitagawaInorganic chemistry 57 11 6222 - 6225 2018年06月 [査読有り]
Neutral triangular macrocyclic compounds, [PdX2(4,7-phen)]3·(DMF)3·Et2O (X = Cl, Br; 4,7-phen = 4,7-phenanthroline; DMF = N, N'-dimethylformamide; Et2O = diethyl ether), were synthesized, and their molecular structures were characterized. Solution-state 1H NMR results suggested the formation of metal-ligand bonds, and single-crystal X-ray crystallography revealed clear triangular structures. A detailed examination of the structures indicated the formation of two kinds of cavities in the solid state, where a triangular unit works as a halogen-based receptor for polar and apolar solvents through weak hydrogen-bonding and dipole-dipole interaction. - S. Yamada; H. Sagayama; K. Sugimoto; T. ArimaJournal of Physics: Conference Series 969 1 2018年04月We have succeeded in growing large high-quality single crystals of double-perovskite NdBaMn2O6 with c-Axis aligned. Curie-Weiss paramagnetism and metallic conduction are observed above 290 K (TMI ). The magnetic susceptibility suddenly drops at TMI accompanied by a metal-insulator transition. Pervious studies using polycrystalline samples proposed that this material undergoes a ferromagnetic phase transition near 300K, and that the magnetic anomaly at TMI should be ascribed to layered antiferromagnetic phase transition. However, single-crystalline samples do not show any anomaly that indicates the ferromagnetic phase transition above TMI . We assign the onset of magnetic anisotropy at 235 K as antiferromagnetic transition temperature TN . Though the magnetization just above TMI shows the ferromagnetic-like magnetic-field dependence, the magnetization does not saturate under 70kOe at 300K. The magnetization behavior implies ferromagnetic fluctuation in the paramagnetic phase. The ferromagnetic fluctuation are also observed just below TMI . Because a metamagnetic transition is observed at a higher magnetic field, the ferromagnetic fluctuation competes with antiferromagnetic fluctuation in this temperature range.
- Jun Zhang; Wataru Kosaka; Kunihisa Sugimoto; Hitoshi MiyasakaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 140 16 5644 - 5652 2018年04月 [査読有り]
A reversible magnetic change in response to external stimuli is a desired function of molecular magnetic materials. The magnetic change induced by a change in the intrinsic spin is significant because the magnetic change is inevitable and could become drastic. In this study, we demonstrate a reversible magnetic change closely associated with electronic state modulations, as well as structural modifications realized by solvation/desolvation cycles of a magnetic sponge. The compound was a D(2)A-type layered magnet, [{Ru-2(O2CPh-2,3,5-Cl-3)(4)}(2)(TCNQMe(2))]center dot 4DCM (1; 2,3,5-Cl3PhCO-2 = 2,3,5-trichlorobenzoate; TCNQMe(2) = 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane; DCM = dichloromethane), where [Ru-2(O2CPh-2,3,5-Cl-3)(4)] ([Ru-2(II,II)) is an electron donor (D) and TCNQMe(2) is an electron acceptor (A). Compound 1 had a one-electron-transferred, charge-ordered state with a [{Ru-2(II,II)}-TCNQMe(2)(center dot-){Ru-2(II,III)}(+) ](1e-I) formula. Strong intralayer antiferromagnetic couplings between [Ru-2(II,II)} with S = 1 or [Ru-2(II,III)](+) with S = 3/2 and TCNQMe(2)(center dot-) with S = 1/2, as well as ferromagnetic interlayer interactions, induced long-range ferrimagnetic ordering at T-c = 101 K. Interstitial DCM molecules were located between layers, and these were gradually eliminated under vacuum at 80 degrees C to form a solvent-free compound (1-dry) without loss of crystallinity. The electronic state of 1-dry thermally fluctuated and eventually provided a charge-disproportionate disordered state, with a [{Ru-2}(0.5+)-TCNQMe(2)(1.5)-{Ru-2(II,III)}(+)] (1.5e-I) formula as the ground state. The T-c in 1-dry was 34 K because of the presence of diamagnetic TCNQMe(2)(2-) in some parts of the framework. A large T-c variation with Delta T-c R approximate to 70 K was switchable; switching was achieved by charge-state modulations accompanied by subtle structural modifications in solvation/desolvation treatments. - Takashi Okubo; Kento Himoto; Koki Tanishima; Sanshiro Fukuda; Yusuke Noda; Masanobu Nakayama; Kunihisa Sugimoto; Masahiko Maekawa; Takayoshi Kuroda-SowaInorganic chemistry 57 5 2373 - 2376 2018年03月 [査読有り]
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. - Hidetaka Kasai; Kasper Tolborg; Mattia Sist; Jiawei Zhang; Venkatesha R Hathwar; Mette Ø Filsø; Simone Cenedese; Kunihisa Sugimoto; Jacob Overgaard; Eiji Nishibori; Bo B IversenNature materials 17 3 249 - 252 2018年03月 [査読有り]
Van der Waals (vdW) solids have attracted great attention ever since the discovery of graphene, with the essential feature being the weak chemical bonding across the vdW gap. The nature of these weak interactions is decisive for many extraordinary properties, but it is a strong challenge for current theory to accurately model long-range electron correlations. Here we use synchrotron X-ray diffraction data to precisely determine the electron density in the archetypal vdW solid, TiS2, and compare the results with density functional theory calculations. Quantitative agreement is observed for the chemical bonding description in the covalent TiS2 slabs, but significant differences are identified for the interactions across the gap, with experiment revealing more electron deformation than theory. The present data provide an experimental benchmark for testing theoretical models of weak chemical bonding. - Akitoshi Nakano; Kento Sugawara; Shinya Tamura; Naoyuki Katayama; Kazuyuki Matsubayashi; Taku Okada; Yoshiya Uwatoko; Kouji Munakata; Akiko Nakao; Hajime Sagayama; Reiji Kumai; Kunihisa Sugimoto; Naoyuki Maejima; Akihiko Machida; Tetsu Watanuki; Hiroshi SawaIUCrJ 5 Pt 2 158 - 165 2018年03月 [査読有り]
The crystal structure of the excitonic insulator Ta2NiSe5 has been investigated under a range of pressures, as determined by the complementary analysis of both single-crystal and powder synchrotron X-ray diffraction measurements. The monoclinic ambient-pressure excitonic insulator phase II transforms upon warming or under a modest pressure to give the semiconducting C-centred orthorhombic phase I. At higher pressures (i.e. >3 GPa), transformation to the primitive orthorhombic semimetal phase III occurs. This transformation from phase I to phase III is a pressure-induced first-order phase transition, which takes place through coherent sliding between weakly coupled layers. This structural phase transition is significantly influenced by Coulombic interactions in the geometric arrangement between interlayer Se ions. Furthermore, upon cooling, phase III transforms into the monoclinic phase IV, which is analogous to the excitonic insulator phase II. Finally, the excitonic interactions appear to be retained despite the observed layer sliding transition. - Kento Himoto; Toshiya Horii; Shoki Oda; Shimpei Suzuki; Kunihisa Sugimoto; Takashi Okubo; Masahiko Maekawa; Takayoshi Kuroda-SowaActa crystallographica. Section E, Crystallographic communications 74 Pt 2 233 - 236 2018年02月 [査読有り]
A new heterometallic CuI-NiII coordination polymer, poly[[tetra-μ3-iodido-μ2-iodido-bis-(μ3-piperidine-1-di-thio-carbamato)propio-nitrilepenta-copper(I)nickel(II)] chloro-form monosolvate], {[CuI5NiIII5(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-di-thio-carbamate) and a penta-nuclear 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 tetra-hedral coordination geometries. In the penta-nuclear 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 mol-ecules via Cl⋯I [3.653 (1) Å] and Cl⋯S [3.4370 (1) Å] short-contact inter-actions. - Yuki Hasegawa; Ayumi Ishii; Yudai Inazuka; Naho Yajima; Shogo Kawaguchi; Kunihisa Sugimoto; Miki HasegawaMolecules (Basel, Switzerland) 23 2 2018年01月 [査読有り]
The luminescence of a Eu complex (EuL) is enhanced by stabilization of the coordination structure in highly viscous ionic liquids. The EuL was found to maintain a stable single helical structure both in organic solvents and in the ionic liquids [BMIM][PF₆] and [EMIM][PF₆]. A colorless solution of EuL dissolved in [BMIM][PF₆] exhibits bright red luminescence with a quantum yield of 32.3%, a value that is much higher than that in acetonitrile (12%). Estimated rate constants for the energy relaxation pathway indicate that the energy transfer efficiency is enhanced in [BMIM][PF₆] as a result of the suppression of molecular fluctuations in the ligands. Additionally, a highly luminescent helical structure is preserved in [EMIM][PF₆] up to 120 °C. - Jae-Hoon Choi; Jing Wu; Azusa Sawada; Syougo Takeda; Hirohide Takemura; Kaoru Yogosawa; Hirofumi Hirai; Mitsuru Kondo; Kunihisa Sugimoto; Tomohiro Asakawa; Makoto Inai; Toshiyuki Kan; Hirokazu KawagishiOrganic letters 20 1 312 - 314 2018年01月 [査読有り]
Plant growth stimulators, 2-azahypoxanthine (AHX) and 2-aza-8-oxohypoxanthine (AOH), were isolated from the fairy-ring-forming fungus, Lepista sordida, and AHX-treated rice, respectively. Further metabolites of AHX were detected in AHX-treated rice by HPLC, and the metabolites 1-4 were isolated from the rice. The structures of 1-4 were determined by spectroscopic analysis and synthesis. Compounds 1-4 exhibited no significant activity against rice, indicating that rice regulates the activity of AHX and AOH by converting them into their glucosides. - Fritzsche, J.; Grzywa, M.; Denysenko, D.; Reschke, S.; Sugimoto, K.; Krug Von Nidda, H.-A.; Schmidtner, D.; Volkmer, D.Dalton Transactions 47 36 2018年
- J. Fritzsche; M. Grzywa; D. Denysenko; S. Reschke; K. Sugimoto; H.-A. Krug von Nidda; D. Schmidtner; D. VolkmerDalton Transactions 2018年
- Kento Sugawara; Kunihisa Sugimoto; Tatsuya Fujii; Takafumi Higuchi; Naoyuki Katayama; Yoshihiko Okamoto; Hiroshi SawaJournal of the Physical Society of Japan 87 2 2018年 [査読有り]
The distribution of d-orbital valence electrons in volborthite [Cu3V2O7(OH)212H2O] was investigated by charge density analysis of the multipole model refinement. Diffraction data were obtained by synchrotron radiation single-crystal X-ray diffraction experiments. Data reduction by detwinning of the multiple structural domains was performed using our developed software. In this study, using high-quality data, we demonstrated that the water molecules in volborthite can be located by the hydrogen bonding in cavities that consist of Kagome lattice layers of CuO4(OH)2 and pillars of V2O7. Final multipole refinements before and after the structural phase transition directly visualized the deformation electron density of the valence electrons. We successfully directly visualized the orbital flipping of the d-orbital dx2–y2, which is the highest level of 3d orbitals occupied by d9 electrons in volborthite. The developed techniques and software can be employed for investigations of structural properties of systems with multiple structural domains. - Kunihisa Sugimoto; Hikaru Takaya; Masahiko Maekawa; Takayoshi Kuroda-SowaCrystal Growth and Design 18 2 571 - 575 2018年 [査読有り]
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. - Kento Sugawara; Kunihisa Sugimoto; Naoyuki Katayama; Masayuki Hagiwara; Zentaro Honda; Hiroshi SawaJOURNAL OF THE PHYSICAL SOCIETY OF JAPAN 86 12 2017年12月 [査読有り]
We present structural studies of the spin-1/2 honeycomb-lattice antiferromagnet, Cu-2(pymca)(3)(ClO4) (pymca: pyrimidine-2-carboxylate), using synchrotron X-ray diffraction experiments. Previous research reported that its crystal structure consists of a regular honeycomb lattice, which exhibits quantum spin-liquid behavior. However, due to its threefold Cu2+ site symmetry, this proposed crystal structure cannot describe Jahn-Teller distortion. We analyzed the structure of Cu-2(pymca)(3)(ClO4), including superlattice reflections that were overlooked during previous X-ray diffraction studies of the material, and clarified that its distorted honeycomb lattice consists of Cu-2(pymca)(3) sections. Further investigation of Cu-2(pymca)(3)(ClO4) crystal structure may reveal magnetic susceptibilities of the distorted honeycomb lattice. - Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataINORGANICA CHIMICA ACTA 467 204 - 211 2017年10月 [査読有り]
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; Shogo Kawaguchi; Michitaka TakemotoPOWDER DIFFRACTION 32 S19 - S26 2017年09月 [査読有り]
In this work, we developed an X-ray powder diffractometer system equipped with six solid-state detectors and used it to perform ab initio structure determination from the powder diffraction pattern data obtained for a caffeine-oxalic acid co-crystal. The crystal structure obtained from the powder diffraction data was consistent with the previously solved single-crystal structure (Trask reference), although slightly larger (by about 2%). The co-crystallization of pharmaceutically active molecules can modulate their physical properties such as solubility, stability, and bioavailability. For the investigation of pharmaceutical complexes, the ability to visualize molecular interactions such as hydrogen bonding would be very helpful toward understanding their physical properties. Given the rate at which the high-throughput screening of pharmaceutical complexes has grown, an analogous high-volume, high-resolution X-ray powder diffraction technique with high-throughput data collection ability would be useful. We also solved the crystal structures of an inorganic complex and metal organic framework, zinc acetate dihydrate and CPL-1, in order to demonstrate the performance of our new diffractometer system. (C) 2017 International Centre for Diffraction Data. - Shunsuke Kitou; Tatsuya Fujii; Tadashi Kawamoto; Naoyuki Katayama; Sachiko Maki; Eiji Nishibori; Kunihisa Sugimoto; Masaki Takata; Toshikazu Nakamura; Hiroshi SawaPhysical review letters 119 6 065701 - 065701 2017年08月 [査読有り]
A quasi-one-dimensional organic charge-transfer salt (TMTTF)_{2}PF_{6} undergoes a multistep phase transition as the temperature decreases. One of these transitions is called a "structureless transition," and these detailed structures were unknown for many years. With synchrotron x-ray diffraction, we observed a slight structural difference owing to the effect of charge-order transition between two TMTTF molecules in a dimer, which corresponds to the charge transfer δ_{CO}=0.20e. The two-dimensional Wigner crystallization was determined from an electron density analysis using core differential Fourier synthesis. Furthermore, we found that the ground state due to tetramerization, called the spin Peierls phase, is a three-dimensional transition with interchain correlation. - Kawaguchi, S; Takemoto, M; Osaka, K; Nishibori, E; Moriyoshi, C; Kubota, Y; Kuroiwa, Y; Sugimoto, KREVIEW OF SCIENTIFIC INSTRUMENTS 88 8 85111 - 85111 AMER INST PHYSICS 2017年08月 [査読有り]
In this study, we developed a user-friendly automatic powder diffraction measurement system for Debye-Scherrer geometry using a capillary sample at beamline BL02B2 of SPring-8. The measurement system consists of six one-dimensional solid-state (MYTHEN) detectors, a compact autosampler, wide-range temperature control systems, and a gas handling system. This system enables to do the automatic measurement of temperature dependence of the diffraction patterns for multiple samples. We introduced two measurement modes in the MYTHEN system and developed new attachments for the sample environment such as a gas handling system. The measurement modes and the attachments can offer in situ and/or time-resolved measurements in an extended temperature range between 25 K and 1473 K and various gas atmospheres and pressures. The results of the commissioning and performance measurements using reference materials (NIST CeO2 674b and Si 640c), V2O3 and Ti2O3, and a nanoporous coordination polymer are presented. Published by AIP Publishing. - Tsuchiya, Mizuho; Sakamoto, Ryota; Shimada, Masaki; Yamanoi, Yoshinori; Hattori, Yohei; Sugimoto, Kunihisa; Nishibori, Eiji; Nishihara, HiroshiChemical communications (Cambridge, England) 53 54 7509 - 7512 ROYAL SOC CHEMISTRY 2017年07月 [査読有り]
Imine-linked BODIPY oligomers show fluorescence quantum yields of up to 0.93. The azine linker may mediate π-conjugation that extends over six BODIPY units with redshifts up to 125 nm. BODIPYs are immobilized on silica gel through heterogeneous imine-bond formation, being fluorescent and robust. - Mizuho Tsuchiya; Ryota Sakamoto; Masaki Shimada; Yoshinori Yamanoi; Yohei Hattori; Kunihisa Sugimoto; Eiji Nishibori; Hiroshi NishiharaCHEMICAL COMMUNICATIONS 53 54 7509 - 7512 2017年07月 [査読有り]
Imine-linked BODIPY oligomers show fluorescence quantum yields of up to 0.93. The azine linker may mediate pi-conjugation that extends over six BODIPY units with redshifts up to 125 nm. BODIPYs are immobilized on silica gel through heterogeneous imine-bond formation, being fluorescent and robust. - Shuhei Ogata; Tomohito Shimizu; Takashi Ishibashi; Yushi Ishiyone; Mitsuhiro Hanami; Minami Ito; Ayumi Ishii; Shogo Kawaguchi; Kunihisa Sugimoto; Miki HasegawaNEW JOURNAL OF CHEMISTRY 41 14 6385 - 6394 2017年07月 [査読有り]
The luminescence and structure of a water-soluble helicate Eu complex with L-COOH, which is a hexadentate ligand with COOH groups, were examined in solutions of various pH. The Eu complex EuLCOOH is more than eight-coordinated around Eu, and one of the two carboxylate groups is not bound, even in the powdered state, based on the FT-IR measurement. The synchrotron X-ray powder diffraction peaks of EuLCOOH broadened because of amorphous-like aggregation. EuLCOOH retains the ff emission of Eu in a wide pH range of 2.6-9.7 and shows spectral reversibility at pH = 1.9-11.9. From Horrocks' equation, the number of coordinated water molecules to Eu of EuLCOOH in the initial condition (3.0 x 10(-5) mol cm(-3); pH 2.6-9.7) was estimated to be 1, but it increased in both strongly alkaline and acidic solutions. Molecular structural changes in these solutions were assumed from the quantum yields and electrospray ionization-mass spectrometry measurements. For instance, one carboxyl group of EuLCOOH could provide hydrophilicity in the initial condition, and the other would be released from Eu at pH 2.1-2.6. Furthermore, EuLCOOH decomposes below pH 1.9, but recovers with adjustments toward the initial pH. The ff emission of TbLCOOH with a coordinated water molecule also appears in the green wavelength region in the initial condition. The luminescence ability of TbLCOOH in water is higher than that in its powder. The luminescence processes of these complexes are discussed as an energy relaxation through the excited triplet state of L-COOH assigned from the phosphorescence band of GdLCOOH. - Lorraine A. Malaspina; Alison J. Edwards; Magdalena Woinska; Dylan Jayatilaka; Michael J. Turner; Jason R. Price; Regine Herbst-Irmer; Kunihisa Sugimoto; Eiji Nishibori; Simon GrabowskyCRYSTAL GROWTH & DESIGN 17 7 3812 - 3825 2017年07月 [査読有り]
The position of the hydrogen atom inside the strong and short intramolecular hydrogen bond of the hydrogen maleate anion strongly varies depending on the crystalline environment. Therefore, it has not been possible in the past to accurately determine it using X-ray diffraction data although there are 292 hydrogen maleate crystal structures with different cations in the literature. In this study, a geometric correlation for the accurate prediction of the hydrogen position in the short intramolecular hydrogen bond is presented. The results used to derive the correlation are obtained from low-temperature neutron-diffraction studies on nine different hydrogen maleate salts that span the whole range from perfectly symmetric to highly asymmetric intramolecular hydrogen bonds. Since the only variable in the correlation as derived from the neutron data is the O center dot center dot center dot O distance, the hydrogen atom position in question can subsequently be predicted using information that is accurately available from routine X-ray data. The procedure is tested using high-resolution low-temperature synchrotron X-ray diffraction structures of the same compounds, before it is applied to X-ray data sets found in the literature in which the hydrogen atom position was not determined accurately or not determined at all, e.g., using a riding model. - Manabu Nakaya; Ryo Ohtani; Kunihisa Sugimoto; Masaaki Nakamura; Leonard F Lindoy; Shinya HayamiChemistry (Weinheim an der Bergstrasse, Germany) 23 30 7232 - 7237 2017年05月 [査読有り]
The nature of the molecular assemblies formed in the crystalline state by cobalt(II) terpyridine (terpy) complexes incorporating appended adenine (A) or thymine (T) bases was found to be controlled by which bases are present. Single-crystals of the cobalt(II) complexes [Co(A-C6-terpy)2 ](BF4 )2 (1) and [Co(T-C6-terpy)2 ](BF4 )2 (2) have needle and block habits, respectively. Subsequent mixing of 1 and 2 in MeOH resulted in isolation of [Co(A-C6-terpy)1.5 (T-C6-terpy)0.5 ](BF4 )2 (3) as plate-like crystals. A 3D network structure is present in 1 that incorporates 1D chains, whereas 2 adopts a 2D stacked structure constructed from ladder-type assemblies. For 3, "dimer-rings" consisting of [Co(A-C6-terpy)2 ]2+ and [Co(A-C6-terpy)(T-C6-terpy)]2+ units are generated by means of base-pairing between A and T. Notably, 3 displays the first crystal structure of a heteroleptic cobalt(II) complex of [Co(A-C6-terpy)(T-C6-terpy)](BF4 )2 . These assembly differences involving the terpyridine cobalt(II) complex units in 1-3 affect the cooperativities influencing their spin crossover (SCO) behavior. The influence of the terminal nucleobases on the resulting assembly has been probed by investigating the co-crystallization of [Co(terpy)2 ](BF4 )2 (4) with [Co(C6-terpy)2 ](BF4 )2 (5) and 1 with 5. - Yasuyo Ogino; Tetsuro Kusamoto; Yohei Hattori; Masaki Shimada; Mizuho Tsuchiya; Yoshinori Yamanoi; Eiji Nishibori; Kunihisa Sugimoto; Hiroshi NishiharaInorganic chemistry 56 7 3909 - 3915 2017年04月 [査読有り]
A paramagnetic, luminescent organometallic gold(I) complex AuI(C6F5)(PyBTM), where PyBTM is a photostable fluorescent polychlorinated diphenyl(4-pyridyl)methyl radical, was prepared, and its crystal and electronic structures and magnetic and optical properties were investigated. Magnetic studies using electron spin resonance spectroscopy and a superconducting quantum interference device magnetometer indicated the existence of S = 1/2 spin per molecule, with the spin density distributed mainly on the PyBTM ligand. The complex exhibited fluorescence in CHCl3 with emission peak wavelength (λem) of 619 nm and the absolute fluorescence quantum yield (ϕem) of 0.04, confirming that AuI(C6F5)(PyBTM) is the first luminescent organometallic complex with a coordinated luminescent radical. Solvent-dependent unique luminescent characteristics were observed in halogenated solvents (CCl4, CHCl3, CH2Cl2, and ClCH2CH2Cl). ϕem decreased, and λem shifted to longer wavelengths as the polarity (dielectric constant) of the solvent increased. Notably, the complex in CCl4 displayed fluorescence with ϕem = 0.23, which was quite high in radicals, while showed dual fluorescence in CH2Cl2 and ClCH2CH2Cl with lifetimes of around 1 and 7 ns for two emissive components. Density functional theory (DFT) and time-dependent (TD)-DFT calculations indicated that the fluorescence occurred from an interligand charge transfer (CT) excited state in CCl4, in which the C6F5 and PyBTM moieties acted as electron donor and acceptor, respectively, while the fluorescence was centered at the PyBTM ligand in the other three solvents. This method, i.e., the formation of an interligand CT state, to enhance ϕem is distinctly different from the methods reported previously. The present study revealed that a coordination bond is available for forming emissive CT excited states that lead to high ϕem, providing a novel method with greater capability for realizing highly emissive radicals. - Akiko Sohmiya; Tadashi Okuyama; Ryohei Suzuki; Katsunori Yamanishi; Kunihisa Sugimoto; Mitsuru KondoCHEMISTRY LETTERS 46 4 485 - 488 2017年04月 [査読有り]
A treatment of MCl2 (M = Zn, Ni, Co, Mg) with the indicator chrome pure blue BX (Na(2)cpb) yielded new coordination polymers, {[M(H2O) 6][M(cpb)(2)(H2O)(2)]center dot(H2O)(9)}(n) (M = Zn (1), Ni (2), Co (3)) and {[Mg(H2O) 6][Mg(cpb) 2(H2O)(2)]center dot (H2O)(6)}(n) (4). These compounds, which are crystallographically isostructural, show helical 1D nanotube structures. - Ogino, Yasuyo; Kusamoto, Tetsuro; Hattori, Yohei; Shimada, Masaki; Tsuchiya, Mizuho; Yamanoi, Yoshinori; Nishibori, Eiji; Sugimoto, Kunihisa; Nishihara, HiroshiInorganic chemistry 56 7 3909 - 3915 AMER CHEMICAL SOC 2017年04月 [査読有り]
A paramagnetic, luminescent organometallic gold(I) complex Au(I)(C6F5)(PyBTM), where PyBTM is a photostable fluorescent polychlorinated diphenyl(4-pyridyl)methyl radical, was prepared, and its crystal and electronic structures and magnetic and optical properties were investigated. Magnetic studies using electron spin resonance spectroscopy and a superconducting quantum interference device magnetometer indicated the existence of S = (1)/2 spin per molecule, with the spin density distributed mainly on the PyBTM ligand. The complex exhibited fluorescence in CHCl3 with emission peak wavelength (λem) of 619 nm and the absolute fluorescence quantum yield (ϕem) of 0.04, confirming that Au(I)(C6F5)(PyBTM) is the first luminescent organometallic complex with a coordinated luminescent radical. Solvent-dependent unique luminescent characteristics were observed in halogenated solvents (CCl4, CHCl3, CH2Cl2, and ClCH2CH2Cl). ϕem decreased, and λem shifted to longer wavelengths as the polarity (dielectric constant) of the solvent increased. Notably, the complex in CCl4 displayed fluorescence with ϕem = 0.23, which was quite high in radicals, while showed dual fluorescence in CH2Cl2 and ClCH2 - Ryota Hashiguchi; Kazuya Otsubo; Mitsuhiko Maesato; Kunihisa Sugimoto; Akihiko Fujiwara; Hiroshi KitagawaAngewandte Chemie (International ed. in English) 56 14 3838 - 3841 2017年03月 [査読有り]
The fabrication of so-called ghost-leg sheets and their electronic properties is reported. This unique sheet structure is composed of one-dimensional mixed-valence nickel chains, which are linked with one another by bis(azamacrocycle) ligands. They are also topologically unique NiII /NiIII mixed-valence complexes, as confirmed by X-ray and optical measurements. Moreover, their magnetic susceptibilities indicated two-dimensional antiferromagnetic behavior following the Fisher 1D chain model with interchain interactions, where spins on NiIII sites mutually interact antiferromagnetically in the sheets. - Nozomi Mihara; Yasuyuki Yamada; Shigehisa Akine; Kunihisa Sugimoto; Kentaro TanakaChemical communications (Cambridge, England) 53 14 2230 - 2232 2017年02月 [査読有り]
The redox potential of a supramolecular porphyrin-phthalocyanine heterodimer was perturbed by the stacking of an extra metalloporphyrin to the phthalocyanine. This stacking gave rise to π-π and electrostatic interactions between the tetracationic dimer and the tetraanionic metalloporphyrin, with a Au(iii) metalloporphyrin exhibiting a larger effect than Cu(ii) and Pd(ii) complexes among square planar complexes. - Kawaguchi Shogo; Sugimoto Kunihisa; Takemoto Michitaka; Kubota YoshikiACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 73 C966 - C966 2017年 [査読有り]
- Kleemiss Florian; Sugimoto Kunihisa; Beckmann Jens; Grabowsky SimonACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 73 C420 - C420 2017年 [査読有り]
- Sugimoto Kunihisa; Maekawa Masahiko; Kuroda-Sowa TakayoshiACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 73 C181 - C181 2017年 [査読有り]
- Malaspina Lorraine Andrade; Sugimoto Kunihisa; Edwards Alison J; Grabowsky SimonACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 73 C148 - C148 2017年 [査読有り]
- Claiser Nicolas; Voufack Ariste Bolivard; Souhassou Mohamed; Wenger Emmanuel; Dahaoui Slimane; Yan Zeyin; Gillet Jean-Michel; Sugimoto Kunihisa; Ito Masa-hisa; Ott HolgerACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 73 C1386 - C1386 2017年 [査読有り]
- S. Yamada; H. Sagayama; K. Higuchi; T. Sasaki; K. Sugimoto; T. ArimaPHYSICAL REVIEW B 95 3 2017年01月 [査読有り]
We have succeeded in growing large single crystals of double-perovskite NdBaMn2O6 with the c axis aligned, and carried out a crystal structure analysis and measurements of resistivity and magnetization. A first-order metal-insulator transition at T-MI similar or equal to 290 K is accompanied by a large jump of magnetization and lattice constants. The distortion of MnO6 octahedra is consistent with a ferroic orbital order of x(2)-y(2) type, although other orbital orders cannot be completely discarded. Neel temperature T-N is determined to be 235 K, which is fairly lower than T-MI, on the basis of the onset of a large magnetic anisotropy. Another structural phase transition from tetragonal to orthorhombic is found at 370 K, which arises from staggered tilting of MnO6 octahedra and little affects the transport and magnetic properties. - Mikihiro Hayashi; Kazuya Otsubo; Mitsuhiko Maesato; Tokutaro Komatsu; Kunihisa Sugimoto; Akihiko Fujiwara; Hiroshi KitagawaInorganic chemistry 55 24 13027 - 13034 2016年12月 [査読有り]
An electrically conductive D-A-D aggregate composed of a single component was first constructed by use of a protonated bimetal dithiolate (complex 1H2). The crystal structure of complex 1H2 has one-dimensional (1-D) π-stacking columns where the D and A moieties are placed in a segregated-stacking manner. In addition, these segregated-stacking 1-D columns are stabilized by hydrogen bonds. The result of a theoretical band calculation suggests that a conduction pathway forms along these 1-D columns. The transport property of complex 1H2 is semiconducting (Ea = 0.29 eV, ρrt = 9.1 × 104 Ω cm) at ambient pressure; however, the resistivity becomes much lower upon applying high pressure up to 8.8 GPa (Ea = 0.13 eV, ρrt = 6.2 × 10 Ω cm at 8.8 GPa). The pressure dependence of structural and optical changes indicates that the enhancement of conductivity is attributed to not only an increase of π-π overlapping but also a unique pressure-induced intramolecular charge transfer from D to A moieties in this D-A-D aggregate. - Shinobu Aoyagi; Hitoshi Osawa; Kunihisa Sugimoto; Shoichi Takeda; Chikako Moriyoshi; Yoshihiro KuroiwaJAPANESE JOURNAL OF APPLIED PHYSICS 55 10 2016年10月 [査読有り]
The momentary crystal structure of a Y-cut langasite oscillator resonantly vibrating under an alternating electric field is revealed by time-resolved crystal structure analysis to understand the microscopic mechanism of piezoelectricity. The thickness-shear lattice strain under an electric field is amplified similar to 10(3) times by the resonant effect. The lattice vibration involves the deformation of GaO4 and Ga0.5Si0.5O4 tetrahedra accompanied by atomic displacements of specific oxygen atoms along the electric field. The deformation of GaO4 and Ga0.5Si0.5O4 tetrahedra enhances the piezoelectricity of langasite. (C) 2016 The Japan Society of Applied Physics - Mattia Sist; Ellen Marie Jensen Hedegaard; Sebastian Christensen; Niels Bindzus; Karl Frederik Færch Fischer; Hidetaka Kasai; Kunihisa Sugimoto; Bo Brummerstedt IversenIUCrJ 3 Pt 5 377 - 388 2016年09月 [査読有り]
SnTe is a promising thermoelectric and topological insulator material. Here, the presumably simple rock salt crystal structure of SnTe is studied comprehensively by means of high-resolution synchrotron single-crystal and powder X-ray diffraction from 20 to 800 K. Two samples with different carrier concentrations (sample A = high, sample B = low) have remarkably different atomic displacement parameters, especially at low temperatures. Both samples contain significant numbers of cation vacancies (1-2%) and ordering of Sn vacancies possibly occurs on warming, as corroborated by the appearance of multiple phases and strain above 400 K. The possible presence of disorder and anharmonicity is investigated in view of the low thermal conductivity of SnTe. Refinement of anharmonic Gram-Charlier parameters reveals marginal anharmonicity for sample A, whereas sample B exhibits anharmonic effects even at low temperature. For both samples, no indications are found of a low-temperature rhombohedral phase. Maximum entropy method (MEM) calculations are carried out, including nuclear-weighted X-ray MEM calculations (NXMEM). The atomic electron densities are spherical for sample A, whereas for sample B the Te electron density is elongated along the 〈100〉 direction, with the maximum being displaced from the lattice position at higher temperatures. Overall, the crystal structure of SnTe is found to be defective and sample-dependent, and therefore theoretical calculations of perfect rock salt structures are not expected to predict the properties of real materials. - Shinobu Aoyagi; Akio Tokumitu; Kunihisa Sugimoto; Hiroshi Okada; Norihisa Hoshino; Tomoyuki AkutagawaJOURNAL OF THE PHYSICAL SOCIETY OF JAPAN 85 9 2016年09月 [査読有り]
Dielectric and X-ray diffraction measurements of [Li@C-60](PF6) single crystals reveal the motion of the Li+ cations inside the C-60 cages at low temperature. An increase in the dielectric permittivity below 100K is consistent with a combined tunneling and hopping motion of the Li+ cation between two positions inside the C-60 cage. A phase transition accompanied by a decrease in the dielectric permittivity at T-C = 24K is explained by an antiferroelectric ordering of the Li+ cations. The Li+ ordering is caused by interactions among electric dipole moments formed between the Li+ cations inside and the PF6- anions outside the C-60 cages. The electric dipole moments that are switched by the Li+ tunneling and interact with each other are potential qubits in a quantum computer using electric dipole moments. - Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataCHEMISTRYSELECT 1 13 3812 - 3822 2016年08月 [査読有り]
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. - Mizuho Tsuchiya; Ryota Sakamoto; Masaki Shimada; Yoshinori Yamanoi; Yohei Hattori; Kunihisa Sugimoto; Eiji Nishibori; Hiroshi NishiharaINORGANIC CHEMISTRY 55 12 5732 - 5734 2016年06月 [査読有り]
This Communication reports the first observation of solid-state photoluminescence in bis(dipyrrinato)zinc(II) complexes with various substituents. The report discusses the effect of their substituents on their crystal structures and spectroscopic properties. Their meso-aryl groups are revealed to play important roles in the spectroscopic properties in the solid state. - Satoshi Tsutsui; Kunihisa Sugimoto; Ryoma Tsunoda; Yusuke Hirose; Takeshi Mito; Rikio Settai; Masaichiro MizumakiJOURNAL OF THE PHYSICAL SOCIETY OF JAPAN 85 6 2016年06月 [査読有り]
A diffraction experiment using high-energy X-rays was carried out on YbInCu4. Below the Yb valence transition temperature, the splitting of Bragg peaks was detected in high-order reflections. No superlattice reflections accompanying the valence ordering were found below the transition temperature. These experimental findings indicate that a structural change from a cubic structure to a tetragonal structure without valence ordering occurs at the transition temperature. Such a structural change free from any valence ordering is difficult to understand only in terms of Yb valence degrees of freedom. This means that the structural change may be related to electronic symmetries such as quadrupolar degrees of freedom as well as to the change in Yb valence. - Takayuki Nakashima; Masaki Shimada; Yu Kurihara; Mizuho Tsuchiya; Yoshinori Yamanoi; Eiji Nishibori; Kunihisa Sugimoto; Hiroshi NishiharaJOURNAL OF ORGANOMETALLIC CHEMISTRY 805 27 - 33 2016年03月 [査読有り]
Various silicon-containing six-membered-ring molecules were synthesized by Pd-catalyzed coupling reaction of 1,2-bis(dimethylsilyl)arenes with 1,2-diiodoarenes in moderate yields. Their optical properties were investigated via UV-vis absorption, fluorescence and phosphorescence spectroscopies, which indicated that the sigma*-pi* conjugated system expanded owing to the silicon atoms. Some of the compounds exhibited enhanced luminescence, larger Stokes shift, and phosphorescence in comparison with 9,9,10,10-tetramethyl-9,10-dihydroanthracene. Density functional theory (DFT) studies were also performed to investigate the photophysical properties of the compounds. (C) 2016 Elsevier B. V. All rights reserved. - Lu Zheng; Xiao Miao; Yusuke Sakai; Hidenori Goto; Eri Uesugi; Ritsuko Eguchi; Saki Nishiyama; Kunihisa Sugimoto; Akihiko Fujiwara; Yoshihiro KubozonoPHYSICAL REVIEW B 93 10 2016年03月 [査読有り]
The superconducting transition temperature T-c of ammoniated metal-doped FeSe (NH3)(y)MxFeSe (M: metal atom) has been scaled with the FeSe plane spacing, and it has been suggested that the FeSe plane spacing depends on the location of metal atoms in (NH3)(y)MxFeSe crystals. Although the crystal structure of (NH3)(y)LixFeSe exhibiting a high T-c (similar to 44 K) was determined from neutron diffraction, the structure of (NH3)(y)MxFeSe exhibiting a low T-c (similar to 32 K) has not been determined thus far. Here, we determined the crystal structure of (NH3)(y)Cs0.4FeSe (T-c = 33 K) through the Rietveld refinement of the x-ray diffraction (XRD) pattern measured with synchrotron radiation at 30 K. The XRD pattern was analyzed based on two different models, on-center and off-center, under a space group of 14/mmm. In the on-center structure, the Cs occupies the 2a site and the N of NH3 may occupy either the 4c or 2b site, or both. In the off-center structure, the Cs may occupy either the 4c or 2b site, or both, while the N occupies the 2a site. Only an on-center structure model in which the Cs occupies the 2a and the N of NH3 occupies the 4c site provided reasonable results in the Rietveld analysis. Consequently, we concluded that (NH3)(y)Cs0.4FeSe can be assigned to the on-center structure, which produces a smaller FeSe plane spacing leading to the lower T-c. - Masaki Shimada; Mizuho Tsuchiya; Ryota Sakamoto; Yoshinori Yamanoi; Eiji Nishibori; Kunihisa Sugimoto; Hiroshi NishiharaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 55 9 3022 - 3026 2016年02月 [査読有り]
The development of disilane-bridged donor-acceptor-donor (D-Si-Si-A-Si-Si-D) and acceptor-donor-acceptor (A-Si-Si-D-Si-Si-A) compounds is described. Both types of compound showed strong emission ((em)=ca. 500 and ca. 400nm, respectively) in the solid state with high quantum yields (phi: up to 0.85). Compound 4 exhibited aggregation-induced emission enhancement in solution. X-ray diffraction revealed that the crystal structures of 2, 4, and 12 had no intermolecular - interactions to suppress the nonradiative transition in the solid state. - Kasai Hidetaka; Tolborg Kasper; Sist Mattia; Hathwar Venkatesha R; Filsoe Mette O; Cenedese Simone; Sugimoto Kunihisa; Overgaard Jacob; Nishibori Eiji; Iversen Bo BACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 72 S85 - S85 2016年 [査読有り]
- Grabowsky Simon; Malaspina Lorraine Andrade; Woinska Magdalena; Nishibori Eiji; Sugimoto Kunihisa; Edwards Alison J; Jayatilaka DylanACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 72 S89 - S89 2016年 [査読有り]
- Masataka Ohtani; Kazutaka Takase; Pengyu Wang; Kouki Higashi; Kimiyoshi Ueno; Nobuhiro Yasuda; Kunihisa Sugimoto; Mamoru Furuta; Kazuya KobiroCRYSTENGCOMM 18 11 1866 - 1870 2016年 [査読有り]
A millimeter-long metal-organic framework fiber has been successfully constructed. The fiber structure was unexpectedly found via the solvent vaporization process of a dispersion of a Zn-based MOF crystal. Detailed experiments and structural analysis indicate that a humid environment is a key to the growth of the fiber structure, inducing drastic transformation of the MOF crystal morphology from the nanoscopic to macroscopic scale. Synchrotron X-ray single-crystal diffraction analysis reveals that the complete crystal transformation from the Zn-MOF sheet to Zn-MOF fiber is accompanied by water coordination and ligand rearrangement. The highly anisotropic MOF fiber is easily converted to an electro conductive fiber while maintaining the long-fiber morphology. - S.kawaguchi; H.Ishibashi; S.Mori; J.Campo; F.Porcher; O.Fabelo; K.Sugimoto; J.Kim; K.Kato; M.Takata; H.Nakao; Y.KubotaPhysical Review B 93 2-1 024108-1 - 024108-9 2016年01月 [査読有り]
© 2016 American Physical Society. Using synchrotron and neutron diffraction measurements, we find a low-temperature orthorhombic phase in vanadium spinel FeV2O4. The orbital order of V3+ ions with tetragonal normal modes occurs at 68 K, and this leads to an appearance of the pseudotetragonal phase at a noncollinear ferrimagnetic transition temperature. Below the magnetic transition temperature, unconventional behavior of the orbital state of Fe2+ ions accompanied by the emergence of the orthorhombic phase was observed by using the normal mode analysis. We have also studied the structural properties of orbitally diluted materials. The orthorhombic phase, which is significantly affected by the other ions, is intrinsic in FeV2O4. We suggest the orthorhombic phase is strongly related with the double orbital states of Fe2+ and V3+ ions. - Masahiko Maekawa; Yukimi Kubo; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataEUROPEAN JOURNAL OF INORGANIC CHEMISTRY 1 78 - 91 2016年01月 [査読有り]
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. - Toshio Nishino; Yasuyuki Yamada; Shigehisa Akine; Kunihisa Sugimoto; Kentaro TanakaDALTON TRANSACTIONS 45 9 3831 - 3837 2016年 [査読有り]
Self-assembly based on reversible metal-ligand bond formation is useful for the synthesis of discrete supramolecular nanoarchitectures. However, the architectures constructed by this technique sometimes suffer from kinetic instability due to the dissociation of metal-ligand bonds, especially under highly diluted conditions or in the presence of competitive ligands or metal ions. In this study, a kinetically stabilized metallomacrocycle was synthesized in one pot via the combination of metal-mediated self-assembly and subsequent oxidative "locking" of the coordination bonds. The macrocycle consists of four Co ions and four bis-bidentate ligands L2-. The complexation of labile Co(II) ions with the ligands afforded the macrocycle with four-fold rotational symmetry, exhibiting the right-angled geometries of the beta-diketonate ligands on the carbazole. The subsequent oxidation of the Co(II) ions inside the macrocycle into Co(III) ions made the metal-ligand bonds almost inert, thus affording a kinetically locked 4 : 4 metallomacrocycle. This macrocycle showed high stability even in the presence of an excess amount of competitive ligands. X-ray crystallography of the macrocycle indicated that it assembled in a columnar manner, forming one-dimensional nanochannels in the middle of the column. - Otake, K.-I.; Otsubo, K.; Sugimoto, K.; Fujiwara, A.; Kitagawa, H.Inorganic Chemistry 55 5 2620 - 2626 2016年 [査読有り]
One-dimensional (1D) electronic systems have attracted significant attention for a long time because of their various physical properties. Among ID electronic systems, ID halogen-bridged mixed-valence transition-metal complexes (the so-called MX chains) have been thoroughly studied owing to designable structures and electronic states. Here, we report the syntheses, structures, and electronic properties of three kinds of novel neutral MX-chain complexes. The crystal structures consist of ID chains of Pt-X repeating units with (1R,2R)-(-)-diaminocychlohexane and CN- in-plane ligands. Because of the absence of a counteranion, the neutral MX chains have short interchain distances, so that strong interchain electronic interaction is expected. Resonance Raman spectra and diffuse reflectance UV-vis spectra indicate that their electronic states are mixed-valence states (charge-density-wave state: Pt2+center dot center dot center dot X-Pt4+-X center dot center dot center dot Pt2+center dot center dot center dot X-Pt4+-X center dot center dot center dot). In addition, the relationship between the intervalence charge-transfer (IVCT) band gap and the degree of distortion of the ID chain shows that the neutral MX chains have a larger IVCT band gap than that of cationic MX-chain complexes. These results provide new insight into the physical and electronic properties of ID chain compounds. - Otake, K.-I.; Otsubo, K.; Sugimoto, K.; Fujiwara, A.; Kitagawa, H.Angewandte Chemie - International Edition 55 22 6451 - 6451 2016年 [査読有り]
We report the structural design and control of electronic states of a new series of ultrafine metal-organic right square prism-shaped nanowires. These nanowires have a very small inner diameter of about 2.0 angstrom, which is larger than hydrogen and similar to xenon atomic diameters. The electronic states of nanowires can be widely controlled by substitution of structural components. Moreover, the platinum homometallic nanowire shows a 100 times higher proton conductivity than a palladium/platinum heterometallic one depending on the electronic states. - Shinobu Aoyagi; Hitoshi Osawa; Kunihisa Sugimoto; Akihiko Fujiwara; Shoichi Takeda; Chikako Moriyoshi; Yoshihiro KuroiwaAPPLIED PHYSICS LETTERS 107 20 2015年11月 [査読有り]
Transient atomic displacements during a resonant thickness-shear vibration of AT-cut alpha-quartz are revealed by time-resolved X-ray diffraction under an alternating electric field. The lattice strain resonantly amplified by the alternating electric field is similar to 10(4) times larger than that induced by a static electric field. The resonantly amplified lattice strain is achieved by fast displacements of oxygen anions and collateral resilient deformation of Si-O-Si angles bridging rigid SiO4 tetrahedra, which efficiently transduce electric energy into elastic energy. (C) 2015 AIP Publishing LLC. - Hayashi M; Otsubo K; Kato T; Sugimoto K; Fujiwara A; Kitagawa HChemical communications (Cambridge, England) 51 87 15796 - 15799 Royal Society of Chemistry 2015年11月 [査読有り]
Accepted 04 Sep 2015We present the first report of a compact, planar and low-energy-gap molecule based on a π-conjugated bimetal system comprising a tetrathiooxalate (tto) skeleton. The observed low HOMO-LUMO energy gap (1.19 eV) is attributed to its donor-acceptor-donor (D-A-D) nature because the skeleton acts as an electron acceptor as well as a tiny and noninnocent bridging moiety. - Shinobu Aoyagi; Hitoshi Osawa; Kunihisa Sugimoto; Makoto Iwata; Shoichi Takeda; Chikako Moriyoshi; Yoshihiro KuroiwaJAPANESE JOURNAL OF APPLIED PHYSICS 54 10 2015年10月 [査読有り]
Structural changes of a stoichiometric LiTaO3 single crystal accompanied by polarization switching are investigated using high-energy X-ray diffraction under static electric fields. The electric field dependence of the c-axis lattice constant depicts a small hysteresis and shows a butterfly curve. Inversion of the crystal structure accompanied by polarization switching is clearly detected with changes in the diffraction intensities of Friedel pairs. The electric field dependences of the atomic positions and volume ratio of the ferroelectric domains are obtained by crystal structure analyses. The results are fully consistent with the bulk properties and ensure that the present experimental techniques are applicable to detecting the transient atomic motions in the nucleation and growth of the ferroelectric domains during polarization switching. (C) 2015 The Japan Society of Applied Physics - Venkatesha R. Hathwar; Mattia Sist; Mads R. V. Jorgensen; Aref H. Mamakhel; Xiaoping Wang; Christina M. Hoffmann; Kunihisa Sugimoto; Jacob Overgaard; Bo Brummerstedt IversenIUCRJ 2 563 - 574 2015年09月 [査読有り]
Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended pi-conjugated core between molecules. We present here the electron density distribution in rubrene at 20 K and at 100 K obtained using a combination of high-resolution X-ray and neutron diffraction data. The topology of the electron density and energies of intermolecular interactions are studied quantitatively. Specifically, the presence of C-pi center dot center dot center dot C-pi interactions between neighbouring tetracene backbones of the rubrene molecules is experimentally confirmed from a topological analysis of the electron density, Non-Covalent Interaction (NCI) analysis and the calculated interaction energy of molecular dimers. A significant contribution to the lattice energy of the crystal is provided by H-H interactions. The electron density features of H-H bonding, and the interaction energy of molecular dimers connected by H-H interaction clearly demonstrate an importance of these weak interactions in the stabilization of the crystal structure. The quantitative nature of the intermolecular interactions is virtually unchanged between 20 K and 100 K suggesting that any changes in carrier transport at these low temperatures would have a different origin. The obtained experimental results are further supported by theoretical calculations. - Masahiro Abe; Takamichi Mori; Itaru Osaka; Kunihisa Sugimoto; Kazuo TakimiyaCHEMISTRY OF MATERIALS 27 14 5049 - 5057 2015年07月 [査読有り]
By developing an efficient synthetic route to the bis[1]benzothieno[2,3-d;2',3'-d]naphtho[2,3-b;6,7-b']dithiophene (BBTNDT) framework, we have successfully synthesized new BBTNDT derivatives with phenyl (DPh-BBTNDT) or n-hexyl groups (C6-BBTNDT) at the 2 and 10 positions. Characterization of their vapor-deposited thin films revealed that, depending on the substituents introduced, their HOMO energy levels were slightly altered, and DPh-BBTNDT with the HOMO energy level of ca. 5.3 eV was supposed to be a stable organic semiconductor under ambient conditions. In fact, the DPh-BBTNDT-based OTFTs showed not only high mobility of up to 7.0 cm(2) V-1 s(-1) under ambient conditions but also excellent operational and thermal stabilities up to 300 degrees C, whereas the parent and the hexyl derivative were less stable against the thermal treatments at high temperatures. The high mobility observed for the DPh-BBTNDT-based OTFTs can be correlated to the interactive packing structure in the bulk single crystal and thin film state of DPh-BBTNDT, which corroborates the existence of the well-balanced two-dimensional electronic structure in the solid state. With these excellent device characteristics, it can be concluded that DPh-BBTNDT is a promising and practical vapor-processable organic semiconductor, which can afford thermally, operationally, and environmentally stable OTFTs as well as high mobility. - Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataINORGANICA CHIMICA ACTA 426 64 - 70 2015年02月 [査読有り]
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. - Ryota Matsuoka; Ryojun Toyoda; Ryota Sakamoto; Mizuho Tsuchiya; Ken Hoshiko; Tatsuhiro Nagayama; Yoshiyuki Nonoguchi; Kunihisa Sugimoto; Eiji Nishibori; Tsuyoshi Kawai; Hiroshi NishiharaCHEMICAL SCIENCE 6 5 2853 - 2858 2015年 [査読有り]
One-dimensional coordination polymers (1D-CPs) tend either to dissociate into constitutive ligands and metals readily in solution, or to aggregate randomly and amorphously, which prevents them from widespread application. In the present research, 1D-CPs comprising bridging dipyrrin ligands and divalent metal ions (Zn2+, Ni2+, and Cu2+) are synthesized. A liquid/liquid interfacial reaction gives rise to single crystals suitable for X-ray diffraction analysis: A dichloromethane solution of the ligand is layered with aqueous metal(II) acetate, such that the coordination reaction proceeds at the liquid/liquid interface. Isolated single fibers of the zinc coordination polymer may be exfoliated from the single crystal or bulk solid upon ultrasonication. Atomic force microscopy (AFM) detects the isolated fibers with lengths of more than several mm. The exfoliated 1D-CP wires feature good processability, realizing a conjugate with single-wall carbon nanotubes (SWCNTs), and a thin film on a transparent SnO2 electrode. The processed materials show electric conversion ability: For example, the modified SnO2 electrode serves as a photoanode for a photoelectric conversion system. The designability and tunability of the present 1D-CPs is demonstrated by a ligand modification, affording a luminescent property and an extension of the photoelectric conversion response to longer wavelengths. - Mikihiro Hayashi; Kazuya Otsubo; Tatsuhisa Kato; Kunihisa Sugimoto; Akihiko Fujiwara; Hiroshi KitagawaCHEMICAL COMMUNICATIONS 51 87 15796 - 15799 2015年 [査読有り]
We present the first report of a compact, planar and low-energy-gap molecule based on a pi-conjugated bimetal system comprising a tetrathiooxalate (tto) skeleton. The observed low HOMO-LUMO energy gap (1.19 eV) is attributed to its donor-acceptor-donor (D-A-D) nature because the tto skeleton acts as an electron acceptor as well as a tiny and noninnocent bridging moiety. - Ryota Matsuoka; Ryojun Toyoda; Ryota Sakamoto; Mizuho Tsuchiya; Ken Hoshiko; Tatsuhiro Nagayama; Yoshiyuki Nonoguchi; Kunihisa Sugimoto; Eiji Nishibori; Tsuyoshi Kawai; Hiroshi NishiharaCHEMICAL SCIENCE 6 5 2853 - 2858 2015年 [査読有り]
One-dimensional coordination polymers (1D-CPs) tend either to dissociate into constitutive ligands and metals readily in solution, or to aggregate randomly and amorphously, which prevents them from widespread application. In the present research, 1D-CPs comprising bridging dipyrrin ligands and divalent metal ions (Zn2+, Ni2+, and Cu2+) are synthesized. A liquid/liquid interfacial reaction gives rise to single crystals suitable for X-ray diffraction analysis: A dichloromethane solution of the ligand is layered with aqueous metal(II) acetate, such that the coordination reaction proceeds at the liquid/liquid interface. Isolated single fibers of the zinc coordination polymer may be exfoliated from the single crystal or bulk solid upon ultrasonication. Atomic force microscopy (AFM) detects the isolated fibers with lengths of more than several mm. The exfoliated 1D-CP wires feature good processability, realizing a conjugate with single-wall carbon nanotubes (SWCNTs), and a thin film on a transparent SnO2 electrode. The processed materials show electric conversion ability: For example, the modified SnO2 electrode serves as a photoanode for a photoelectric conversion system. The designability and tunability of the present 1D-CPs is demonstrated by a ligand modification, affording a luminescent property and an extension of the photoelectric conversion response to longer wavelengths. - Mikihiro Hayashi; Kazuya Otsubo; Tatsuhisa Kato; Kunihisa Sugimoto; Akihiko Fujiwara; Hiroshi KitagawaCHEMICAL COMMUNICATIONS 51 87 15796 - 15799 2015年 [査読有り]
We present the first report of a compact, planar and low-energy-gap molecule based on a pi-conjugated bimetal system comprising a tetrathiooxalate (tto) skeleton. The observed low HOMO-LUMO energy gap (1.19 eV) is attributed to its donor-acceptor-donor (D-A-D) nature because the tto skeleton acts as an electron acceptor as well as a tiny and noninnocent bridging moiety. - Soonchul Kang; Hui Zheng; Tao Liu; Kohei Hamachi; Shinji Kanegawa; Kunihisa Sugimoto; Yoshihito Shiota; Shinya Hayami; Masaki Mito; Tetsuya Nakamura; Motohiro Nakano; Michael L. Baker; Hiroyuki Nojiri; Kazunari Yoshizawa; Chunying Duan; Osamu SatoNature Communications 6 2015年01月 [査読有り]
Self-assembly of artificial nanoscale units into superstructures is a prevalent topic in science. In biomimicry, scientists attempt to develop artificial self-assembled nanoarchitectures. However, despite extensive efforts, the preparation of nanoarchitectures with superior physical properties remains a challenge. For example, one of the major topics in the field of molecular magnetism is the development of high-spin (HS) molecules. Here, we report a cyanide-bridged magnetic nanocage composed of 18 HS iron(III) ions and 24 low-spin iron(II) ions. The magnetic iron(III) centres are ferromagnetically coupled, yielding the highest ground-state spin number (S = 45) of any molecule reported to date. - Masaki Shimada; Yoshinori Yamanoi; Tomonori Matsushita; Takashi Kondo; Eiji Nishibori; Akari Hatakeyama; Kunihisa Sugimoto; Hiroshi NishiharaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 137 3 1024 - 1027 2015年01月 [査読有り]
A series of disilane-bridged donor-acceptor architectures 1-9 containing strong electron-donating and -withdrawing substituents were designed and synthesized in acceptable yields. The substituents substantially affected the fluorescence and nonlinear optical properties of the compounds. In the solid state, the compounds showed purple-blue fluorescence (lambda(em) = 360-420 nm) with high quantum yields (up to 0.81). Compound 3, which had p-N,N-dimethylamino and o-cyano substituents, exhibited optical second harmonic generation (activity 2.9 times that of urea, calculated molecular hyperpolarizability beta = 1.6 x 10(-30) esu) in the powder state. Density functional theory calculations for the ground and excited states indicated that both the locally excited state and the intramolecular charge transfer excited state make important contributions to the luminescence behavior. - Shin-ichiro Noro; Junya Mizutani; Yuh Hijikata; Ryotaro Matsuda; Hiroshi Sato; Susumu Kitagawa; Kunihisa Sugimoto; Yasutaka Inubushi; Kazuya Kubo; Takayoshi NakamuraNATURE COMMUNICATIONS 6 2015年01月 [査読有り]
The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs. - Sagayama, H.; Toyoda, S.; Sugimoto, K.; Maeda, Y.; Yamada, S.; Arima, T.Physical Review B - Condensed Matter and Materials Physics 90 24 2014年12月 [査読有り]
- Magdalena Woinska; Dylan Jayatilaka; Mark A. Spackman; Alison J. Edwards; Paulina M. Dominiak; Krzysztof Wozniak; Eiji Nishibori; Kunihisa Sugimoto; Simon GrabowskyACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 70 5 483 - 498 2014年09月 [査読有り]
High-resolution low-temperature synchrotron X-ray diffraction data of the salt L-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z' > 1 treatments in the framework of wavefunction-based refinement methods. L-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O-H center dot center dot center dot O intramolecular hydrogen bond present in the hydrogen maleate anion (O center dot center dot center dot O distance is about 2.41 angstrom). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM; transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e. g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position. (C) 2014 International Union of Crystallography - Yasuyuki Yamada; Satoru Matsumoto; Kazushi Yamada; Toshio Nishino; Nozomi Mihara; Kunihisa Sugimoto; Kentaro TanakaCHEMISTRY LETTERS 43 8 1377 - 1379 2014年08月 [査読有り]
Single-crystal X-ray structures of stacked ionic assemblies of meso-tetrakis(N-alkylpyridinium-4-yl)porphyrin and meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4-) were revealed. The tetracationic porphyrin and the tetraanionic porphyrin stacked alternately in a J-aggregation manner to form an oblique columnar array. To the best of our knowledge, this is the first report on the detailed structure of 1:1 stacked assemblies of tetracationic and tetraanionic porphyrins. - Tonegawa S; Kasahara S; Fukuda T; Sugimoto K; Yasuda N; Tsuruhara Y; Watanabe D; Mizukami Y; Haga Y; Matsuda T D; Yamamoto E; Onuki Y; Ikeda H; Matsuda Y; Shibauchi TNature communications 5 Nature Publishing Group 2014年06月直接観測された物質物理学の謎「隠れた秩序」. 京都大学プレスリリース. 2014-06-19.Since the 1985 discovery of the phase transition at THO=17.5 K in the heavy-fermion metal URu2Si2, neither symmetry change in the crystal structure nor large magnetic moment that can account for the entropy change has been observed, which makes this hidden order enigmatic. Recent high-field experiments have suggested electronic nematicity that breaks fourfold rotational symmetry, but direct evidence has been lacking for its ground state in the absence of magnetic field. Here we report on the observation of lattice symmetry breaking from the fourfold tetragonal to twofold orthorhombic structure by high-resolution synchrotron X-ray diffraction measurements at zero field, which pins down the space symmetry of the order. Small orthorhombic symmetry-breaking distortion sets in at THO with a jump, uncovering the weakly first-order nature of the hidden-order transition. This distortion is observed only in ultrapure samples, implying a highly unusual coupling nature between the electronic nematicity and underlying lattice.
- David S. Ellis; Hiroshi Uchiyama; Satoshi Tsutsui; Kunihisa Sugimoto; Kenichi Kato; Alfred Q. R. BaronPHYSICA B-CONDENSED MATTER 442 34 - 38 2014年06月 [査読有り]
Inelastic and elastic X-ray scattering are used to investigate the structural phase transition which occurs in EuTiO3 at similar to 287 K. The dispersion of the soft phonon mode associated with the transition was measured about the R-point at 300 K, slightly above the transition, and is compared against a shell model. Below the structural transition temperature, a single R-point Bragg peak was observed, without any indication of more complex streaking reported from differently prepared samples. (C) 2014 Elsevier B.V. All rights reserved. - Jungeun Kim; Akihiko Fujiwara; Tomohiro Sawada; Younghun Kim; Kunihisa Sugimoto; Kenichi Kato; Hiroshi Tanaka; Motoyuki Ishikado; Shin-ichi Shamoto; Masaki TakataIUCRJ 1 155 - 159 2014年05月 [査読有り]
Understanding the nature of superconductivity in iron-based compounds is essential in the development of new strategies to increase T-c. Using a charge density analysis based on synchrotron radiation X-ray powder diffraction data, we found that the charge carriers only accumulated in the iron layer of the superconducting phase of LaFeAsO1-xFx at low temperatures. Analysis of the electrostatic potential distribution revealed the concerted enhancement of the electronic polarization of the As ions and the carrier redistribution. This suggests that the enhanced electronic polarization of the As ion plays an important role in inducing high T-c superconductivity, and that the polaron concept, which has been previously regarded as an untenable mechanism, should be reconsidered for the description of the iron-arsenide superconducting phase. - Younghun Kim; Jungeun Kim; Akihiko Fujiwara; Hiroki Taniguchi; Sungwng Kim; Hiroshi Tanaka; Kunihisa Sugimoto; Kenichi Kato; Mitsuru Itoh; Hideo Hosono; Masaki TakataIUCRJ 1 160 - 164 2014年05月 [査読有り]
Electric dipole engineering is now an emerging technology for high electron-mobility transistors, ferroelectric random access memory and multiferroic devices etc. Although various studies to provide insight into dipole moment behaviour, such as phase transition, order and disorder states, have been reported, macroscopic spontaneous polarization has been mainly discussed so far. Here, visualization of the electric dipole arrangement in layered ferroelectrics Bi2SiO5 by means of combined analysis of maximum entropy charge density and electrostatic potential distribution analysis based on synchrotron radiation X-ray powder diffraction data is reported. It was found that the hierarchical dipole orders, the weak-ferroelectric and ferroelectric configurations, were observed in the Bi2O2 and the SiO3 layers, respectively, and the ferrielectric configuration was realised by the interlayer interaction. This discovery provides a new method to visualize the local polarization in ferroelectric materials. - Masahiko Maekawa; Ai Minamino; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataINORGANICA CHIMICA ACTA 414 257 - 263 2014年04月 [査読有り]
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. - Yuki Sado; Shinobu Aoyagi; Noriko Izumi; Ryo Kitaura; Tim Kowalczyk; Jian Wang; Stephan Irle; Eiji Nishibori; Kunihisa Sugimoto; Hisanori ShinoharaCHEMICAL PHYSICS LETTERS 600 38 - 42 2014年04月 [査読有り]
The molecular structures of Tm-2@C-82(C-s(6)) and Tm2C2@C-82(C-s(6)) are determined by means of single crystal X-ray diffraction using the co-crystals with nickel octaethylporphyrin (Ni(OEP)). The molecular orientations and Tm positions of Tm-2@C-82(C-s(6)) and Tm2C2@C-82(C-s(6)) are basically the same each other. One of the two Tm positions is very close to the Tm position of Tm@C-82(C-s(6)). These facts demonstrate that the stable endohedral Tm positions are not fundamentally affected by the addition of the other Tm atoms but dependent on the kind of the fullerene cage structure. (C) 2014 Elsevier B.V. All rights reserved. - Tatsuya Toriyama; Masao Kobori; Takehisa Konishi; Yukinori Ohta; Kunihisa Sugimoto; Jungeun Kim; Akihiko Fujiwara; Sunseng Pyon; Kazutaka Kudo; Minoru NoharaJOURNAL OF THE PHYSICAL SOCIETY OF JAPAN 83 3 2014年03月 [査読有り]
Single-crystal X-ray diffraction was employed to study the structural-electronic phase transition of IrTe2 at approximately 270 K. The low-temperature structure was found to be a triclinic (space group P (1) over bar) characterized by the partial formation of Ir-2 dimers in the triangular lattice of IrTe2, resulting in a structural modulation with a wave vector of q = (1/5, 0, -1/5). First-principles band calculations demonstrate that tilted two-dimensional Fermi surfaces emerge in the triclinic phase, suggesting that switching of the conducting planes occurs from the basal plane of the trigonal IrTe2 to the tilted plane normal to q of the triclinic IrTe2. - Kawaguchi Shogo; Sugimoto Kunihisa; Takemoto Michitaka; Kubota YoshikiACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 70 C966 2014年 [査読有り]
- Claiser Nicolas; Voufack Ariste Bolivard; Souhassou Mohamed; Wenger Emmanuel; Dahaoui Slimane; Yan Zeyin; Gillet Jean-Michel; Sugimoto Kunihisa; Ito Masa-hisa; Ott HolgerACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 70 C1386 2014年 [査読有り]
- Kleemiss Florian; Sugimoto Kunihisa; Beckmann Jens; Grabowsky SimonACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 70 C420 2014年 [査読有り]
- Sugimoto Kunihisa; Maekawa Masahiko; Kuroda-Sowa TakayoshiACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 70 C181 2014年 [査読有り]
- Malaspina Lorraine Andrade; Sugimoto Kunihisa; Edwards Alison J; Grabowsky SimonACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 70 C148 2014年 [査読有り]
- Magdalena Woińska; Dylan Jayatilaka; Mark A. Spackman; Alison J. Edwards; Paulina M. Dominiak; Krzysztof Woźniak; Eiji Nishibori; Kunihisa Sugimoto; Simon GrabowskyActa Crystallographica Section A: Foundations and Advances 70 5 483 - 498 2014年 [査読有り]
High-resolution low-temperature synchrotron X-ray diffraction data of the salt l-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z′ > 1 treatments in the framework of wavefunction-based refinement methods. l-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O - H⋯O intramolecular hydrogen bond present in the hydrogen maleate anion (O⋯O distance is about 2.41Å). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e.g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position. © 2014 International Union of Crystallography. - Masahiko Maekawa; Takeshi Miyazaki; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaINORGANICA CHIMICA ACTA 410 46 - 53 2014年01月 [査読有り]
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. - Shinobu Aoyagi; Norihisa Hoshino; Tomoyuki Akutagawa; Yuki Sado; Ryo Kitaura; Hisanori Shinohara; Kunihisa Sugimoto; Rui Zhang; Yasujiro MurataCHEMICAL COMMUNICATIONS 50 5 524 - 526 2014年 [査読有り]
We report the crystal structure and dielectric properties of a pure H2O@C-60 crystal at low temperature. The caged water molecules free from the hydrogen bonds rotate even at 8 K. The antifreeze rotating water molecules respond to an external electric field due to their permanent dipole moment. - Kazuya Otsubo; Atsushi Kobayashi; Kunihisa Sugimoto; Akihiko Fujiwara; Hiroshi KitagawaINORGANIC CHEMISTRY 53 2 1229 - 1240 2014年01月 [査読有り]
Ladder systems situated in a crossover from one dimensionality to two dimensionalities have been an attractive research target, because the physical properties, which are associated with dimensionality, are strongly dependent on the number of constituent legs. However, control of the intraladder configuration and electronic properties based on the substitution of structural components remain challenging tasks in materials science. On the other hand, structural design using coordination chemistry offers crucial advantages for architectural and electronic variations through substitutions, of metal-organic building blocks. Here, we show the rational design and electronic properties of novel metal complex-based two-legged ladder compounds with several organic rung units: 4,4'-bipyridine, trans-1,4-diaminocyclohexane, and 4,4'-azopyridine. Single-crystal X-ray studies show that these two-legged ladder compounds are composed of halogen-bridged mixed-valence one-dimensional chains (MX chains) as their constituent legs. Depending on the molecular shape of the organic rung units, unique configurations of two-legged ladder lattices with periodic distortion of the legs are achieved. In addition, the electronic absorption spectra show that intervalence charge-transfer (IVCT) band gap of the two-legged ladder system increases with increasing degree of distortion of the leg. We have demonstrated for the first time that a two-legged ladder system shows a unique relationship between IVCT energy and the distortion parameter of the leg, as distinct from a single MX chain system. These systematic investigations, not only of configurations based on the rung variation but also of electronic states in metal-organic ladder system, provide the possibility for wide and rational tunings of physical and electronic properties of metal complex-based functional materials. - S.Niitaka; H Ohsumi; K.Sugimoto; S.Lee; Y.Oshima; K.kato; D.Hashizume; T.Arima; M.Takata; H.TakagiPhysical Review Letters 111 26 267201-1 - 267201-5 2013年12月 [査読有り]
We conduct a detailed structural analysis of the S=1 pyrochlore antiferromagnet MgV2O4, which exhibits an antiferromagnetic ordering marginally at TN=40 K, triggered by a structural transition from cubic to tetragonal symmetry at TS=62 K, using high resolution synchrotron x-ray diffraction and convergent beam electron diffraction. We reveal that the tetragonal phase below TS has the symmetry of I41/a and that the distortion pattern of VO6 octahedra is consistent with A-type antiferro-orbital ordering with alternating stacking of layers with yz/xy orbital chains and zx/xy orbital chains along the tetragonal c axis. This implies that an anisotropic coupling of V moments produced by the orbital ordering below TS primarily brings about the antiferromagnetic ordering. © 2013 American Physical Society. - Mette Stokkebro Schmokel; Lasse Bjerg; Finn Krebs Larsen; Jacob Overgaard; Simone Cenedese; Mogens Christensen; Georg K. H. Madsen; Carlo Gatti; Eiji Nishibori; Kunihisa Sugimoto; Masaki Takata; Bo Brummerstedt IversenACTA CRYSTALLOGRAPHICA SECTION A 69 6 570 - 582 2013年11月 [査読有り]
CoSb3 is an example of a highly challenging case for experimental charge-density analysis due to the heavy elements (suitability factor of similar to 0.01), the perfect crystallinity and the high symmetry of the compound. It is part of a family of host-guest structures that are potential candidates for use as high-performance thermoelectric materials. Obtaining and analysing accurate charge densities of the undoped host structure potentially can improve the understanding of the thermoelectric properties of this family of materials. In a previous study, analysis of the electron density gave a picture of covalent Co-Sb and Sb-Sb interactions together with relatively low atomic charges based on state-of-the-art experimental and theoretical data. In the current study, several experimental X-ray diffraction data sets collected on the empty CoSb3 framework are compared in order to probe the experimental requirements for obtaining data of high enough quality for charge-density analysis even in the case of very unsuitable crystals. Furthermore, the quality of the experimental structure factors is tested by comparison with theoretical structure factors obtained from periodic DFT calculations. The results clearly show that, in the current study, the data collected on high-intensity, high-energy synchrotron sources and very small crystals are superior to data collected at conventional sources, and in fact necessary for a meaningful charge-density study, primarily due to greatly diminished effects of extinction and absorption which are difficult to correct for with sufficient accuracy. - Yasuyuki Yamada; Nozomi Mihara; Shinya Shibano; Kunihisa Sugimoto; Kentaro TanakaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 135 31 11505 - 11508 2013年08月 [査読有り]
We report the preparation and crystal structure of a triply stacked metal complex array in which a Cu-phthalocyanine is sandwiched between different Cu-porphyrins. The discrete heterogeneous assembly was prepared through formation of a fourfold rotaxane from a tetradactyl porphyrin with alkylammonium moieties and a phthalocyanine bearing four crown ethers and the subsequent formation of an ionic complex between the fourfold rotaxane and a tetraanionic porphyrin. The tetraanionic porphyrin, Cu-TPPS4-, is selectively bound to the fourfold rotaxane through cooperative pi-pi and ionic interactions. The crystal structure revealed the columnar stacked array of the three planar building components in a precise order and spatial arrangement that promote intermolecular electronic communication. - Kenya Ohgushi; Jun-Ichi Yamaura; Hiroyuki Ohsumi; Kunihisa Sugimoto; Soshi Takeshita; Akihisa Tokuda; Hidenori Takagi; Masaki Takata; Taka-Hisa ArimaPhysical Review Letters 110 21 1 - 217212 2013年05月 [査読有り]
We performed resonant x-ray diffraction experiments at the L absorption edges for the post-perovskite-type compound CaIrO3 with a (t 2g)5 electronic configuration. By observing the magnetic signals, we could clearly see that the magnetic structure was a striped ordering with an antiferromagnetic moment along the c axis and that the wave function of a t 2g hole is strongly spin-orbit entangled, the Jeff=1/2 state. The observed spin arrangement is consistent with theoretical work predicting a unique superexchange interaction in the Jeff=1/2 state and points to the universal importance of the spin-orbit coupling in Ir oxides, independent of the octahedral connectivity and lattice topology. We also propose that nonmagnetic resonant scattering is a powerful tool for unraveling an orbital state even in a metallic iridate. © 2013 American Physical Society. - Katsuo Fukuhara; Shin-ichiro Noro; Kunihisa Sugimoto; Tomoyuki Akutagawa; Kazuya Kubo; Takayoshi NakamuraINORGANIC CHEMISTRY 52 8 4229 - 4237 2013年04月 [査読有り]
Porous coordination polymer (PCP) polymorphs with the formula [Cu(CF3SO3)(2)(bpp)(2)](n) [1 and 2, where bpp = 1,3-bis(4-pyridyl)propane] have been synthesized and crystallographically characterized, and their distinguishable porous properties have been investigated. 1 was obtained by the removal of guest acetone molecules from one-dimensional PCP {[Cu(CF3SO3)(bpp)(2)]center dot CF3SO3 center dot 2acetone}(n) (1 superset of 2acetone), while 2 was derived from two-dimensional PCP {[Cu(CF3SO3)(2)(bpp)(2)]center dot H2O} (2 superset of H2O) by the loss of guest H2O molecules. The desolvated PCPs 1 and 2 with the same formula [Cu(CF3SO3)(2)(bpp)(2)] showed distinguishable structures, suggesting PCP polymorphs. In addition, their adsorption behaviors were completely different: 1 showed adsorption with the structural transformation from closed to open forms, while 2 appeared to expand its framework for only as long as was required for the passage of guest molecules. To the best of our knowledge, PCP polymorphs showing either of two different types of flexible pores are very rare. - Sagayama, H.; Uematsu, D.; Arima, T.; Sugimoto, K.; Ishikawa, J.J.; O{'}Farrell, E.; Nakatsuji, S.Physical Review B - Condensed Matter and Materials Physics 87 10 2013年03月 [査読有り]
- Yuki Sado; Shinobu Aoyagi; Ryo Kitaura; Yasumitsu Miyata; Eiji Nishibori; Hiroshi Sawa; Kunihisa Sugimoto; Hisanori ShinoharaJOURNAL OF PHYSICAL CHEMISTRY C 117 12 6437 - 6442 2013年03月 [査読有り]
The molecular structure of Tm@C-82 (isomer I) is revealed by single-crystal X-ray diffraction of the 1:2 cocrystal with nickel octaethylporphyrin (Ni(OEP)). A rotational movement of Tm@C-82(I) molecule in the 1:1 cocrystal is dramatically suppressed by the coordination of two Ni(OEP) ligands in the 1:2 cocrystal. The structure of Tm@C-82(I) in the crystal is explained by the orientation disorder with two different orientations. The so-obtained carbon cage structure is C-5(6)-C-82. The restricted molecular orientations of Tm@C-82(I) in the 1:2 cocrystal are achieved by the molecular dipole moment of Tm@C-82(1) that interacts with two Ni(OEP) ligands. The present study suggests that the intermolecular interactions can reduce the degree of freedom in the orientation of spherical metallofullerene molecules in the crystals and complexes. - Kunihisa Sugimoto; Hiroshi Uemachi; Masahiko Maekawa; Akihiko FujiwaraCrystal Growth and Design 13 2 433 - 436 2013年02月 [査読有り]
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. - Sugimoto Kunihisa; Uemachi Hiroshi; Maekawa Masahiko; Fujiwara AkihikoACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 69 S542 - S543 2013年 [査読有り]
- Niitaka S; Ohsumi H; Sugimoto K; Lee S; Oshima Y; Kato K; Hashizume D; Arima T; Takata M; Takagi HPhysical Review Letters 111 26 267201 2013年 [査読有り]
- Robert E. Dinnebier; Tomče Runčevski; Kunihisa SugimotoZeitschrift fur Anorganische und Allgemeine Chemie 639 1 59 - 64 2013年01月 [査読有り]
Laboratory X-ray powder diffraction data were used to investigate the dehydration process of magnesium bromide hexahydrate in the temperature range 300 K ≤ T ≤ 420 K. By heating of the as synthesized hexahydrate (MgBr 2·6H2O, observed in the temperature range 300 K ≤ T ≤ 349 K), three lower hydrates can be obtained in overlapped temperature regions: MgBr2·4H2O (332 K ≤ T ≤ 367 K), MgBr2·2H2O (361 K ≤ T ≤ 380 K) and MgBr2·H2O (375 K ≤ T ≤ 390 K). Although the crystal structure of the hexahydrate was published almost eighty years ago, there are no data on the structures of the lower hydrates. The crystal structures are reported and are found to be isotypical with the structures of the respective chlorides. The structure of MgBr2·6H 2O is characterized by discrete Mg(H2O)6 octahedra and is the only hydrate of this group that contains unbonded Br - anions. MgBr2·4H2O is composed of discrete MgBr2(H2O)4 octahedra, and the structure was found to be disordered. The crystal structure of MgBr 2·2H2O is formed by single chains of edge-sharing MgBr4(H2O)2 octahedra, while in the case of MgBr2·H2O double chains of edge-shared MgBr 5H2O are formed. By increasing the temperature, as expected, positive thermal expansion was evidenced. Thermal expansion coefficients, based on the changes of the unit cell parameters, were derived for the following hydrates: MgBr2·6H2O, MgBr 2·4H2O, and MgBr2·2H 2O. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. - Mette Stokkebro Schmokel; Lasse Bjerg; Jacob Overgaard; Finn Krebs Larsen; Georg Kent Hellerup Madsen; Kunihisa Sugimoto; Masaki Takata; Bo Brummerstedt IversenANGEWANDTE CHEMIE-INTERNATIONAL EDITION 52 5 1503 - 1506 2013年 [査読有り]
- Masahiko Maekawa; Takeshi Miyazaki; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaDALTON TRANSACTIONS 42 12 4258 - 4266 2013年 [査読有り]
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. - Noro S; Fukuhara K; Sugimoto K; Hijikata Y; Kubo K; Nakamura TDalton transactions (Cambridge, England : 2003) 42 31 11100 - 11110 2013年 [査読有り]
We report the syntheses and crystal structures of novel porous assemblies of coordination complexes (PACs) with/without guest molecules, alpha-[Cu(A)(2)(py)(4)] (alpha-PAC-2-A (A = PF6, BF4, CF3SO3, and CH3SO3); py = pyridine), gamma-{[Cu(PF6)(2)(py)(4)]center dot 2guest} (gamma-PAC-2-PF6 superset of 2guest (guest = acetone and py)), gamma-{[Cu(BF4)(2)-(py)(4)]center dot 2acetone} (gamma-PAC-2-BF4 superset of 2acetone), and beta-{[Cu(CH3SO3)(2)(py)(4)]center dot 2.67H(2)O} (beta-PAC-2-CH3SO3 superset of 2.67H(2)O). The single-crystal X-ray diffraction analyses of alpha-PAC-2-A show that alpha-PAC-2-A have dense packing structures, in which anions of the discrete coordination complexes form weak hydrogen-bonding and anion-pi interactions. In contrast, gamma-PAC-2-PF6 superset of 2guest, gamma-PAC-2-BF4 superset of 2acetone, and beta-PAC-2-CH3SO3 superset of 2.67H(2)O form guest-including structures with coordination environments around the Cu-II atoms similar to the a-forms. The vapour adsorption measurements for MeCN and acetone in alpha-PAC-2-A suggest that the adsorption associated with structural transformations is induced by weak Lewis-base PF6- and BF4- anions covered only with fluorine atoms, which weaken the host-host interactions. - David S. Ellis; Hiroshi Uchiyama; Satoshi Tsutsui; Kunihisa Sugimoto; Kenichi Kato; Daisuke Ishikawa; Alfred Q. R. BaronPhysical Review B - Condensed Matter and Materials Physics 86 22 2012年12月 [査読有り]
We measured phonon dispersion in single-crystal EuTiO3 using inelastic x-ray scattering. A structural transition to an antiferrodistortive phase was found at a critical temperature T0=287±1 K using powder and single-crystal x-ray diffraction. Clear softening of the zone boundary R-point q=(0.50.50.5) acoustic phonon shows this to be a displacive transition. The mode energy plotted against reduced temperature could be seen to nearly overlap that of SrTiO3, suggesting a universal scaling relation. Phonon dispersion was measured along Γ-X (000)→(0.500). Mode eigenvectors were obtained from a shell model consistent with the q dependence of intensity and energy, which also showed that the dispersion is nominally the same as in SrTiO3 at room temperature, but corrected for mass. The lowest-energy optical mode, determined to be of Slater character, softens approximately linearly with temperature until the 70-100 K range where the softening stops, and at low temperature, the mode disperses linearly near the zone center. © 2012 American Physical Society. - Ellis, D.S.; Uchiyama, H.; Sugimoto, K.; Kato, K.; Baron, A.Q.R.Ferroelectrics 441 1 42 - 47 2012年12月 [査読有り]
- Yamaura J; Ohsumi H; Sugimoto K; Tsutsui S; Yoda Y; Takeshita S; Tokuda A; Kitao S; Kurokuzu M; Seto M; Yamauchi I; Ohgushi K; Takigawa M; Arima T; Hiroi ZJournal of Physics: Conference Series 391 1 012112 2012年12月 [査読有り]
The 5d transition metal oxide Cd2Os2O7 having a pyrochlore lattice of Os atoms exhibits a metal-insulator transition with a magnetic ordering at 227 K, but the magnetic structure in the ordered state and the origin of the transition have not yet been specified. The commensurate magnetic reflection with the propagation vector k (0, 0, 0) was first observed in the resonant X-ray scattering using a high-quality single crystal. We also clarified the only one kind of magnetic moment via the synchrotron radiation-based Mössbauer effect. We propose that a strong spin-orbit interaction is notably apparent in the spin arrangement and the insulating mechanism in this compound. © Published under licence by IOP Publishing Ltd. - David S. Ellis; Hiroshi Uchiyama; Satoshi Tsutsui; Kunihisa Sugimoto; Kenichi Kato; Daisuke Ishikawa; Alfred Q. R. BaronPHYSICAL REVIEW B 86 22 2012年12月 [査読有り]
We measured phonon dispersion in single-crystal EuTiO3 using inelastic x-ray scattering. Astructural transition to an antiferrodistortive phase was found at a critical temperature T-0 = 287 +/- 1K using powder and single-crystal x-ray diffraction. Clear softening of the zone boundary R-point q = (0.5 0.5 0.5) acoustic phonon shows this to be a displacive transition. The mode energy plotted against reduced temperature could be seen to nearly overlap that of SrTiO3, suggesting a universal scaling relation. Phonon dispersion was measured along Gamma-X (0 0 0) -> (0.5 0 0). Mode eigenvectors were obtained from a shell model consistent with the q dependence of intensity and energy, which also showed that the dispersion is nominally the same as in SrTiO3 at room temperature, but corrected for mass. The lowest-energy optical mode, determined to be of Slater character, softens approximately linearly with temperature until the 70-100 K range where the softening stops, and at low temperature, the mode disperses linearly near the zone center. - Fujiyama S; Ohashi K; Ohsumi H; Sugimoto K; Takayama T; Komesu T; Takata M; Arima T; Takagi HPHYSICAL REVIEW B 86 17 2012年11月 [査読有り]
The antiferromagnetic structure of Sr 3Ir 2O 7, the bilayer analog of a spin-orbital Mott insulator Sr 2IrO 4, was revealed by resonant magnetic x-ray diffraction. Contrasting intensities of the magnetic diffraction at the Ir L III and L II edges show a J eff=1/2 character of the magnetic moment as is argued in Sr 2IrO 4. The magnitude of moment, however, was found to be smaller than that of Sr 2IrO 4 by a factor of 5 to 6, implying that Sr 3Ir 2O 7 is no longer a Mott insulator but a weak antiferromagnet. An evident change of the temperature dependence of the resistivity at T N, from almost temperature-independent resistivity to insulating, strongly suggests that the emergent weak magnetism controls the charge gap. The magnetic structure was found to be an out-of-plane collinear antiferromagnetic ordering in contrast to the in-plane canted antiferromagnetism in Sr 2IrO 4, originating from the strong bilayer antiferromagnetic coupling. © 2012 American Physical Society. - Nii Y; Sagayama H; Arima T; Aoyagi S; Sakai R; Maki S; Nishibori E; Sawa H; Sugimoto K; Ohsumi H; Takata MPHYSICAL REVIEW B 86 12 2012年09月 [査読有り]
Spinel FeV2O4 exhibits successive structural phase transitions, reflecting the interplay between the Fe2+ (3d6) and V3+ (3d2) ions, both of which have orbital and spin degrees of freedom. The temperature-dependent orbital shapes of Fe2+ and V3 + were investigated by means of single-crystal structure analysis, and were compared with those in MnV2O4, where only the V3+ ions are Jahn-Teller active. The highest-temperature transition from the cubic to the high-temperature tetragonal phase was driven by a ferroic Fe2+ 3z2-r2 orbital order (OO). At 110 K, where the ferrimagnetic transition takes place, the magnetic order modified the orbital shape through intratomic spin-orbit coupling, causing an orthorhombic distortion. The V3 + orbital order (V-OO) contributed to the lowest temperature transition from the orthorhombic to the low-temperature tetragonal phase. The V-OO in FeV2O4 was qualitatively different from that in MnV2O4. We propose that ferro-OO contains a complex orbital in FeV2O4 in contrast to the V-OO of real orbitals observed in MnV2O4. © 2012 American Physical Society. - Kasahara, S.; Shi, H.J.; Hashimoto, K.; Tonegawa, S.; Mizukami, Y.; Shibauchi, T.; Sugimoto, K.; Fukuda, T.; Terashima, T.; Nevidomskyy, A.H.; Matsuda, Y.Nature 486 7403 382 - 385 2012年06月 [査読有り]
- Yamaura J; Ohgushi K; Ohsumi H; Hasegawa T; Yamauchi I; Sugimoto K; Takeshita S; Tokuda A; Takata M; Udagawa M; Takigawa M; Harima H; Arima T; Hiroi ZPHYSICAL REVIEW LETTERS 108 24 2012年06月 [査読有り]
Cd 2Os 2O 7 shows a peculiar metal-insulator transition at 227 K with magnetic ordering in a frustrated pyrochlore lattice, but its magnetic structure in the ordered state and the transition origin are yet uncovered. We observed a commensurate magnetic peak by resonant x-ray scattering in a high-quality single crystal. X-ray diffraction and Raman scattering experiments confirmed that the transition is not accompanied with any spatial symmetry breaking. We propose a noncollinear all-in-all-out spin arrangement on the tetrahedral network made of Os atoms. Based on this we suggest that the transition is not caused by the Slater mechanism as believed earlier but by an alternative mechanism related to the formation of the specific tetrahedral magnetic order on the pyrochlore lattice in the presence of strong spin-orbit interactions. © 2012 American Physical Society. - Taguchi Y; Sakai H; Okuyama D; Ishiwata S; Fujioka J; Fukuda T; Hashizume D; Kagawa F; Takahashi Y; Shimano R; Tokunaga Y; Kaneko Y; Nakao A; Nakao H; Murakami Y; Sugimoto K; Takata M; Yamauchi K; Picozzi S; Baron A. Q. R; Arima T; Tokura YPHYSICA B-CONDENSED MATTER 407 11 1685 - 1688 2012年06月 [査読有り]
Perovskite-type manganites exhibit various interesting phenomena arising from complex interplay among spin, charge, orbital, and lattice degrees of freedom. One such example is the keen competition between phases with different spin/charge/orbital orders. Keen competition between antiferromagnetic metal and orbital-ordered insulator is found in the slightly electron-doped regime near Mn 4 state which is stabilized by the high oxygen-pressure condition. Another one is the emergence of ferroelectricity either induced by the magnetic ordering or independently of the magnetic ordering. As the respective examples, perovskite-type YMnO 3 and Sr 1-xBa xMnO 3 are discussed. In the YMnO 3, the ferroelectric lattice distortion associated with the E-type spin order is observed for the first time. Displacement-type ferroelectricity with off-center magnetic ions is discovered for Sr 0.5Ba 0.5MnO 3, which shows both large polarization value and strong coupling between ferroelectricity and magnetism. © 2012 Elsevier B.V. All rights reserved. - Takuya Shiga; Akio Mishima; Kunihisa Sugimoto; Hisashi Okawa; Hiroki Oshio; Masaaki OhbaEUROPEAN JOURNAL OF INORGANIC CHEMISTRY 16 2784 - 2791 2012年06月 [査読有り]
A series of one-dimensional heterotrimetallic assemblies, [Cu2Ln(L)2(H2O)4][M(CN)6]center dot nH2O [Ln = Gd, M = Co (1), Fe (2), Cr (3), and Ln = La, M = Co (4), Fe (5), Cr (6)], were prepared by the reaction of a Cu2Ln precursor complex, [Cu2Ln(L)2(NO3)3], with K3[M(CN)6] in water. All of the assemblies were isomorphous and formed a 1D zigzag chain, in which the [Cu2Ln(L)2(H2O)4]3+ and [M(CN)6]3 units were alternately positioned and were linked in a CuNCMCNCu manner. Compound 1 showed magnetic behaviour similar to that of the discrete precursor complex, [Cu2Gd(L)2(NO3)3], owing to the diamagnetic nature of the [CoIII(CN)6]3 unit. In the case of 2, a simple summation of the magnetic behaviour of the [Cu2Gd(L)2(H2O)4]3+ and [Fe(CN)6]3 units was observed, whereas ferromagnetic interactions were found to be operative between the Cu2+ and Cr3+ ions in compound 3. The same magnetic interactions between Cu2+ and M3+ were confirmed in compounds 4 to 6, which included the diamagnetic La3+ ion. The differences in the magnetic behaviours of 2 and 3 can be explained by the overlap of the d?z?2(Cu)p pi(CN) orbitals in the bent CuN C linkage and the spin-density on the cyanide nitrogen of the [Cr(CN)6]3 unit. - Koji Ohara; Laszlo Temleitner; Kunihisa Sugimoto; Shinji Kohara; Toshiyuki Matsunaga; Laszlo Pusztai; Masayoshi Itou; Hiroyuki Ohsumi; Rie Kojima; Noboru Yamada; Takeshi Usuki; Akihiko Fujiwara; Masaki TakataADVANCED FUNCTIONAL MATERIALS 22 11 2251 - 2257 2012年06月 [査読有り]
Ge2Sb2Te5 (GST) has demonstrated its outstanding importance among rapid phase-change (PC) materials, being applied for optical and electrical data storage for over three decades. The mechanism of nanosecond phase change in GST, which is vital for its application, has long been disputed: various, quite diverse scenarios have been proposed on the basis of various experimental and theoretical approaches. Nevertheless, one central question still remains unanswered: why is amorphous GST stable at room temperature for long time while it can rapidly transform to the crystalline phase at high temperature? Here it is revealed for the first time, by modelling the amorphous structure based on synchrotron radiation anomalous X-ray scattering data, that germanium and tellurium atoms form a core Ge-Te network with ring formation. It is also suggested that the Ge-Te network can stabilize the amorphous phase at room temperature and can persist in the crystalline phase. On the other hand, antimony does not contribute to ring formation but constitutes a pseudo network with tellurium, in which the characteristic SbTe distance is somewhat longer than the covalent SbTe bond distance. This suggests that the Sb-Te pseudo network may act as a precursor to forming critical nuclei during the crystallization process. The findings conclude that the Ge-Te core network is responsible for the outstanding stability and rapid phase change of the amorphous phase while the Sb-Te pseudo network is responsible for triggering critical nucleation. - Masahiko Maekawa; Yukimi Kubo; Kunihisa Sugimoto; Toshie Minematsu; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataPOLYHEDRON 40 1 145 - 152 2012年06月 [査読有り]
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. - Akihiko Fujiwara; Kunihisa Sugimoto; Che-Hsiu Shih; Hiroshi Tanaka; Jun Tang; Yoichi Tanabe; Jingtao Xu; Satoshi Heguri; Katsumi Tanigaki; Masaki TakataPHYSICAL REVIEW B 85 14 2012年04月 [査読有り]
In order to quantitatively characterize the effect of motion of the guest atom in type-I clathrates X8Ga16Ge30 (X = Sr, Ba) on thermal conductivity, electrostatic potential in the crystal was visualized by synchrotron radiation x-ray diffraction. The obtained electrostatic potential clearly exhibited structural aspects of the guest atom, rattling, which is considered as a cause of suppression of thermal conductivity kappa. The parameterized degree of rattling "rattling factor," f(R), being defined as a volume ratio of the electrostatic interaction region of the guest atom to the spherical volume estimated by the covalent radius of the guest atom, was found to well classify kappa. The. monotonously decreases with increasing the f(R). Consequently, f(R) was judged as a better criterion to explore high-performance thermoelectric system of the clathrates. - Masahiko Maekawa; Toshi Tominaga; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaCRYSTENGCOMM 14 4 1345 - 1353 2012年 [査読有り]
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 14 18 5955 - 5962 2012年 [査読有り]
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. - Chou-Fu Sheu; Che-Hsiu Shih; Kunihisa Sugimoto; Bing-Ming Cheng; Masaki Takata; Yu WangCHEMICAL COMMUNICATIONS 48 46 5715 - 5717 2012年 [査読有り]
In addition to the generally observed LIESST phenomenon, polymorph D of trans-[Fe-II(abpt)(2)(NCS)(2)] exhibits a long-lived photo-induced metastable state through linkage isomerization accompanied with a spin crossover transition, which is stable up to 108 K. - Chikako Moriyoshi; Shozo Hiramoto; Hisanori Ohkubo; Yoshihiro Kuroiwa; Hitoshi Osawa; Kunihisa Sugimoto; Shigeru Kimura; Masaki Takata; Yuuki Kitanaka; Yuji Noguchi; Masaru MiyayamaJAPANESE JOURNAL OF APPLIED PHYSICS 50 9 2011年09月 [査読有り]
The dynamic response of an intrinsic lattice strain in a tetragonal BaTiO3 single crystal to an electric field is investigated. Time-resolved diffraction measurement using high-energy synchrotron radiation enables us to detect the time dependence of the small change in the tetragonality of BaTiO3 during polarization reversal and piezoelectric vibration after a step like electric field antiparallel to the spontaneous polarization is applied to the sample. (C) 2011 The Japan Society of Applied Physics - Okuyama D; Ishiwata S; Takahashi Y; Yamauchi K; Picozzi S; Sugimoto K; Sakai H; Takata M; Shimano R; Taguchi Y; Arima T; Tokura YPHYSICAL REVIEW B 84 5 2011年08月 [査読有り]
Magnetically driven ferroelectric atomic displacements of the order of 10-3 Å have been observed in orthorhombic (perovskite like) YMnO3 by a single-crystal synchrotron x-ray diffraction. The refined polar structure shows the characteristic bond alternation driven by the exchange striction in staggered Mn-O-Mn arrays with ↑↑↓↓ type ordering, giving rise to a spontaneous polarization along the a axis. First-principles calculations based on the Berry phase method as well as on the experimentally refined crystal structure can reproduce the observed polarization value. © 2011 American Physical Society. - Yuki Utsumi; Hitoshi Sato; Chikako Moriyoshi; Yoshihiro Kuroiwa; Hirofumi Namatame; Masaki Taniguchi; Koichi Hiraoka; Kenichi Kojima; Kunihisa SugimotoJAPANESE JOURNAL OF APPLIED PHYSICS 50 5 2011年05月 [査読有り]
The structural change of an YbInCu4 single crystal has been investigated associated with the first-order valence-transition at T-V = 42 K using synchrotron radiation diffraction. The Yb-Cu and In-Cu interatomic distances abruptly increase below T-V, following the lattice expansion with no change in the C15b-type crystal structure. We find that the distance between Cu ions forming the Cu-4 cluster in the crystal is almost unchanged across the valence transition. No abrupt change in the thermal rotational motion of the Cu-4 cluster is observed at T-V. (C) 2011 The Japan Society of Applied Physics - Bagautdinov Bagautdin; Tanaka Hiroshi; Shih Che-Hsiu; Sugimoto Kunihisa; Sasaki Sono; Tashiro Kohji; Takata MasakiACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 67 C27 - C28 2011年 [査読有り]
- Yohei Takashima; Virginia Martinez Martinez; Shuhei Furukawa; Mio Kondo; Satoru Shimomura; Hiromitsu Uehara; Masashi Nakahama; Kunihisa Sugimoto; Susumu KitagawaNATURE COMMUNICATIONS 2 2011年01月 [査読有り]
Chemosensors detect a single target molecule from among several molecules, but cannot differentiate targets from one another. In this study, we report a molecular decoding strategy in which a single host domain accommodates a class of molecules and distinguishes between them with a corresponding readout. We synthesized the decoding host by embedding naphthalenediimide into the scaffold of an entangled porous framework that exhibited structural dynamics due to the dislocation of two chemically non-interconnected frameworks. An intense turn-on emission was observed on incorporation of a class of aromatic compounds, and the resulting luminescent colour was dependent on the chemical substituent of the aromatic guest. This unprecedented chemoresponsive, multicolour luminescence originates from an enhanced naphthalenediimide-aromatic guest interaction because of the induced-fit structural transformation of the entangled framework. We demonstrate that the cooperative structural transition in mesoscopic crystal domains results in a nonlinear sensor response to the guest concentration. - Masahiko Maekawa; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu MunakataPOLYHEDRON 29 14 2807 - 2813 2010年09月 [査読有り]
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. - Shinobu Aoyagi; Eiji Nishibori; Hiroshi Sawa; Kunihisa Sugimoto; Masaki Takata; Yasumitsu Miyata; Ryo Kitaura; Hisanori Shinohara; Hiroshi Okada; Takeshi Sakai; Yoshihiro Ono; Kazuhiko Kawachi; Kuniyoshi Yokoo; Shoichi Ono; Kenji Omote; Yasuhiko Kasama; Shinsuke Ishikawa; Takashi Komuro; Hiromi TobitaNATURE CHEMISTRY 2 8 678 - 683 2010年08月 [査読有り]
If the physical properties of C-60 fullerene molecules can be controlled in C-60 products already in use in various applications, the potential for industrial development will be significant. Encapsulation of a metal atom in the C-60 fullerene molecule is a promising way to control its physical properties. However, the isolation of C-60-based metallofullerenes has been difficult due to their insolubility. Here, we report the complete isolation and determination of the molecular and crystal structure of polar cationic Li@C-60 metallofullerene. The physical and chemical properties of Li@C-60 cation are compared with those of pristine C-60. It is found that the lithium cation is located at off-centre positions in the C-60-I-h cage interior and that the [Li+@C-60] salt has a unique two-dimensional structure. The present method of purification and crystallization of C-60-based metallofullerenes provides a new C-60 fullerene material that contains a metal atom. - Hiroshi Sato; Ryotaro Matsuda; Kunihisa Sugimoto; Masaki Takata; Susumu KitagawaNATURE MATERIALS 9 8 661 - 666 2010年08月 [査読有り]
Porous compounds are ubiquitous and indispensable in daily life as adsorbents and catalysts. The discovery of a new porous compound with unique properties based on intrinsic nanosized space and surface functionalities is scientifically and technologically important. However, the functional species used in this context are limited to those that are sufficiently inert to not spoil the porous structures. Here, we show a new strategy to achieve a crystalline porous material with the pore surface regularly decorated with highly reactive 'bare' nitrenes that are photonically generated from stable 'dormant' precursors at will. The bare triplet nitrenes were accessible to and reacted with adsorbed oxygen or carbon monoxide molecules, which showed not only activation of the pore surface, but also a high probability of chemical trapping and conversion of guest molecules by light stimulation on demand. - Shinobu Aoyagi; Eiji Nishibori; Hiroshi Sawa; Kunihisa Sugimoto; Masaki Takata; Yasumitsu Miyata; Ryo Kitaura; Hisanori Shinohara; Hiroshi Okada; Takeshi Sakai; Yoshihiro Ono; Kazuhiko Kawachi; Kuniyoshi Yokoo; Shoichi Ono; Kenji Omote; Yasuhiko Kasama; Shinsuke Ishikawa; Takashi Komuro; Hiromi TobitaNATURE CHEMISTRY 2 8 678 - 683 2010年08月 [査読有り]
If the physical properties of C-60 fullerene molecules can be controlled in C-60 products already in use in various applications, the potential for industrial development will be significant. Encapsulation of a metal atom in the C-60 fullerene molecule is a promising way to control its physical properties. However, the isolation of C-60-based metallofullerenes has been difficult due to their insolubility. Here, we report the complete isolation and determination of the molecular and crystal structure of polar cationic Li@C-60 metallofullerene. The physical and chemical properties of Li@C-60 cation are compared with those of pristine C-60. It is found that the lithium cation is located at off-centre positions in the C-60-I-h cage interior and that the [Li+@C-60] salt has a unique two-dimensional structure. The present method of purification and crystallization of C-60-based metallofullerenes provides a new C-60 fullerene material that contains a metal atom. - Hiroshi Sato; Ryotaro Matsuda; Kunihisa Sugimoto; Masaki Takata; Susumu KitagawaNATURE MATERIALS 9 8 661 - 666 2010年08月 [査読有り]
Porous compounds are ubiquitous and indispensable in daily life as adsorbents and catalysts. The discovery of a new porous compound with unique properties based on intrinsic nanosized space and surface functionalities is scientifically and technologically important. However, the functional species used in this context are limited to those that are sufficiently inert to not spoil the porous structures. Here, we show a new strategy to achieve a crystalline porous material with the pore surface regularly decorated with highly reactive 'bare' nitrenes that are photonically generated from stable 'dormant' precursors at will. The bare triplet nitrenes were accessible to and reacted with adsorbed oxygen or carbon monoxide molecules, which showed not only activation of the pore surface, but also a high probability of chemical trapping and conversion of guest molecules by light stimulation on demand. - Shinobu Aoyagi; Eiji Nishibori; Hiroshi Sawa; Kunihisa Sugimoto; Masaki Takata; Yasumitsu Miyata; Ryo Kitaura; Hisanori Shinohara; Hiroshi Okada; Takeshi Sakai; Yoshihiro Ono; Kazuhiko Kawachi; Kuniyoshi Yokoo; Shoichi Ono; Kenji Omote; Yasuhiko Kasama; Shinsuke Ishikawa; Takashi Komuro; Hiromi TobitaNATURE CHEMISTRY 2 8 678 - 683 2010年08月 [査読有り]
If the physical properties of C-60 fullerene molecules can be controlled in C-60 products already in use in various applications, the potential for industrial development will be significant. Encapsulation of a metal atom in the C-60 fullerene molecule is a promising way to control its physical properties. However, the isolation of C-60-based metallofullerenes has been difficult due to their insolubility. Here, we report the complete isolation and determination of the molecular and crystal structure of polar cationic Li@C-60 metallofullerene. The physical and chemical properties of Li@C-60 cation are compared with those of pristine C-60. It is found that the lithium cation is located at off-centre positions in the C-60-I-h cage interior and that the [Li+@C-60] salt has a unique two-dimensional structure. The present method of purification and crystallization of C-60-based metallofullerenes provides a new C-60 fullerene material that contains a metal atom. - Hiroshi Sato; Ryotaro Matsuda; Kunihisa Sugimoto; Masaki Takata; Susumu KitagawaNATURE MATERIALS 9 8 661 - 666 2010年08月 [査読有り]
Porous compounds are ubiquitous and indispensable in daily life as adsorbents and catalysts. The discovery of a new porous compound with unique properties based on intrinsic nanosized space and surface functionalities is scientifically and technologically important. However, the functional species used in this context are limited to those that are sufficiently inert to not spoil the porous structures. Here, we show a new strategy to achieve a crystalline porous material with the pore surface regularly decorated with highly reactive 'bare' nitrenes that are photonically generated from stable 'dormant' precursors at will. The bare triplet nitrenes were accessible to and reacted with adsorbed oxygen or carbon monoxide molecules, which showed not only activation of the pore surface, but also a high probability of chemical trapping and conversion of guest molecules by light stimulation on demand. - Hiromichi Kuriyama; Jobu Matsuno; Seiji Niitaka; Masaya Uchida; Daisuke Hashizume; Aiko Nakao; Kunihisa Sugimoto; Hiroyuki Ohsumi; Masaki Takata; Hidenori TakagiAPPLIED PHYSICS LETTERS 96 18 2010年05月 [査読有り]
Single-crystalline thin film of an iridium dioxide polymorph Ir(2)O(4) has been fabricated by the pulsed laser deposition of Li(x)Ir(2)O(4) precursor and the subsequent Li-deintercalation using soft chemistry. Ir(2)O(4) crystallizes in a spinel (AB(2)O(4)) without A cations in the tetrahedral site, which is isostructural to lambda-MnO(2). Ir ions form a pyrochlore sublattice, which is known to give rise to a strong geometrical frustration. This Ir spinel was found to be a narrow gap insulator, in remarkable contrast to the metallic ground state of rutile-type IrO(2). We argue that an interplay of a strong spin-orbit coupling and a Coulomb repulsion gives rise to an insulating ground state as in a layered perovskite Sr(2)IrO(4). (C) 2010 American Institute of Physics. [doi:10.1063/1.3374449] - Hitoshi Miyasaka; Natsuko Motokawa; Satoshi Matsunaga; Masahiro Yamashita; Kunihisa Sugimoto; Tatsuya Mori; Naoki Toyota; Kim R. DunbarJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 132 5 1532 - 1544 2010年02月 [査読有り]
The isostructural series of two-dimensional (2-D) fishnet-type network compounds, [{Ru-2(O2CCF3)(4)}(2)-(TCNQR(x))]center dot n(solv) (R-x = H-4, 1; Br-2, 2; Cl-2, 3; F-2, 4; F-4, 5), has been synthesized from the reactions of a paddlewheel diruthenium(II, II) complex, [Ru-2(II,II)(O2CCF3)(4)], and neutral TCNQ derivatives (TCNQR(x) = 2,3,5,6- or 2,5-halogen-substituted 7,7,8,8-tetracyanoquinodimethane) under anaerobic conditions. Corresponding Rh compounds 1-Rh-5-Rh, which are diamagnetic and redox-inactive, were also synthesized for the purpose of comparison with 1-5. According to the electron affinity of TCNQR(x), which is related to its first reduction potential, the Ru-2 series (1-5) has the requisite driving force for charge transfer from [Ru-2(II,II)(O2CCF3)(4)] to TCNQR(x), which can lead to a mixed-valence state of [{Ru-2(4.5+)}-(TCNQR(x)(center dot-))-{Ru-2(4.5+)}] for the 2-D network Such a charge (or electron) transfer results in magnetic exchange interactions between [Ru-2] units (S = 1 for [Ru-2(II,II)] and S = 3/2 for [Ru-2(II,III)](+)) via TCNQR(x)(center dot-) S = 1/2 radicals that lead to long-range magnetic ordering in the layer. In the present series, only 5 demonstrated the full electron transfer (1-e(-) transfer) to the mixed-valence state, whereas other members are essentially in the state [{Ru-2(4+)}- (TCNQR(x)(0)){Ru-2(4+)}]. Whereas 1-4 are paramagnetic, 5 is a metamagnet undergoing 3-D long-range antiferromagnetic ordering at 95 K (= T-N) and reverts to a magnetic-field-induced ferromagnetic state exhibiting coercivity up to 60 K. This result is consistent with the fact that TCNQF(4) has the strongest electron affinity among the TCNQR(x) molecules. Even in neutral forms, however, 1-4 can be observed to undergo thermally and/or field-activated charge transfers from [Ru-2(II,II)] to TCNQR(x) to give semiconductors with an activation energy of 200-300 meV, which is a driving force to transport electrons over the lattice. As determined by their conducting properties, the ease of thermally and/or field-activated charge transfers is on the order of 1 < 4 < 2 approximate to 3 << 5, which is in agreement with the order of electron affinity of TCNQR(x). Indeed, a magnetic anomaly with short-range order associated with the localization of charge-transferred electrons was revealed in the low-temperature susceptibility data for 2 and 3. Finally, 5 was subjected to terahertz time-domain spectroscopy, the data from which revealed that transport hopping electrons scattered at high temperatures interact with magnetically ordered spins with the scattering being suppressed at T-N, at which temperature the real part of the complex electronic Conductivity (sigma(1)) and dielectric permeability (epsilon(1)) are dramatically altered. From these collective data, we conclude that molecular design based on an interunit charge transfer in a paramagnetic lattice is an efficient route to the design of materials with synergism between magnetic and conducting properties. - Sugimoto Kunihisa; Sasaki Sono; Tashiro Kohji; Nakamura Yoshie; Takata MasakiACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 66 S283 - S284 2010年 [査読有り]
- Kunihisa Sugimoto; Hiroyuki Ohsumi; Shinobu Aoyagi; Eiji Nishibori; Chikako Moriyoshi; Yoshihiro Kuroiwa; Hiroshi Sawa; Masaki TakataSRI 2009: THE 10TH INTERNATIONAL CONFERENCE ON SYNCHROTRON RADIATION INSTRUMENTATION 1234 887 - + 2010年 [査読有り]
The investigation of accurate structure at charge density level will not only understand the function mechanism of physical property but also lead to design new functional materials. We have successfully installed large cylindrical camera at the BL02BI/SPring-8. In conceptual design, the image plate (IP) was selected as the detector, because such IP will not only detect wide range in one shot but also yield reliable data. In commissioning, the performance of this camera demonstrated to be suitable for the direct observation of d-electron system. - Che-Hsiu Shih; Chou-Fu Sheu; Kenichi Kato; Kunihisa Sugimoto; Jungeun Kim; Yu Wang; Masaki TakataDALTON TRANSACTIONS 39 41 9794 - 9800 2010年 [査読有り]
The photo-induced superstructure of polymorph C of trans-[Fe(abpt)(2)(NCS)(2)] (abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole) is discovered as a commensurate modulated structure by single-crystal X-ray diffraction under irradiation. The crystal structure at 25 K before the photo-irradiation composed of two crystallographically independent iron molecules, one of which exhibits high spin (HS) state and the other at low spin (LS) state. Under green laser light (lambda = 532 nm) irradiation, the LS molecule (Fe1) is found to be excited to a metastable HS state and gives rise to a commensurate tripled superstructure along the c axis. In addition, it is confirmed that this modulation persists until the HS -> LS relaxation temperature beyond 52 K. Our structural findings suggest that the structural modulation and the site-selective LS -> HS excitation are highly correlated. - Masahiko Maekawa; Atsuhiro Nabei; Toshi Tominaga; Kunihisa Sugimoto; Toshie Minematsu; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu KitagawaDALTON TRANSACTIONS 3 415 - 417 2009年 [査読有り]
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 37 12 1216 - 1217 2008年12月 [査読有り]
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. - Hideki Sugimoto; Koichiro Suyama; Kunihisa Sugimoto; Hiroyuki Miyake; Isao Takahashi; Shun Hirota; Shinobu ItohINORGANIC CHEMISTRY 47 21 10150 - 10157 2008年11月 [査読有り]
Mono(dithiolene)sulfidomolybdenum(IV) complexes, [MoS(S-4)(bdt)](2-) (2) and (MoS(S4)(bdtCl(2))](2-) (3) (1,2-benzenedithiolate = bdt, 3,6-dichloro-1,2-benzenedithiolate = bdtCl(2)), were prepared by the substitution reaction of a tetrasulfido ligand in known [MoS(S-4)(2)](2-) (1) with the corresponding dithiol. Complexes 2 and 3 were irreversibly oxidized to give bis(mu-sulfido) dimolybdenum(V) species, {[MoS(bdt)](2)(mu-S)(2)}(2-) (4) and {[MoS(bdtCl(2))](2)(mu-S)(2)}(2-) (5), in aerobic acetonitrile. Mono(dithiolene)oxomolybdenum(IV) complexes, [MoO(S-4)(bdt)](2-) (7) and [MoO(S-4)(bdtCl(2))](2-) (8), that are oxo derivatives of 2 and 3 were also synthesized from a known [MoO(S-4)(2)](2-) (6) of an oxo derivative of 1 and the corresponding dithiol. Further, the electrophilic addition of dimethyl acetylenedicarboxylate to 7 gave [MoO(bdt)(S2C2(COOMe)(2))](2-) (9), and ligand substitution of the tetrasulfido group of 7 with bdt and bdtCl(2) yielded [MoO(bdt)(2)](2-) (10) and [MoO(bdt)(bdtCl(2))](2-) (11), respectively. New sulfido/oxo molybdenum complexes were characterized by H-1 NMR, IR, ESI-MS, Raman, and UV-vis spectroscopies; cyclic voltammetry; and elemental analysis, and crystal structures of 2, 3, 5, 7, and 8 were determined by X-ray analysis. - Hideki Sugimoto; Kunihisa SugimotoINORGANIC CHEMISTRY COMMUNICATIONS 11 1 77 - 80 2008年01月 [査読有り]
First examples of tungsten complexes, (Et4N)(2)[WO(L-0)(2)]((Et4N)(2) [1a]) and (Et4N)(2)[WO2(L-0)(2)]((Et4N)(2) [1b]), containing pyranodithiolene were synthesized as new models of reaction center of tungsten enzymes. The complexes were characterized by IR, UV-Vis, Raman spectroscopics, and cyclic voltammogram (CV). The crystal structures were determined by X-ray crystallography. The pyrane ring affected the W=O bond stretchings in 1a and 1b, the redox potential of 1a, and LMCT bands of 1b. (c) 2007 Elsevier B.V. All rights reserved. - Natsuko Motokawa; Tomomi Oyama; Satoshi Matsunaga; Hitoshi Miyasaka; Kunihisa Sugimoto; Masahiro Yamashita; Nazario Lopez; Kim R. DunbarDALTON TRANSACTIONS 31 4099 - 4102 2008年 [査読有り]
The slow diffusion reaction of [Ru(2)(O(2)CCF(3))(4)(THF)(2)] with TCNQ in CH(2)Cl(2)/4-chlorotoluene, respectively, leads to the formation of ladder chain composed of [Ru(2)] rails and TCNQ rungs in a 2 : 1 ratio. - Kunihisa Sugimoto; Robert E. Dinnebier; Marek ZakrzewskiJOURNAL OF PHARMACEUTICAL SCIENCES 96 12 3316 - 3323 2007年12月 [査読有り]
The crystal structures of the analgesic compounds anhydrous naloxone and naltrexone hydrochloride were determined ab initio from high resolution laboratory X-ray powder diffraction data. Both compounds crystallize in the orthorhombic space group P2(1)2(1)2(1) with lattice parameters of a = 14.6588(10) angstrom, b = 17.4363(9) angstrom, c = 7.96200(22) angstrom, and V= 2035.06(23) angstrom(3) for naloxone hydrochloride and a = 15.4560(5) angstrom, b = 14.9809(4) angstrom, c = 7.84121(18) angstrom, and V= 1815.58(11) angstrom(3) for naltrexone hydrochloride. The crystal structure of anhydrous naloxone hydrochloride forms one-dimensional chains through hydrogen bonds. In the crystal structure of anhydrous naltrexone hydrochloride, two-dimensional sheets are formed by hydrogen bonds. The dehydration processes of naloxone hydrochloride dehydrate and naltrexone hydrochloride tetrahydrate was analyzed by DTA, DSC, TG, and MG. (c) 2007 Wiley-Liss, Inc. - Kunihisa Sugimoto; Robert E. Dinnebier; Thomas SchlechtACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE 63 6 805 - 811 2007年12月 [査読有り]
The crystal structure with the idealized formula Mg-3(OH)(5)Cl center dot 4H(2)O, the so-called F5 phase according to 5Mg(OH)(2)center dot MgCl2 center dot 8H(2)O in the system MgCl2-MgO-H2O, has been solved ab initio from high- quality laboratory powder diffraction data at room temperature. The F5 phase is structurally related to 3Mg(OH)(2)center dot MgCl2 center dot 8H(2)O (F3 form). The F5 phase consists of infinite triple chains with one Mg(OH)(6) and two Mg(OH)(4)(OH2)(2) octahedra as building units intercalated by chlorides, which are partly substituted by disordered hydroxides in the real structure. The F5 phase is of technological importance as the most important binder phase in Sorel cements. Knowledge of the crystal structure enables the full quantitative phase analysis of magnesia cements for the first time, which turns out to be very helpful in the search for possible causes of broken or bleached magnesia floors. Two real-life examples are given. - Shin-ichi Takekuma; Kazutaka Mizutani; Kanako Inoue; Masaru Nakamura; Masato Sasaki; Toshie Minematsu; Kunihisa Sugimoto; Hideko TakekumaTETRAHEDRON 63 18 3882 - 3893 2007年04月 [査読有り]
Reaction of azulene (1) with all-trans-retinal in diethyl ether in the presence of hexafluorophosphoric acid at - 10 degrees C for 1 h in a dark room gives the corresponding monocarbenium-ion compound, (2E,4E,6E,8E)-1-azulenyl-3,7-dimethyl-9-(2,6,6-trimethyl-1-cyclohexen- 1 -yl)-2,4,6,8-nonatetraen-1-ylium hexafluorophosphate (3), in 74% isolated yield. The spectroscopic, chemical, and electrochemical properties of 3 compared with those of the previously-documented (2E,4E,6E,8E)-1-(3-guaiazulenyl)-3,7-dimethyl-9-(2,6,6-trimethyl-lcyclohexen-1-yl)-2,4,6,8-nonatetraen-1-ylium hexafluorophosphate (4) are reported. Along with the above delocalized monocarbeniumion compounds 3 and 4, stabilized by the expanded pi-electron systems possessing an azulenyl (or 3-guaiazulenyl) group, an efficient preparation as well as the spectroscopic, chemical, and electrochemical properties of (2E)-1-azulenyl-3-phenyl-2-propen-1-ylium and (2E)1-(3-guaiazulenyl)-3-phenyl-2-propen-1-ylium hexafluorophosphates (5 and 6) (90 and 96% isolated yields), having a similar partial structure [i.e., the (2E)-1-azulenyl-2-propen-1-ylium-ion or (2E)-1-(3-guaiazulenyl)-2-propen-1-ylium-ion part] to those of 3 and 4, is documented. Moreover, the crystal structure of 6, whose carbenium-ion framework is planar, is shown. (C) 2007 Elsevier Ltd. All rights reserved. - Kunihisa Sugimoto; Robert E. Dinnebier; Jonathan C. HansonACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE CRYSTAL ENGINEERING AND MATERIALS 63 2 235 - 242 2007年04月 [査読有り]
High-quality in situ synchrotron powder diffraction data have been used to investigate the decomposition products of bischofite in the temperature range 298 <= T <= 873 K. At least eight phases could be identified: MgCl2 . nH(2)O (n = 1, 2, 4 and 6), MgOHCl . nH(2)O (0 <= n <= 1.0), MgCl2 and MgO. The crystal structures of three magnesium chloride hydrates MgCl2 . nH(2)O (n = 1, 2, 4) were determined ab initio, replacing published Rietveld refinements from low-quality powder diffraction data based on similarity criteria. MgCl2 . 4H(2)O was found to be disordered and has been correctly determined for the first time. The crystal structures of bischofite and MgCl2 . 4H(2)O consist of discrete Mg(H2O)(6) and MgCl2(H2O)(4) octahedra, respectively. The crystal structure of MgCl2 . 2H(2)O is formed by single chains of edge-sharing MgCl2(H2O)(4) octahedra, while in the case of MgCl2 . H2O double chains of edge-sharing MgCl(H2O)(5) octahedra are found. The phases in the system MgCl2-H2O are intermediates in the technologically important process of MgO and subsequently Mg production. The same phases were recently found to be of key importance in the understanding of cracks in certain magnesia concrete floors. - Kunihisa Sugimoto; Robert E. Dinnebier; Thomas SchlechtPOWDER DIFFRACTION 22 1 64 - 67 2007年03月 [査読有り]
In the course of an investigation of cracks in certain magnesia floors containing the mineral chlorartinite [Mg-2(CO3)(H2O)(OH)]Cl center dot H2O, the dehydration process of chlorartinite was carried out in high vacuum. The crystal structure of dehydrated chlorartinite [Mg-2(CO3)(H2O)(OH)]Cl was refined from laboratory X-ray powder diffraction data using the Rietveld method [R3c, a=22.6791(5) angstrom, c=7.22336(14) angstrom, V=3217.52(11) angstrom(3), Z=18, R-p=4.13%, R-wp=5.82%]. Dehydrated chlorartinite exhibits the same type of 3D honeycomb zeolite-like crystal structure with large channels as the hydrated form. Compared to the hydrated form, the channels of dehydrated chlorartinite are empty because of the removal of all non-coordinating water molecules with the cell volume shrinking by 4.0%, leading to a more distorted environment of the magnesium atoms. (C) 2007 International Centre for Diffraction Data. - Kunihisa Sugimoto; Robert E. Dinnebier; Thomas SchlechtJOURNAL OF APPLIED CRYSTALLOGRAPHY 39 739 - 744 2006年10月 [査読有り]
The volcanic exhalation product chlorartinite, [Mg-2(CO3)(H2O)(OH)]Cl center dot H2O, has recently been found to be a minor, and in some samples a major, component of magnesia floors for industrial use. In order to be able to perform quantitative phase analysis using the Rietveld method, its crystal structure was determined from high-resolution synchrotron powder diffraction data by the global optimization technique of simulated annealing and Rietveld refinement. The final R-p and R-wp values are 5.23% and 6.56%, respectively. Chlorartinite crystallizes in the rhombohedral space group R3c (No. 161), with a = 23.14422 (16) angstrom, c = 7.22333 (5) angstrom, V = 3350.84 (5) angstrom(3), Z = 18. The building units of chlorartinite consist of MgO6 octahedra forming 15-membered puckered rings which are interconnected by CO3 triangular moieties. The rings are stacked to form a honeycomb-like three-dimensional framework structure with large isolated channels. Within the channels, free chlorine atoms and disordered water molecules are located. - Hitoshi Miyasaka; Tomokura Madanbashi; Kunihisa Sugimoto; Yasuhiro Nakazawa; Wolfgang Wernsdorfer; Ken-ichi Sugiura; Masahiro Yamashita; Claude Coulon; Rodolphe CleracCHEMISTRY-A EUROPEAN JOURNAL 12 27 7029 - 7040 2006年09月 [査読有り]
An alternated 1:1 chain compound of a Mn-III salen derivative and the TCNQ monoradical was synthesized: [Mn(5-TMAMsaltmen)(TCNQ)](ClO4)(2) (1) (TCNQ=tetra-cyano-p-quinodimethane; 5-TMAM-saltmen = N,N-(1,1,2,2-tetramethyleth-ylene) bis(5-trimethylammoniomethyl-salicylideneiminato)). Compound I has a zigzag chain structure packed with adjacent chains with an interchain Mn center dot center dot center dot Mn distance of over 8 angstrom. As compound I contains no crystallization solvent, the void spaces between chains are occupied only by ClO4- counter ions. Compound I has a structure reminiscent of what has been observed in the family of Mn-III(porphyrin)-TCNE or -TCNQ compounds reported previously by Miller and co-workers and we demonstrate herein its unique single-chain magnet behavior among this family of compounds. The direct current (dc) magnetic measurements established the one-dimensional nature of compound I with an antiferromagnetic exchange coupling, J/k(B) approximate to -96 K, between the Mn-III ion and TCNQ radical and with an activated correlation length (Delta(xi) = 26.5 K) at low temperatures (50-15 K). The slow relaxation of the magnetization was shown in compound I by the field hysteresis of the magnetization observed below 3.5 K (with a coercive field up to 14 kOe at 1.8 K). Single-crystal magnetization measurements demonstrated the uniaxial symmetry of this compound and allowed an estimation of the anisotropy field, H-a approximate to 97 kOe. The absence of magnetic ordered phase or spin-glass behavior was established by heat-capacity calorimetry measurements that exhibit no abnormality of C-p between 0.5 K and 10 K. The study of the magnetization relaxation by combined ac (alternating current) and dc techniques showed that compound I possesses a single relaxation time (tau). As the consequence of the finite size of the chain, the temperature dependence of tau presents two activated regimes above and below 4.5 K with tau(01) = 2.1 x 10(-10) s, Delta(tau 1) = 94.1 K and tau(02) = 6.8 x 10(-8) s and Delta(tau 2) = 67.7 K, respectively. The detailed analysis of these dynamics properties together with the correlation length, allows an unambiguous demonstration of the single-chain magnet behavior in 1. - H. Miyasaka; T. Madanbashi; K. Sugimoto; Y. Nakazawa; W. Wernsdorfer; K. Sugiura; M. Yamashita; C. Coulon; R. CleracChem. Eur. J., 12 7028 - 7040 2006年04月 [査読有り]
- Hitoshi Miyasaka; Toru Izawa; Shinya Takaishi; Kunihisa Sugimoto; Ken-ichi Sugiura; Masahiro YamashitaBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 79 4 612 - 620 2006年04月 [査読有り]
Three diruthenium compounds, [Na(18-crown-6)(thf)(2)][Ru-2(O2CCH3)(2)(t-Busalpy)(2)] (1), [K(18-crown-6)(thf)(2)][Ru-2(O2CCH3)(2)(t-Busal-4-Mepy)(2)] (2), and [K(18-crown-6)(thf)(H2O)][K(18-crown-6)(thf)(MeO)][Ru-2(O-2)CCH3)(2)(t-Busal-5-Mepy)(2)] (3) (18-crown-6 = 1,4,7,10,13,16-hexaoxocyclooctadecane; 18-crown-6-ether), have been synthesized by the ligand substitution reaction of Ru-2(O2CCH3)(4)Cl with newly prepared tridentate bridging/chelating ligands, N-(2-pyridyl)-2-oxido-3,5-di-tert-butylbenzylaminato (t-Busalpy(2-)), N-(4-methyl-2-pyridyl)-2-oxido-3,5-di-tert-butylbenzylaminato (t-Busal-4-Mepy(2-)), and N-(5-methyl-2-pyridyl)-2-oxido-3,5-di-tert-butylbenzylaminato (t-Busal-5-Mepy(2-)), respectively, and isolated using [Na(18-crown-6)](+) or [K(18-crown-6)]+ as the counter cation. The structural features of the anionic parts are very similar to those of the previously synthesized family of [Ru-2(O2CCH3)(2)(5-Rsalpy)(2)](-) (R = H, Me, Cl, Br, and NO2); two acetate and two t-Busal-R'py(2-) ligands are respectively located around the Ru-2 unit in a trans fashion, where the t-Busal-R'py(2-) ligand acts as a tridentate ligand having both bridging and chelating characters to form the M-M bridging/axial-chelating mode. Their Ru-Ru bonded core with an electronic configuration of sigma(2)pi(4)delta(2)(pi*delta*)(3) is axial-capped by the di-t-butylphenolate groups of the t-Busal-R'py2- ligands, and experiences multi-redox properties: a one-electron reduction to Ru-2(4+) and two one-electron oxidations to Ru-2(6+) followed by Ru-2(7+), in addition to t-Busal-R'py(2-) ligand-centered redox. The strong electron-donating ability of the t-butyl groups compared with the other R-groups leads to negative shifts of the redox potentials according to the Hammett law. - H Sugimoto; M Harihara; M Shiro; K Sugimoto; K Tanaka; H Miyake; H TsukubeINORGANIC CHEMISTRY 44 18 6386 - 6392 2005年09月 [査読有り]
The cis-dioxo-molybdenum(VI) complexes, [MoO2(L-H)(2)](2-) (1b), [MoO2(Ls)(2)](2-) (2b), and [MoO2(L-O)(2)](2-) (3b) (L-H = cyclohexene-1,2-dithiolate, Ls = 2,3-dihydro-2H-thiopyran-4,5-dithiolate, and L-O = 2,3-dihydro-2H-pyran-4,5-dithiolate), with new aliphatic dithiolene ligands were prepared and investigated by infrared (IR) and UV-vis spectroscopic and electrochemical methods. The mono-oxo-molybdenum(IV) complexes, [MoO(L-H)(2)](2-) (1a), [MoO(L-S)(2)](2-) (2a), and [MoO(L-O)(2)](2-) (3a), were further characterized by X-ray crystal structural determinations. The IR and resonance Raman spectroscopic studies suggested that these cis-dioxo molybdenum(VI) complexes (1b-3b) had weaker Mo=O bonds than the common (MoO2)-O-VI complexes, Complexes 1b-3b also exhibited strong absorption bands in the visible regions assigned as charge-transfer bands from the dithiolene ligands to the CiS-MoO2 cores. Because the oxygen atoms of the CiS-(MOO2)-O-VI cores are relatively nucleophilic, these complexes were unstable in protic solvents and protonation might occur to produce (MoO)-O-VI(OH), as observed with the oxidized state of arsenite oxidase. - Guo Qing Bian; Takayoshi Kuroda-Sowa; Tadahiro Nogami; Kunihisa Sugimoto; Masahiko Maekawa; Megumu Munakata; Hitoshi Miyasaka; Masahiro YamashitaBulletin of the Chemical Society of Japan 78 6 1032 - 1039 Chemical Society of Japan 2005年06月The preparation and physical characterization are reported for three Mn12single-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 1-2CH2Cl2· 4.5H2O crystallizes in the monoclinic space group C2/c, with cell dimensions at -160 °C of a = 28.524 Å, b = 17.819 Å, c = 36.058 Å, β= 92.399°, and Z = 4. The X-ray structure analysis of 1 · 2CH2Cl2· 4.5H2O reveals that each [Mn12] molecule is connected to the neighboring molecules through eight π⋯π interactions to form a two-dimensional structure within the bc-plane. This is the first SMM that self-assembles two-dimensionally via π⋯π interaction. From Arrhenius plots of the frequency dependence of the temperatures of the χ″Mpeaks, the effective energy barriers Uefffor 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 (LT) phases of 1 and 3, respectively. The analysis of the reduced magnetization data suggests that the LT phase of 1 has an S = 9 ground state with g = 1.998 and D = -0.61 K. © 2005 The Chemical Society of Japan.
- H Miyasaka; T Nezu; K Sugimoto; K Sugiura; M Yamashita; R CleracCHEMISTRY-A EUROPEAN JOURNAL 11 5 1592 - 1602 2005年02月 [査読有り]
Mn-III-Ni-II-Mn-III linear-type trinuclear complexes bridged by oximate groups were selectively synthesized by the assembly reaction of [Mn-2(5-Rsaltmen)(2)(H2O)(2)] (ClO4)(2) (5-Rsaltmen(2-)=N,N'-(1,1,2,2-tetramethylethylene) bis(5-R-salicylideneiminate); R=Cl, Br) with [Ni(pao)(2)(phen)] (pao(-)=pyridine-2-aldoximate; phen=1,10-phenanthroline) in methanol/water: [Mn-2(5-Rsaltmen)(2)Ni(pao)(2)(phen)](ClO4)(2) (R=Cl, 1; R=Br, 2). Structural analysis revealed that the [Mn-III-ON-Ni-II-NO-Mn-III] skeleton of these trimers is in every respect similar to the repeating unit found in the previously reported series of 1D materials [Mn-2(saltmen)(2)Ni(pao)(2)(L-1)(2)](A)(2) (L-1=pyridine, 4-picoline, 4-tert-butylpyridine, N-methylimidazole; A=ClO4-, BF4-, PF6-, ReO4-). Recently, these 1D compounds have attracted a great deal of attention for their magnetic properties, since they exhibit slow relaxation of the magnetization (also called single-chain magnet (SCM) behavior). This unique magnetic behavior wag explained in the framework of Glauber's theory, generalized for chains of ferromagnetically coupled anisotropic spins. Thus, in these ID compounds, the [Mn-III-ON-Ni-II-NO-Mn-III] unit was considered as an S-T=3 anisotropic spin. Direct-current magnetic measurements on 1 and 2 confirm their S-T=3 ground state and strong uniaxial anisotropy (D/k(B)approximate to-2.4 K), in excellent agreement with the magnetic characteristic deduced in the study on the SCM series. The ac magnetic susceptibility of these trimers is strongly frequency-dependent and characteristic of single-molecule magnet (SMM) behavior. The relaxation time tau shows a thermally activated (Arrhenius) behavior with tau(0)approximate to 1x10(-7) s and Delta(eff)/k(B)approximate to 18 K. The effective energy barrier for reversal of the magnetization Delta(eff) is consistent with the theoretical value (21 K) estimated from vertical bar D vertical bar S-T(2). The present results reinforce consistently the interpretation of the SCM behavior observed in the [Mn-2(saltmen)(2)Ni(pao)(2)(L-1)(2)](A)(2) series and opens new perspectives to design single-chain magnets. - Sugimoto Kunihisa; Taguchi Takeyoshi; Kuribayashi MasaruACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES 61 C145 - C145 2005年 [査読有り]
- 前川 雅彦; 峯松 敏江; 小中 尚; 黒田 孝義; 末永 勇作; 宗像 惠; 杉本邦久Inorganica Chimica Acta 357 12 3456 - 3472 Elsevier 2004年09月多座窒素配位子として、2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz)、2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz)および1,4-bis(2,2':6',2''-terpyridine-4'-yl)benzene (bted)と前駆体のイリジウム錯体[Ir(H)2(PPh3)2(Me2CO)2]X (X=PF6 and BF4)を反応させ、新規な5つの単核および二核イリジウムヒドリド錯体 [Ir(H)2(PPh3)2(tptz)]PF6、 [Ir2(H)4(PPh3)4(tptz)](PF6)2?2H2O 、 [Ir(H)2(PPh3)2(tppz)]BF4、[Ir2(H)4(PPh3)4(tppz)](BF4)2および [Ir2(H)4(PPh3)4(bted)](BF4)2?6CHCl3を系統的に合成し、その固体および溶液内構造を単結晶X線構造解析および1D,2D NMR法より特徴付けた。
- H Miyasaka; T Nezu; K Sugimoto; KC Sugiura; M Yamashita; R CleracINORGANIC CHEMISTRY 43 18 5486 - 5488 2004年09月 [査読有り]
Heterometallic linear tetramers [Mn(5-R-saltmen)Ni(pao)(bpy)(2)](2)-(ClO4)(4) (5-R-saltmen(2)- = N,N'-1,1,2,2-tetramethylethylene bis(5-R-salicylideneiminate); pao(-) = pyridine-2-aldoximate; bpy = 2,2'-bipyridine, R = H, 1; Cl, 2; Br, 3; MeO, 4) have been synthesized and structurally characterized. These compounds exhibit a [Ni-II-NO-Mn-III-(O)(2)-Mn-III-ON-Ni-II] skeleton where -ON- is an oximate bridge between Mn-III and Ni-II ions and -(O)(2)- is a bi-phenolate bridge between Mn-III ions. These tetramers can be seen as oligomeric units of the heterometallic Mn-2(III)-Ni-II chain observed in a family of single-chain magnets (Clerac, R.; Miyasaka, H.; Yamashita, M.; Coulon, C. J Am. Chem. Soc. 2002, 124, 12837. Miyasaka, H.; Clerac, R.; Mizushima, K.; Sugiura, K.; Yamashita, M.; Wernsdorfer, W.; Coulon, C. Inorg. Chem. 2003, 42, 8203.). Magnetic measurements on these tetramers confirm the nature of the magnetic interactions reported for the Mn-2(III)-Ni-II chains: a strong antiferromagnetic Mn-III/Ni-II coupling via the oximate bridge (J(Ni-Mn), ranges from -23.7 to -26.1 K) and a weak ferromagnetic Mn-III/Mn-III coupling through the bi-phenolate bridge (J(Mn-Mn) ranges from +0.4 to +0.9 K). These magnetic interactions lead to tetramers with an S = 2 ground state. - 前川 雅彦; 小中 尚; 末永 勇作; 黒田 孝義; 宗像 惠; 杉本邦久Analytical Science 20 2 X71 - X72 日本分析化学会 2004年06月表題の銅(II)錯体[Cu(phen)2Cl]BF4 (phen=1,10-phenanthroline)の構造をX線構造解析を用いて明らかにした。 この錯体は現在知られている5配位の[Cu(phen)2Cl+類縁化合物の中で最も正三角両錐型構造に近い構造を有する錯体である。
- H Miyasaka; T Nezu; F Iwahori; S Furukawa; K Sugimoto; R Clerac; K Sugiura; M YamashitaINORGANIC CHEMISTRY 42 15 4501 - 4503 2003年07月 [査読有り]
The heterometallic (Mn4Ni2II)-Ni-II title compound has been synthesized and characterized by X-ray crystallography. The compound consists of a Ni-Mn-Ni linear moiety, [{Ni-(mu-NO)(3)}(2)-Mn], linked by oximate bridges and three Mn(11) hfac terminal units attached by oximate oxygens in a di-mu-oxo fashion, forming a novel heterometallic cluster. Mn{Mn(hfac)(2)}(3){Ni(pao)(3)}(2) (1). Magnetic measurements reveal the antiferromagnetic nature of the oximate pathway between Mn(11) and Ni(II) metal ions, which imposes an unusual high-spin ground state (S = 8) for 1. - Shigeya Kobayashi; Shinji Wakumoto; Yoshihiro Yamaguchi; Tateaki Wakamiya; Kunihisa Sugimoto; Yoshio Matsubara; Zen-Ichi YoshidaTetrahedron Letters 44 9 1807 - 1810 2003年02月 [査読有り]
Novel thiaarenecyclynes 3 and 4 in which two thioether units and two benzene rings are alternately inserted into the single bonds of cyclooctatetrayne are synthesized. Their unique properties are described. © 2003 Elsevier Science Ltd. All rights reserved. - Shigeya Kobayashi; Yoshihiro Yamaguchi; Tateaki Wakamiya; Yoshio Matsubara; Kunihisa Sugimoto; Zen-Ichi YoshidaTetrahedron Letters 44 7 1469 - 1472 2003年02月 [査読有り]
Simple members of arene-azaarenecyclynes as a novel family of geometrically-controlled and shape-persistent azamacrocycles have been synthesized. Noteworthy is the specific recognition function for Sb(V). The synthesized azamacrocycles, in particular the Sb(V) complex, have unusually strong light-emitting property. © 2003 Elsevier Science Ltd. All rights reserved. - 前川 雅彦; 橋本 直樹; 黒田 孝義; 末永 勇作; 宗像 惠; 杉本邦久Inorganica Chimica Acta 344 143 - 157 Elsevier Science 2003年02月新規な9種のロジウムおよびイリジウム[2.2]パラシクロファン錯体を合成し、その分子構造および性質を単結晶X線構造解析、1H NMR法などより始めて明らかにした。いずれも有機金属配位高分子を構築する上で有用なビルデングブロックとなることが明らかとなった。(英文)
- Miyasaka, H.; Sugimoto, K.; Sugiura, K.-I.; Ishii, T.; Yamashita, M.Molecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals 379 197 - 204 2002年12月The reactions of Mn(III) quadridentate Schiff base compounds, [Mn(saltmen)(H2O)]ClO4 (1; saltmen2- = N, N′-(1, 1, 2, 2-tetramethylethylene)bis(salicylideneiminato)) and [Mn(naphtmen)(H2O)]ClO4 (2; naphtmen2- = N, N′-(1, 1, 2, 2-tetramethylethylene)bis(naphthylideneiminato)), with LiTCNQ gave three type compounds according to reaction conditions: [Mn(saltmen)(H 2O)](TCNQ) (3), [Mn(saltmen)(MeOH)(TCNQ-OMe)] (4, TCNQ-OMe - = p-(α,α-dicyano-α-methoxytolyl)dicyanomethide), and [Mn(naphtmen)(MeOH)(TCNQA-OMe)] (5, TCNQA-OMe- = p-(α-cyano-α-methoxy-α-methylamidetolyl)dicyanomethide). Compounds 3 and 4 are distinguishable according to synthetic condition either anaerobic or not. Compound 5 is synthesized in aerobic condition as well as 4. For 4 and 5, unusual addition reactions on the anionic TCNQ molecule occur to form (TCNQ-OMe)- for 4 and (TCNQA-OMe)- for 5.
- Kazuya Nakata; Hitoshi Miyasaka; Kunihisa Sugimoto; Tomohiko Ishii; Ken Ichi Sugiura; Masahiro YamashitaChemistry Letters 2002 7 658 - 659 2002年07月Treatment of a mixed-valence Mn6 cluster, [Mn6O2(t-BuCO2)10 (t-BuCO2H)4] (1), with 4,4′-bipyridine (bpy) in dichloromethane/1,2-dichloroethane solution gave a one-dimensional polymeric chain compound, [Mn6O2(t-BuCO2)10 (t-BuCO2H)2(bpy)] (2), in which the parent cluster cote was maintained as a building block.
- Yoshihiro Yamaguchi; Shigeya Kobayashi; Nobuhiro Amita; Tateaki Wakamiya; Yoshio Matsubara; Kunihisa Sugimoto; Zen-Ichi YoshidaTetrahedron Letters 43 18 3277 - 3280 2002年04月 [査読有り]
Novel nanoscale oxaarenecyclynes (3 and 4) consisting of diethynylbenzene and ether units were synthesized, which form supramolecular complexes with C60. © 2002 Elsevier Science Ltd. All rights reserved. - Hitoshi Miyasaka; Kunihisa Sugimoto; Ken-Ichi Sugiura; Tomohiko Ishii; Masahiro YamashitaMolecular Crystals and Liquid Crystals 379 1 197 - 204 2002年01月
- Kalo, T.; Sugimoto, K.; Yamasaki, M.Acta Crystallographica Section C: Crystal Structure Communications 57 11 2001年
- K Sugimoto; T Kuroda-Sowa; SG Yan; M Maekawa; M MunakataACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS 56 414 - 415 2000年04月 [査読有り]
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. - Takashi Kawamura; Hisanori Kachi; Hiroshi Fujii; Chihiro Kachi-Terajima; Yuzuru Kawamura; Naohiro Kanematsu; Masahiro Ebihara; Kunihisa Sugimoto; Takayoshi Kuroda-Sowa; Megumu MunakataBulletin of the Chemical Society of Japan 73 3 657 - 668 2000年03月 [査読有り]
The odd electron in the δ(RhRh) orbital of (3,1)-[Rh2(mhq)4py]+ (1+ Hmhq = 4-methyl-2-quinolinol) was estimated to be delocalized onto each π system of the four mhq bridges to the extent of ca. 9% based on its 1H NMR paramagnetic shifts. The experimental spin distribution in the mhq ligands is consistent with a model of mixing of the Jr HOMOs of the mhq ligands into the δ(RhRh)/* singly occupied molecular orbital (SOMO). In crsystals of (3,1)-[Rh2(hq)4py] (2 Hhq = 2-quinolinol) and its cationic radical salts, 2 or 2+ molecules form intermolecular π-stack arrangements of hq ligands. Intermolecular interaction between 2+ molecules in crystal was studied by examining electronic spectra, magnetic susceptibility, ESR, and electrical conductance of its salts. - K Sugimoto; T Kuroda-Sowa; T Goto; M Maekawa; M MunakataBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 73 3 651 - 655 2000年03月 [査読有り]
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 73 2 391 - 394 2000年02月 [査読有り]
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. - Sugimoto, K.; Kuroda-Sowa, T.; Maekawa, M.; Munakata, M.Bulletin of the Chemical Society of Japan 73 2 2000年
- Masahiko Maekawa; Kunihisa Sugimoto; Takayoshi Kuroda-Sowa; Yusaku Suenaga; Megumu MunakataJournal of the Chemical Society - Dalton Transactions 24 4357 - 4362 1999年12月 [査読有り]
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. - GL Ning; LP Wu; K Sugimoto; M Munakata; T Kuroda-Sowa; M MaekawaJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS 15 2529 - 2536 1999年08月 [査読有り]
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. - Wu, L.P.; Yamagiwa, Y.; Ino, I.; Sugimoto, K.; Kuroda-Sowa, T.; Kamikawa, T.; Munakata, M.Polyhedron 18 15 2047 - 2053 1999年06月Copper(II) and iron(II, III) complexes of the tripodal ligand, tris(1-methyl-1H-imidazol-2-yl)methanol (Htmim), have been synthesized and characterized by elemental analysis, 1 H NMR and IR spectroscopies, magnetic moment measurement and X-ray crystallography. The structure of the copper complex, [Cu 4 (tmim) 4 (CF 3 SO 3 ) 2 ](CF 3 SO 3 ) 2 ·2MeOH (1), can be regarded as a polyimidazole-linked tetranuclear cluster where each copper atom adopts a five-coordinate square-pyramidal geometry ligated by the tmim anion. The two iron complexes, [Fe II (Htmim) 2 ][Fe II Cl 4 ]·4MeOH (2) and [Fe III (Htmim) 2 ][Fe III Cl 4 ] 2 Cl (3), contain the isostructural [Fe(Htmim) 2 ] cation and tetrahedral [FeCl 4 ] - anion. While Htmim shows a normal tripodal tridentate mode in the iron complexes capping one face of an essentially octahedral coordination sphere, its deprotonated species exhibit an unusual non-tripodal tetradentate coordination with copper(II) ions. The observed magnetic moment at room temperature for 1 is 1.13 BM per Cu atom, consistent with antiferromagnetic coupling between the copper(II) atoms of the tetramer. Both 2 and 3 show magnetic properties consistent with low-spin electronic configurations of the cation and high-spin nature of the metal ion in the anion. © Elsevier Science Ltd.
- K Sugimoto; T Kuroda-Sowa; M Maekawa; M MunakataCHEMICAL COMMUNICATIONS 5 455 - 456 1999年03月 [査読有り]
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 3 373 - 378 1999年02月 [査読有り]
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. - MAEKAWA M; SUGIMOTO K; KURODA‐SOWA T; SUENAGA Y; MUNAKATA MJ. Chem. Soc., Dalton Trans. 24 4357 - 4362 1999年
- MUNAKATA M; WU L P; SUGIMOTO K; KURODA‐SOWA T; MAEKAWA M; SUENAGA Y; MAENO N; FUJITA MInorg. Chem. 38 25 5674 - 5680 1999年
- NING G L; MUNAKATA M; WU L P; MAEKAWA M; SUENAGA Y; KURODA‐SOWA T; SUGIMOTO KInorg. Chem. 38 25 5668 - 5673 1999年
- MUNAKATA M; NING G L; SUENAGA Y; SUGIMOTO K; KURODA‐SOWA T; MAEKAWA MJ. Chem. Soc. , Chem. Commun. 16 1545 - 1546 1999年
- MAEKAWA M; MUNAKATA M; KURODA‐SOWA T; SUENAGA Y; SUGIMOTO KInorganica Chimica Acta 290 2 153 - 158 1999年Synthesis and crystal structure of tetranuclear copper((]G0001[)) and silver((]G0001[)) complexes bridge by 2-amono-1,3,4-thiadiazole(atdz) : [Cu<sub>4</sub>(atdz)<sub>6</sub>](ClO<sub>4</sub>)<sub>4</sub>・2CH<sub>3</sub>OH and [Ag<sub>4</sub>(atdz)<sub>6</sub>](ClO<sub>4</sub>)<sub>4</sub>(共著)
- NING G L; MUNAKATA M; WU L P; MAEKAWA M; KURODA‐SOWA T; SUENAGA Y; SUGIMOTO KInorg. Chem. 38 7 1376 - 1377 1999年
- M Munakata; LP Wu; T KurodaSowa; M Maekawa; Y Suenaga; K SugimotoINORGANIC CHEMISTRY 36 21 4903 - 4905 1997年10月 [査読有り]
MISC
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- 河口彰吾; 杉本邦久; 竹本道教 日本結晶学会年会講演要旨集 2016 59 2016年11月
- 大竹研一; 大坪主弥; 杉本邦久; 佐藤寛泰; 北川宏 日本化学会春季年会講演予稿集(CD-ROM) 96th 2016年
- 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年
- 杉本邦久 ひょうご科学技術協会研究成果報告書(Web) 2016 2016年
- 橋口良太; 大坪主弥; 前里光彦; 河口彰吾; 杉本邦久; 藤原明比古; 北川宏 分子科学討論会講演プログラム&要旨(Web) 10th ROMBUNNO.2C08 (WEB ONLY) 2016年
- 岡崎宏之; 上野若菜; 辻成希; 中村哲也; 中村哲也; 杉本邦久; 河口彰吾; 広沢哲 日本金属学会講演概要(CD-ROM) 158th ROMBUNNO.S1.23 2016年
- 水牧 仁一朗; 筒井 智嗣; 杉本 邦久; 広瀬 雄介; 角田 竜馬; 水戸 毅; 摂待 力生 日本物理学会講演概要集 71 (0) 2299 -2299 2016年
- 菅原 健人; 樋口 貴文; 澤 博; 杉本 邦久; 高田 昌樹; 有馬 孝尚; 田口 康二郎; 十倉 好紀 日本物理学会講演概要集 71 (0) 2673 -2673 2016年
- 青柳 忍; 青柳 鮎美; 大沢 仁志; 杉本 邦久; 竹田 翔一; 森吉 千佳子; 黒岩 芳弘; 岩田 真 日本物理学会講演概要集 71 (0) 2723 -2723 2016年
- 河口 彰吾; 石橋 広記; 下野 聖矢; 杉本 邦久; 竹本 道教; 久保田 佳基 日本物理学会講演概要集 71 (0) 1732 -1732 2016年
- R. Murata; T. Sato; T. Okuda; Y. Horibe; H. Tsukasaki; S. Mori; N. Yamaguchi; K. Sugimoto; S. Kawaguchi; M. Takata; T. Katsufuji Physical Review B - Condensed Matter and Materials Physics 92 (22) 2015年12月
- 大竹研一; 大坪主弥; 大坪主弥; 杉本邦久; 藤原明比古; 北川宏; 北川宏 分子科学討論会講演プログラム&要旨(Web) 9th 2015年
- 上野若菜; 辻成希; 中村哲也; 中村哲也; 杉本邦久; 藤原明比古; 宝野和博; 広沢哲 日本金属学会講演概要(CD-ROM) 156th 2015年
- 杉本邦久; 藤原明比古 SPring-8/SACLA利用研究成果集(Web) 3 (1) 2015年
- 杉本邦久; 安田伸広 SPring-8/SACLA利用研究成果集(Web) 3 (1) 2015年
- 藤井 達也; 菅原 健人; 樋口 貴文; 片山 尚幸; 澤 博; 獅子堂 達也; 杉本 邦久; 高田 昌樹; 有馬 孝尚; 田口 康二郎; 十倉 好紀 日本物理学会講演概要集 70 (0) 2422 -2422 2015年
- 下野 聖矢; 石橋 広記; 河口 彰吾; 杉本 邦久; 久保田 佳基 日本物理学会講演概要集 70 (0) 2430 -2430 2015年
- 青柳 忍; 大沢 仁志; 杉本 邦久; 藤原 明比古; 竹田 翔一; 森吉 千佳子; 黒岩 芳弘 日本物理学会講演概要集 70 (0) 2742 -2742 2015年
- 大本 優; 竹田 翔一; 森吉 千佳子; 黒岩 芳弘; 大沢 仁志; 杉本 邦久; 北中 佑樹; 野口 祐二; 宮山 勝 日本物理学会講演概要集 70 (0) 2474 -2474 2015年
- 杉本 邦久; 藤原 明比古; 上町 裕史 日本結晶学会誌 56 (1) 49 -53 2014年02月
- 大竹研一; 大坪主弥; 大坪主弥; 杉本邦久; 藤原明比古; 藤原明比古; 北川宏; 北川宏 日本化学会講演予稿集 94th (2) 2014年
- 大竹研一; 大坪主弥; 大坪主弥; 杉本邦久; 藤原明比古; 北川宏; 北川宏 錯体化学会討論会講演要旨集 64th 2014年
- 大竹研一; 大坪主弥; 大坪主弥; 杉本邦久; 藤原明比古; 北川宏; 北川宏 分子科学討論会講演プログラム&要旨(Web) 8th 2014年
- 吉田健; 石橋広紀; 河口彰吾; 杉本邦久; 加藤健一; 高田昌樹; 久保田佳基 日本結晶学会年会講演要旨集 2014 58 2014年
- 長見和樹; 石橋広記; 河口彰吾; 杉本邦久; 加藤健一; 高田昌樹; 久保田佳基 日本結晶学会年会講演要旨集 2014 55 2014年
- 青柳 忍; 杉本 邦久; 岡田 洋史; 星野 哲久; 芥川 智行 日本物理学会講演概要集 69 (0) 621 -621 2014年
- 佐々木 崇; 佐賀山 基; 樋口 幸希; 山田 重樹; 杉本 邦久; 有馬 孝尚 日本物理学会講演概要集 69 (0) 340 -340 2014年
- 三木 郁也; 石橋 広記; 河口 彰吾; 杉本 邦久; 加藤 健一; 高田 昌樹; 久保田 佳基 日本物理学会講演概要集 69 (0) 413 -413 2014年
- 吉田 健; 石橋 広記; 河口 彰吾; 杉本 邦久; 加藤 健一; 高田 昌樹; 久保田 佳基 日本物理学会講演概要集 69 (0) 414 -414 2014年
- 長見 和樹; 石橋 広記; 河口 彰吾; 杉本 邦久; 加藤 健一; 高田 昌樹; 久保田 佳基 日本物理学会講演概要集 69 (0) 414 -414 2014年
- 杉本 邦久; 藤原 明比古; 上町 裕史; 前川 雅彦 日本結晶学会誌 56 (1) 49 -53 2014年
- 杉本 邦久 日本結晶学会誌 56 (0) s16 -s16 2014年
- 杉本 邦久 日本結晶学会誌 56 (5) 296 -300 2014年
- 芝内 孝禎; 笠原 成; 松田 祐司; 福田 竜生; 杉本 邦久 日本結晶学会誌 55 (2) 128 -134 2013年04月
- 谷垣 勝己; 藤原 明比古; 杉本 邦久; 田中 宏志; 高田 昌樹 日本結晶学会誌 55 (2) 142 -147 2013年04月
- 谷垣勝己; 藤原明比古; 杉本邦久; 田中宏志; 高田昌樹 日本結晶学会誌 55 (2) 142 -152 2013年04月
- 大竹研一; 大坪主弥; 大坪主弥; 杉本邦久; 藤原明比古; 藤原明比古; 北川宏; 北川宏 日本化学会講演予稿集 93rd (2) 2013年
- 大竹研一; 大坪主弥; 大坪主弥; 杉本邦久; 藤原明比古; 北川宏; 北川宏 錯体化学会討論会講演要旨集 63rd 2013年
- 大竹研一; 大坪主弥; 大坪主弥; 杉本邦久; 藤原明比古; 北川宏; 北川宏 分子科学討論会講演プログラム&要旨(Web) 7th 2013年
- 菅原 健人; 片山 尚幸; 西堀 英治; 澤 博; 杉本 邦久; 高田 昌樹; 有馬 孝尚; 田口 康二郎; 十倉 好紀 日本物理学会講演概要集 68 (0) 676 -676 2013年
- 大竹 研一; 大坪 主弥; 杉本 邦久; 藤原 明比古; 北川 宏 日本物理学会講演概要集 68 (0) 922 -922 2013年
- 佐賀山 基; 有馬 孝尚; 杉本 邦久; 吉野 貴文; 宮坂 等 日本物理学会講演概要集 68 (0) 937 -937 2013年
- 鶴見 淳人; 酒井 謙一; 岡田 悠悟; 北岡 慎; 植村 隆文; 岡本 敏宏; 佐藤 寛泰; 山野 昭人; 杉本 邦久; 藤原 明比古; 竹谷 純一 日本物理学会講演概要集 68 (0) 943 -943 2013年
- 酒井 謙一; 岡田 悠悟; 北岡 慎; 鶴見 純人; 植村 隆文; 佐藤 寛泰; 山野 昭人; 杉本 邦久; 藤原 明比古; 山岸 正和; 三津井 親彦; 岡本 敏宏; 竹谷 純一 日本物理学会講演概要集 68 (0) 944 -944 2013年
- 引地 奈津子; 森吉 千佳子; 黒岩 芳弘; 大沢 仁志; 杉本 邦久; 北中 佑樹; 野口 祐二; 宮山 勝 日本物理学会講演概要集 68 (0) 1016 -1016 2013年
- 青柳 忍; 星野 哲久; 芥川 智行; Sado Yuki; 北浦 良; 篠原 久典; 杉本 邦久; Rui Zhang; 村田 靖次郎 日本物理学会講演概要集 68 (0) 854 -854 2013年
- 佐々木 崇; 佐賀山 基; 山田 重樹; 有馬 孝尚; 杉本 邦久 日本物理学会講演概要集 68 (0) 517 -517 2013年
- 鳥山 達矢; 小堀 正雄; 小西 健久; 太田 幸則; 卞 舜生; 工藤 一貴; 野原 実; 杉本 邦久; 金 廷恩; 藤原 明比古 日本物理学会講演概要集 68 (0) 551 -551 2013年
- 利根川 翔; 笠原 成; 鶴原 悠悟; 福田 竜生; 杉本 邦久; 安田 伸広; 水上 雄太; 渡邊 大樹; 芳賀 芳範; 松田 達磨; 山本 悦嗣; 大貫 惇睦; 池田 浩章; 松田 祐司; 芝内 孝禎 日本物理学会講演概要集 68 (0) 553 -553 2013年
- 笠原 成; 史 宏杰; 橋本 顕一郎; 水上 雄太; 利根川 翔; 福田 竜生; 杉本 邦久; Nevidomskyy A. H; 寺嶋 孝仁; 芝内 孝禎; 松田 祐司 日本物理学会講演概要集 67 (0) 557 -557 2012年
- 金 栄勲; 高田 昌樹; 金 廷恩; 田中 宏志; 杉本 邦久; 谷口 博基; 金 聖雄; 加藤 健一; 伊藤 満; 細野 秀雄 日本物理学会講演概要集 67 (0) 985 -985 2012年
- 豊田 新悟; 大川 竜徳; 佐賀山 基; 阿部 伸行; 有馬 孝尚; 杉本 邦久 日本物理学会講演概要集 67 (0) 449 -449 2012年
- 鶴原 悠悟; 笠原 成; 利根川 翔; 水上 雄太; 渡辺 大樹; 史 宏杰; 福田 竜生; 杉本 邦久; Nevidomskyy A. H; 寺嶋 孝仁; 芝内 孝禎; 松田 祐司 日本物理学会講演概要集 67 (0) 475 -475 2012年
- 佐賀山 基; 豊田 新悟; 有馬 孝尚; 前田 陽一; 山田 重樹; 森川 大輔; 津田 健治; 杉本 邦久 日本物理学会講演概要集 67 (0) 544 -544 2012年
- 大竹 研一; 大坪 主弥; 杉本 邦久; 藤原 明比古; 北川 宏 日本物理学会講演概要集 67 (0) 801 -801 2012年
- 貞清正彰; 山田鉄兵; 山田武; 名越篤史; 山室修; 杉本邦久; 藤原明比古; 山田武; 名越篤史; 山室修; 杉本邦久; 藤原明比古; 大川尚士; 北川宏; 北川宏 錯体化学会討論会講演要旨集 61st 100 2011年09月
- 藤原 明比古; 杉本 邦久; Shih Che-Hsiu; 田中 宏志; Tang Jun; 田邉 洋一; Xu Jingtao; 平郡 諭; 谷垣 勝己; 高田 昌樹 日本物理学会講演概要集 66 (0) 846 -846 2011年
- 森吉 千佳子; 平本 尚三; 大久保 寿紀; 黒岩 芳弘; 大沢 仁志; 杉本 邦久; 北中 佑樹; 野口 祐二; 宮山 勝 日本物理学会講演概要集 66 (0) 970 -970 2011年
- 史 宏杰; 笠原 成; 岡崎 竜二; 山下 穣; 橋本 顕一郎; 福田 竜生; 杉本 邦久; 芝内 孝禎; 寺嶋 孝仁; 松田 祐司 日本物理学会講演概要集 66 (0) 503 -503 2011年
- 山浦 淳一; 大串 研也; 山内 一宏; 瀧川 仁; 広井 善二; 長谷川 巧; 宇田川 眞行; 大隅 寛幸; 竹下 聡史; 杉本 邦久; 徳田 哲久; 有馬 孝尚 日本物理学会講演概要集 66 (0) 567 -567 2011年
- 藤原 明比古; 杉本 邦久; Shih Che-Hsiu; 田中 宏志; Tang Jun; 田邉 洋一; Xu Jingtao; 平郡 諭; 谷垣 勝己; 高田 昌樹 日本物理学会講演概要集 66 (0) 867 -867 2011年
- 森吉 千佳子; 平本 尚三; 大久保 寿紀; 黒岩 芳弘; 大沢 仁志; 杉本 邦久; 北中 佑樹; 野口 祐二; 宮山 勝 日本物理学会講演概要集 66 (0) 1006 -1006 2011年
- Shih Che-Hsiu; Sheu Chou-Fu; Kato Kenichi; Sugimoto Kunihisa; Kim Jungeun; Wang Yu; Takata Masaki 日本物理学会講演概要集 65 (2) 670 -670 2010年08月
- 石渡 晋太郎; 奥山 大輔; 酒井 英明; 徳永 祐介; 杉本 邦久; 田口 康二郎; 有馬 孝尚; 十倉 好紀 日本物理学会講演概要集 65 (0) 596 -596 2010年
- 山浦 淳一; 大串 研也; 広井 善二; 大隅 寛幸; 杉本 邦久; 徳田 哲久; 有馬 孝尚 日本物理学会講演概要集 65 (0) 628 -628 2010年
- 橋本 隆; 吉田 芙美子; 森吉 千佳子; 黒岩 芳弘; 杉本 邦久 日本物理学会講演概要集 65 (0) 1000 -1000 2010年
- 新居 陽一; 佐賀山 基; 有馬 孝尚; 酒井 理宇; 青柳 忍; 西堀 英治; 澤 博; 杉本 邦久; 大隅 寛幸; 高田 昌樹 日本物理学会講演概要集 65 (0) 500 -500 2010年
- 山浦 淳一; 大串 研也; 広井 善二; 大隅 寛幸; 竹下 聡史; 杉本 邦久; 徳田 哲久; 有馬 孝尚 日本物理学会講演概要集 65 (0) 607 -607 2010年
- 藤山 茂樹; 新高 誠司; 杉本 邦久; 大隅 寛幸; 竹下 聡史; 有馬 孝尚; 高木 英典 日本物理学会講演概要集 65 (0) 608 -608 2010年
- 藤山 茂樹; 新高 誠司; 杉本 邦久; 栗山 博道; 松野 丈夫; 大隅 寛幸; 有馬 孝尚; 高木 英典 日本物理学会講演概要集 65 (0) 608 -608 2010年
- 澤田 智博; 金 廷恩; 杉本 邦久; 加藤 健一; 石角 元志; 社本 真一; 高田 昌樹 日本物理学会講演概要集 65 (0) 616 -616 2010年
- 新高 誠司; 大隈 寛幸; 杉本 邦彦; 橋爪 大輔; 加藤 健一; 有馬 孝尚; 高田 昌樹; 高木 英典 日本物理学会講演概要集 64 (2) 535 -535 2009年08月
- 大串 研也; 大隅 寛幸; 杉本 邦久; 山浦 淳一; 片山 尚幸; 有馬 孝尚; 高木 英典 日本物理学会講演概要集 64 (0) 527 -527 2009年
- 内海 有希; 佐藤 仁; 橋本 隆; 森吉 千佳子; 黒岩 芳弘; 谷口 雅樹; 平岡 耕一; 小島 健一; 杉本 邦久; 大久保 寿紀 日本物理学会講演概要集 64 (0) 543 -543 2009年
- 大橋 啓; 高山 知弘; 藤山 茂樹; 福永 武男; 橋爪 大輔; 杉本 邦久; 大隈 寛幸; 有馬 孝尚; 高田 昌樹; 高木 英典 日本物理学会講演概要集 64 (0) 566 -566 2009年
- 施 哲修; 許 朝富; 杉本 邦久; 金 廷恩; 加藤 健一; 王 瑜; 高田 昌樹 日本物理学会講演概要集 64 (0) 787 -787 2009年
- 奥山 大輔; 青柳 忍; 杉本 邦久; 森吉 千佳子; 大隅 寛幸; 施 哲修; 岡林 弘卓; 佐藤 亮太; 橋本 隆; 黒岩 芳弘; 澤 博; 西堀 英治; 高田 昌樹; 田口 康二郎; 有馬 孝尚; 金子 良夫; 十倉 好紀 日本物理学会講演概要集 63 (0) 483 -483 2008年
- 杉本 邦久 リガクジャーナル 38 (2) 1 -5 2007年
- 加藤 隆幸; 山崎 幹緒; 杉本 邦久 Viva origino 34 (1) 33 -33 2006年03月
共同研究・競争的資金等の研究課題
- 超セラミックスの高度構造解析日本学術振興会:科学研究費助成事業 学術変革領域研究(A)研究期間 : 2022年06月 -2027年03月代表者 : 杉本 邦久
- 日本学術振興会:科学研究費助成事業 基盤研究(S)研究期間 : 2022年04月 -2027年03月代表者 : 北川 進; 杉本 邦久; 大竹 研一; Packwood Daniel
- 日本学術振興会:科学研究費助成事業研究期間 : 2022年06月 -2027年03月代表者 : 前田 和彦; 本橋 輝樹; 杉本 邦久; 高橋 雅英; 廣井 善二; 桑原 彰秀; 片桐 清文; 大谷 亮; 堀毛 悟史代表・分担者9名、協力者1名で構成される本領域の総括班では、領域内のリソースと研究の進捗を把握・共有し、審査所見・評価委員会の助言等に基づき領域全体の方向性・戦略を決定するとともに、連携促進・領域活性化に必要な支援・調整を領域代表と計画班代表のリードのもと一致団結して行った。 採択後、領域運営に関する打合わせをオンラインで行い、2022年8月18日にキックオフ会議を開催した。2023年1月26-27日には、対面形式での領域会議を開催することで、新規な共同研究を多数立ち上げた。 国際活動として、2022年12月5日に外国人研究者3名を招き、「新物質」をキーワードとする国際シンポジウムを開催した。さらには、陰山(総括班協力者)、タッセル(A01分担)が主導するcore-to-coreプロジェクトとも協働して、国際シンポジウム(2023年3月14-16日)をオックスフォード大学で開催した。国内での活動としては、物性科学領域横断研究会の新たなメンバーとして企画に加わり、11月25-26日に16回会議をオンラインで開催した。また、日本セラミックス協会のサテライトプログラムの一環として、第1回の領域公開シンポジウム(2023年3月8日)を開催した。 渉外・広報の活動として、ニュースレターの第1号を3月に発行した。また、領域ホームページ・ツイッターをキックオフ会議にあわせて8月に開設し、その後、随時更新を進めることで成果の発信に努めた。「若手育成」の具体的な取り組みとして班間・班内留学を実施し、10月には研究項目AーCを跨いだ若手研究者による合同研究打ち合わせを九州大学で実施した。コロナ禍の影響を受ける中ではあったが、若手研究者の海外派遣(米国ペンシルベニア大学での分光計測実験)についても1件実施した。アウトリーチ活動の積極参加も促し、高校生を対象とした講義・実習等を行った。
- 日本学術振興会:科学研究費助成事業 新学術領域研究(研究領域提案型)研究期間 : 2016年06月 -2021年03月代表者 : 阿部 正明; 杉本 邦久; 小野 利和本研究は、多核金属錯体およびそれらをモチーフとした多様な超分子構造体を結晶相ならびに異相界面へと集積化することにより、非対称場において特異的に発現する構造化学、レドックス・光・触媒化学、超高圧下での構造・物性化学を開拓することを目的としている。本年度は以下の成果を得た。 結晶相をはじめとする固相中で構築される非対称環境や外場に応答する多核金属錯体の機能開発と評価を行った。結晶相でフォトクロミズムを示すロジウム二核錯体の構造相転移のメカニズムと非線形応答性を共同研究者とともに見出した。ベンズイミダゾールチオール二座配位子とする銅(I)多核錯体においては、同一組成で異なる核数の化合物の結晶を作り分けることに成功し、それぞれ可視または近赤外部に固体二重発光性を示すことを見出した。今後の多重発光性を示す物質群の開発と学理構築、安価金属を用いた固体発光温度センサやセキュリティセンサへの展開が期待される。 分子レベルでの電子的な非対称性の制御として、外部刺激応答性を導入した新たな混合原子価錯体を開発した。トリアリールアミン二量体を混合原子価ユニットとし、ホウ素置換基を電子アクセプターとして利用した。光励起により、窒素中心からホウ素中心へ分子内電荷移動が進行し、電荷分離した混合原子価状態にアクセスできることを見出した。フェムト秒過渡吸収光スペクトルによって高速ダイナミクスを検討し、片方のトリアリールアミンがジアリールアミンに似た電子構造となり、基底状態よりも電荷分布が偏ることを明らかにした。ビフェロセンを混合原子価ユニットとし、ホウ素中心をルイス酸サイトとして利用した系では、よりハードなルイス塩基性ゲストアニオンとの結合に伴い、混合原子価を担う正電荷がクーロン引力によってより局在化することを見出した。
- 放射光を用いたX線精密構造解析による医薬品共結晶体の物性予測制御法の研究ひょうご科学技術協会:学術研究助成研究期間 : 2016年04月 -2017年03月代表者 : 杉本邦久
- 文部科学省:科学研究費補助金(基盤研究(C))研究期間 : 2014年 -2016年代表者 : 杉本 邦久Caffeine-Oxalic acid及びCaffeine-Malonic acidの共結晶体の精密構造解析により、Malonic acidにより構築されるCaffeine共結晶体は、Oxalic acidにより構築されるCaffeine共結晶体に比べて弱い水素結合により構築されていることが定量的に分かった。本研究による共結晶体の物理量の可視化法は、熱・湿度安定性や溶解性などを制御している分子間相互作用を定量的に解析することができる。これらは、医薬品共結晶体の迅速な安定性予測や効率的な分子設計が可能であり、今後、新規医薬品の物性を制御する標準的な技術として発展することが期待される。
- 日本学術振興会:科学研究費助成事業 基盤研究(A)研究期間 : 2011年04月 -2015年03月代表者 : 澤 博; 杉本 邦久放射光X線回折を用いた精密解析を通して,強相関電子系物質の平衡状態の観測を行った。スピンと軌道の自由度が極低温まで凍結しない平衡状態を維持するという学術的に重要な量子液体状態を銅酸化物の構造物性研究によって得られた。この量子液体状態は,ヤン-テラー活性な二価の銅イオンにおいて数千度のエネルギー利得を得られる対称性の低下を抑えて実現しており,固体物理の常識を覆す大きな発見となった。更に,特異な結晶構造中の軌道分裂を利用した蛍光体の開発,希土類元素の含有量を極力抑えた40K級の転移温度を持つ鉄砒素系超伝導体の発見など,応用上も重要な新規物質開発に多大に貢献することが出来た。
- 文部科学省:科学研究費補助金(若手研究(B))研究期間 : 2012年 -2013年代表者 : 杉本 邦久医薬品原末は、直接的な薬効だけでなく保存時の安定性も医薬品としての価値を決める。2つ以上の有機分子が静電的相互作用により構築される共結晶体は、医薬的効能を保持しながら物性の制御が可能であり、新しい創薬技術として注目されている。本研究では、物性可視化の方法論として放射光X線回折を用いた精密構造解析による電子密度分布について実験的な直接観察を行った。その結果、静電ポテンシャルの可視化により、シュウ酸とカフェイン分子の電荷密度の様子を明確に表現することに成功した。本研究成果によって、精密構造解析を用いた物理量の定量化による医薬品共結晶体の物性予測への応用が期待できる。
産業財産権
- 特許第4177344号:分子構造表示装置 2008年08月29日吉田 博喜, 杉本 邦久 株式会社リガク 201103062865170466
- 特開2006-268453:分子構造表示装置 2006年10月05日吉田 博喜, 杉本 邦久 株式会社リガク 200903087891135649