集積型金属錯体の次元構造の合理的制御

2001 年度 実績報告書

• 研究課題/領域番号: 10149104
• 研究機関: 東京工業大学
• 研究代表者: 山本 隆一 東京工業大学, 資源化学研究所, 教授 (10016743)
• 研究分担者: 北川 宏 筑波大学, 化学系, 助教授 (90234244) ; 山下 正廣 東京都立大学, 大学院・理学研究科, 教授 (60167707) ; 宗像 恵 近畿大学, 理工学部, 教授 (80090942) ; 橋本 和仁 東京大学, 先端科学技術研究センター, 教授 (00172859)
• キーワード: 集積型金属錯体 / 次元構造 / 導電性 / 光学的特性 / 磁性 / 遷移金属錯体 / 電気化学的応答 / 高分子金属錯体

研究概要

集積型金属錯体の次元構造の合理的制御について研究を推進した。すなわち、銀、パラジウム、白金、銅、コバルト、鉄、金、ルテニウム及びニッケルの金属錯体について、ハロゲン、ビスチエニルエテン類、ピレン等の多環芳香族化合物類、シアノ基、シクロペンタジエニル基、アミン類等が配位した3次元、2次元、一次元的に秩序ある構造を有する金属錯体を合成し、その物性、機能を評価した。また、これらの集積型金属錯体を形成させるための新規配位子を合成した。
集積型金属錯体の物性、機能としては、導電性、光機能性、磁気的応答、電気化学的応答について研究し、集積型金属錯体の分子構造との対比から解析した。その結果、フォトクロミック性銀錯体、ホールドーピングが可能なニッケル-コバルト混合型導電性集積金属錯体、磁場誘起軌道整列と水素ドーピングによる電子・プロトン伝導性を示す金属二量体骨格を有する新規金属錯体、ポリフェロセン構造を有しサイクリックボルタモグラムにおいてピーク電流値が掃引速度の平方根に比例する関係が確認されるポリマー金属錯体が合成され、機能化のための基礎を解明した。集積型金属錯体の構造解析はX線回折法、NMR法等により行なった。

研究成果

• [文献書誌] T.Yamamoto, H.Kokubo, T.Morikita: "Molecular Alignment of Head-to-Tail-Type Poly(3-hexylthiophene-2,5-diy) and Related Polymers and Compounds on Substrates"J.Polym.Sci.B, Polym.Phys.. 39. 1713-1718 (2001)
• [文献書誌] I.Nurulla, T.Morikita, H.Fukumoto, T.Yamamoto: "Preparation and Properties of Poly [(2-alkylbenzimidazole)-alt-thiophenels with Long Alkyl Side Chain"Macromol.Chem.Phys.. 202. 2335-2340 (2001)
• [文献書誌] T.Yamamoto, K.Shiraishi, M.Abla, I.Yamaguchi, L.B.Groenendaal: "Neutral Poly (3,4-ethylenedioxythiophene-2,5-diyl)s : Preparation by Organometallic Polycondensation and Their Unique p-doping Behavior"Polymer. 43. 711-719 (2001)
• [文献書誌] K.Shiraishi, T.Kanbara, T.Yamamoto, L.B.Groenendaal: "Preparation of a Soluble and Neutral Alkyl Derivative of Poly(3,4-ethylenedioxythiophene) and its Optical Properties"Polymer. 42. 7229-7232 (2001)
• [文献書誌] T.Yamamoto, I.Nurulla, A Ushiro: "Organometallic C-N Coupling between N, N'-dichloro-p-benzoquinone Diimine and Grignard Reagents and its Application to Synthesis of Polyanilines"Tetrahedron Lett.. 42. 8653-8656 (2001)
• [文献書誌] T.Morikita, T.Yamamoto: "Electrochemical Determination of Diffusion Coefficient of π-Conjugated Polymers Containing Ferrocene Unit"J.Organometal.Chem.. 637-639. 809-812 (2001)
• [文献書誌] J.C.Zhong, M.Munakata, T.K.-Sowa, et al.: "Spiral, Herringbone and Triple-decker Silver(I) Complexes of Benzopyrene Derivatives Assembled with Their h2-Coordinations"Inorg.Chem.. 40. 3191-3199 (2001)
• [文献書誌] M.Munakata, J.C.Zhong, T.K.-Sowa, M.Maekawa, Y.Suenaga, M.Kasahara, H.Konaka: "A Double-decker Silver(1) Coordination Polymer of 1-Methylpyrene with Columnar Aromatic Stacks. Effect of Substituting Groups on Structure of Silver(I) Complexes with Polycyclic Aromatic Hydrocarbons"Inorg.Chem.. 40. 7087-7090 (2001)
• [文献書誌] J.C.Zhong, M.Munakata, Y.Suenaga, T.K.-Sowa, M.Maekawa, et al.: "Silver(I) Coordination Polymer of 2,5-Bis(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-1,3,4,6-tetra-thiapentalene (TTM-TTP) and Its High Conductive Iodine Derivative"Inorg.Chem.. 40. 7096-7098 (2001)
• [文献書誌] M.Munakata, G.-L.Ning, T.K.-Sowa, et al.: "Construction of Metallocyclophanes from Silver(I) h2-Coordination Complexes with Tri, 1,2-Benztriphenylenes and Phenanthrene"J.Am.Chem.Soc.. (in press). (2001)
• [文献書誌] J.C.Zhong, M.Munakata, T.K.-Sowa, M.Maekawa, Y.Suenaga: "A Novel 2-D Silver(I)-acyclicpolyene Coordination Polymer Assembled with Linear Unsaturated Bridges"Inorg.Chi.Acta. 322. 150-156 (2001)
• [文献書誌] M.Wen, M.Munakata, Y.Suenaga, T.K.-Sowa, M.Maekawa: "Silver(I) Coordination Polymers of Cyclic Sulfur Ligand, 2,2,3-Tetrahydro-4,4-dithia-1, 1-binaphthylidene"Inorg.Chim.Acta. 322. 133-137 (2001)
• [文献書誌] M.Munakata et al.: "1-D Cyano-Bridged Heterometallic Complexes Consisting of 1,4,8,11-Tetraazacyclotetradecanesilver(II) and Tetracyanopalladium(II) or Tetracyanoplatinum(II)"Inorg.Chim.Acta. 317. 268-275 (2001)
• [文献書誌] M.Munakata, M.Wen, Y.Suenaga et al.: "Carbon and Nitrogen Atoms-Coordinated Silver(I) Polymers of 2,4.6-Triphenoxy-1,3,5-triazine"Polyhedron. 20. 2321-2327 (2001)
• [文献書誌] M.Munakata, M.Wen et al.: "Silver(I) Complexes of Triazine Derivatives Having Stepped Interaction and 2D Sheets"Polyhedron. 20. 2037-2037 (2001)
• [文献書誌] S.Onaka, Y.Katsukawa, M.Shiotsuka, O.Kanegawa, M.Yamashita: "Synthesis, X-ray Molecular Structure Analysis, and Study on Ligand Scambling Reactions of New Thiolatogold(I) Complexes with Various Phosphines"Inorg.Chim.Acta. 312. 100-102 (2001)
• [文献書誌] T.Manabe, T.Kawashima, T.Ishii, H.Matsuzaka, M.Yamashita, K.Marumoto, H.Tanaka, S.Kuroda, H.Kitagawa, T.Mitani, H.Okamoto: "Syntheses and Physical Properties of Quasi-One-Dimensional Chioro-Bridged Ni-Pd Mixed-Metal MX-Chain Compounds, Nil-xPdx(chxn)2C13"Synth.Met. 116. 415-417 (2001)
• [文献書誌] T.C.Kobayashi, K.Tanaka, K.Fujiwara, K.Amaya, N.Aizawa, T.Ishii, M.Yamashita: "Proton NMR Study of the Field-induced Long Range Ordering in Haldane Gap System NDMAP"J.Mag.Mag.Mat. 70. 813-817 (2001)
• [文献書誌] T.C.Kobayashi, H.Tatewaki, A.Koda, K.Amaya, Y.Narumi, K.Kindo, N.Aizawa, T.Ishii, M.Yamashita: "Field-induced Long Range Ordering in Haldane Gap System NDMAZ"J.Phys.Soc.Jpn. 70. 813-823 (2001)
• [文献書誌] H.Matsuzaka, H.Okimura, Y.Sato, T.Ishii, M.Yamashita, M.Kondo, S.Kitagawa, M.Shiro, M.Yamasaki: "Synthesis, Structure and Reactivities of the Dinuclear μ-η1:η 6-Arylethnyl Ruthenium Complexes"J.Organomet.Chem.. 625. 133-137 (2001)
• [文献書誌] T.C.Kobayashi, H.Tanaka, K.Fujiwara, K.Amaya, N.Aizawa, T.Ishii, M.Yamashita: "Proton NMR study of the field-induced long-range ordering in Haldane gap system NDMAP"J.Mag.Mag.Mat.. 226・230. 423-424 (2001)
• [文献書誌] K.Marumoto, H.Tanaka, S.Kozaki, S.Kuroda, S.Miya, T.Kawashima, M.Yamashita: "ESR Observation of Average-Valence and Charge-Density-Wave States in Quasi-One-Dimensional Halogen-Bridged Binuclear Metal Complexes"Solid State Commun.. 120. 101 (2001)
• [文献書誌] T.Ishii, N.Aizawa, M.Yamashita, H.Matsuzaka, I.Ikemoto, K.Kikuchi, T.Kodama, Y.Iwasa: "Intermolecular interaction of Complexes with Anti-formed Metal Octaethylporphyrins with C60"Synth.Met.. 121. 1165-1166 (2001)
• [文献書誌] T.Aso, T.Manabe, T.Kawashima, T.Ishii, H.Matsuzaka, M.yamashita, N.Kuroda: "Doping Effect on MX-Chain Compounds"Synth.Met.. 120. 775-776 (2001)
• [文献書誌] H.Tanaka, K.Marumoto, S.Kuroda, T.Manabe, M.Yamashita: "ESR detection of induced moments Pd3+ in halogen-bridged Ni-Pd mixed-metal complexes"Synth.Met.. 120. 949-950 (2001)
• [文献書誌] T.Manabe, T.Ishii, H.Matsuzaka, M.Yamashita, T.Kawashima, K.Marumoto, H.Tanaka: "Syntheses and Physical Properties of Halogen-Bridged Ni-Pd Mixed-Metal Complexes, Ni1-xPdx(chxn)_2XY_2"Synth.Met. 120. 925-926 (2001)
• [文献書誌] N.Kimura, M.Kano, T.Manabe, M.Yamashita, R.Ikeda: "Metal Valence Structures in 1-D Mixed-Metal Complexes [Ni1-xPdxX(chxn)_2]X_2 Studied by Solid NMR"Synth.Met. 120. 777-778 (2001)
• [文献書誌] T.Ishii, N.Aizawa, R.Kanehama, M.Yamashita, H.Matsuzaka, T.Kodama, K.Kikuchi.I.Ikemoto: "DV-Xα Calculation for the Syntheses and Electronic Structure of Macrocyclic Metal Complexes with Fulleren C60"Inorg.Chim. Acta. 317. 81-90 (2001)
• [文献書誌] N.Kimura, S.Ishmaru, T.Kawashima, S.Miya, T.Manabe, M.Yamashita, R.Ikeda: "Valence Structure and Magnetic Interaction in MMX-Type 1D Complexes, A4[Pt_2I(P_2O_5H_2)_4].nH_2O, Studied by 31P Solid NMR"Synth. Met.. 120. 779-780 (2001)
• [文献書誌] T.Ishii, N.Aizawa, H.Hara, M.Yamashita, H.Matsuzaka: "Electronic Structure of the Haldane Gap System derived using DV-Xα Calculation"Polyhedron. 20. 1297-1304 (2001)
• [文献書誌] T.Ishii, R.Kanehama, N.Aizawa, M.Yamashita, H.Matsuzaka, K.Sugiura, H.Miyasaka, T.Kodama, K.Kikuchi, I.Ikemoto: "Fulleren C60 exhibiting a strong intermolecular interaction in a cocrystallite with C4 symmetrical cobalt tetraki (di-tert-butylphenyl) porphyrin"J.Chem.Soc., Dalton Trans/. 2975 (2001)
• [文献書誌] H.Miyasaka, C.Kachi-Terajima, T.Ishii, M.Yamashita: "A New Metal-Metal Bonded Diruthenium(II, III) Compound Bridged by the Dianionic Trident Ligand N-(2-Pyridyl)-2-Oxy-5-Chlorobenzylaminate (5-Clsalpy2-)"J.Chem.Soc., Dalton Trans. 1929-1930 (2001)
• [文献書誌] N.Metoki, Y.Koike, Y.Matsuoka, T.Kobayasi, abd M.Yamashita: "Neutron scattering study of linear-chain Haldane compounds NDMAZ and NDMAP"J.Mag.Mag.Mat.. 226-230. 414-416 (2001)
• [文献書誌] T.Ishii, N.Aizawa, R.Kanehama, M.Yamashita, H.Matsuzaka, H.Miyasaka, T.Kodama, K.Kikuthi, I.Ikemoto, Y.Iwasa, T.Mochida: "Synthesis of Cocrystallite with Biferrocene and C60"Trans.Mater.Res.Soc.Jpn.. 26. 1147 (2001)
• [文献書誌] M.Mitsumi, T.Murase, H.Kishida, T.Yoshinari, Y.Ozawa, K.Toriumi, H.Kitagawa.T.Mitani: "Metallic Behavior and Periodical Valence-Ordering in a New MMX Chain Compound, Pt_2(EtCS_2)_4I"J.Am.Chem.Soc. 123. 11179-11192 (2001)
• [文献書誌] Y.Qi Wang, A.Sato, K.Saito, M.Yamamoto, H.Kitagawa, T.Mitani, M.Sorai: "Heat Capacity of the Halogen-Bridged Mixed-Valence Complex Pt_2(dta)_4I (dta=CH3CS2-)"J.Phys.Chem.. 106. 197-202 (2001)
• [文献書誌] R.Makiura, I.Nagasawa, N.Kimura, S.Ishimaru, H.Kitagawa, R.Ikeda: "An Unusual Six-Co-Ordinate Platinum(II) Complex Containing A Neutral I_2 Ligand"Chem.Commun.. 17. 1642-1643 (2001)
• [文献書誌] M.Fujishima, S.Kanda, T.Mitani, H.Kitagawa: "Hydrogen-Induced Properties of Copper Coordination Polymer : catena-N, N'-bis(hydroxyethyl)dithiooxamidatocopper"Synth.Met. 119. 485-486 (2001)
• [文献書誌] S.Maki, Y.Morita, H.Kitagawa, T.Mitani, K.Nakasuji: "A Novel Charge-Transfer Complex of TTF Having Uracil Moiety with TCNQ"Synth.Met. 120. 741-742 (2001)
• [文献書誌] H.Kitagawa, N.Onodera, T.Mitani: "Low-Temperature X-Ray Single-Crystal Analysis of a Conductive Mixed-Valence MMX-Chain System, Pt_2(dta)_4I (dta=CH_3CS_<2->)"Synth.Met. 116. 401-404 (2001)
• [文献書誌] T.Manabe, T.Kawashima, T.Ishii, H.Matsuzaka, M.Yamashita, K.Marumoto, H.Tanaka, S.Kuroda, H.Kitagawa, T.Mitani, H.Okamoto: "Syntheses and Physical Properties of Quasi-One-Dimensional Chloro-Bridged Ni-Pd Mixed-Metal MX-Chain Compounds, Ni1-xPdx(chxn)_2Cl_3"Synth.Met. 116. 415-418 (2001)
• [文献書誌] T.Kawashima, K.Takai, H.Aso, T.Manabe, K.Takizawa, C.Kachi-Terajima, T.Ishii, H.Miyasaka, H.Matsuzaka, M.Yamashita, H.Okamoto, H.Kitagawa, M.Shiro, K.Toriumi: "Syntheses and Physical Properties of Quasi-One-Dimensional Halogen-Bridged CuII-PtIV Mixed-Metal Complexes, [Cu(chxn)2] [PtX2(chxn)2]X4"Inorg.Chem. 40. 6651-6655 (2001)
• [文献書誌] M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Electronic State of A Hydrogen-Doped Copper Coordination Polymer : catena-オ-N, N'-bis-(hydroxyethyl)dithiooxamidatocopper(II), (HOC_2H_4)_2dtoaCu"Mol.Cryst.Liq.Cryst.. (in press). (2001)
• [文献書誌] Y.Nagao, S.Kanda, R.Ikeda, H.Kitagawa: "Complex-Plane Impedance Study on A Hydrogen-Doped Copper Coordination Polymer : N, N'-bis-(2-hydroxy-ethyl)dithiooxamidatocopper(II)"Mol.Cryst.Liq.Cryst.. (in press). (2001)
• [文献書誌] S.Ohkoshi, K.Hashimoto: "Photo-magnetic and Magneto-optical effects of Functionalized Prussian Blue Analogs"J.Photochem.Photobio.C. 2. 71-88 (2001)
• [文献書誌] S.Ohkoshi, N.Machida, Z.Zhong, K.Hashimoto: "Photo-induced magnetization in copper (II) octacyanomolybdate (IV)"Synth.Metal. 122. 523-527 (2001)
• [文献書誌] S.Ohkoshi, N.Machida, Y.Abe, Z.Zhong, K.Hashimoto: "Visible light-induced reversible photomagnetism in copper(II) octacyano molybdate(IV)"Chem.Lett.. 312-313 (2001)
• [文献書誌] S.Ohkoshi, T.Houzumi, K.Hashimoto: "The first observation of an inverted hysteresis loop in a bulk magnet"Phys.Rev.B. 64. 132404 (2001)
• [文献書誌] K.Ikeda, S.Ohkoshi, K.Hashimoto: "Second harmonic generation (SHG) and magnetization-induced second harmonic generation (MSHG) in electrochemically synthesized magnetic films of ternary metal Prussian blue analogs"Chem.Phys.Lett.. 349. 371 (2001)
• [文献書誌] T.Yokoyama, K.Okamoto, T.Ohta, S.Ohkoshi, K.Hashimoto: "Local structure and electronic state of a photo-and x-ray-induced magnet of CoW cyanide studied by x-ray-absorption fine structure spectroscopy"Phys.Rev.B. 65. 64438 (2001)
• [文献書誌] S.Ohkoshi, H.Tokoro, M.Utsunomiya, M.Mizuno, M.Abe, K.Hashimoto: "The first observation of spin transition of an otahedorally coordinated magnese(II) compound"J.Phys.Chem B. (in press). (2001)
• [文献書誌] N.Shimamoto, S.Ohkoshi, O.Sato, K.Hashimoto: "Control of charge-transfer induced spin transition temperature on cobal t-iron Prussian blue analogues"Inorg.Chem. (in press). (2001)