1999 年度実績報告書

集積型金属錯体の次元構造の合理的制御

研究課題

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	北川宏北陸先端科学技術大学, 大学院・材料科学研究科, 助手 (90234244) 山下正廣東京都立大学, 大学院・理学研究科, 教授 (60167707) 宗像惠近畿大学, 理工学部, 教授 (80090942)
キーワード	集積型金属錯体 / 次元構造 / ニッケル錯体 / パラジウム錯体 / 銀錯体 / 導電性 / 光機能 / ポリポルフィリン
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、銅、パラジウム、白金及び銀の金属錯体について、3-チェニルエテン類、多座アミン類等の配位子が配位した、3次元あるいは2次元的に秩序ある構造を有する錯体を合成した。また、この集積型金属錯体についてX線構造解析により、Ag-S相互作用、π-πの相互作用を評価し、フォトクロミズム等の光応答性を明らかにした。さらに、ニッケル、パラジウムのハルデンギャップ化合物(たとえば[Ni(AA)_2X]Y型錯体;AAは多座アミン、X、Yはアニオン)である集積型金属錯体について、一次元構造中におけるスピンの状態を明らかにし低次元磁性体の創製について研究を推進した。この際、一次元鎖を形成するアニオンとして金属間架橋を形成するNO_2配位子を用いた。さらに、ルベアン酸銅錯体について錯体ポリマーの電気化学的還元により水素吸蔵を行なわせ、その結果を各種分光法により解析した。また、この金属錯体の導電性は水素のドーピングにより9桁増大し、温度変化は絶縁体→半導体→金属の転移を示していることが分かった。また、本研究においては、ポリ(ピリミドピリミジン)のような配位子について、銅やルテニウム等の金属種と錯体化させ、その分光学的挙動、電気化学的応答及び触媒作用を明らかにした。また、亜鉛-ポルフィリン錯体(Por(Zn))が主鎖に沿って約50ケ結合した高分子集積型金属錯体を合成し、この錯体中においては主鎖π共役方向に沿った次元性に基づく電子の相関作用を持っている系であることが紫外可視分光法などにより分った。さらに、これらの金属錯体は発光特性を有することが分った。

研究成果

(36件)

すべてその他

すべて文献書誌 (36件)

[文献書誌] N. Hayashida: "Synthesis of Ru- and Os-Complexes of π-Conjuated Oligomers of 2,2'-Bipyridine and 5,5'-Bipyrimidine"Bull. Chem. Soc. Jpn.. 72. 1153-1162 (1999)
[文献書誌] B.-L. Lee: "Synthesis of New Alternating CT-Type Copolymers of Thiophene and Pyrido 3,4-b pyazine Units"Macromolecules. 32. 1375-1382 (1999)
[文献書誌] T. Yamamoto: "Redox Behavior of Poly (diphenylamine-4,4'-diyl) in Acidic Media and Electonic Properties"Jpn. J. Appl. Phys.. 38. L273-L276 (1999)
[文献書誌] Y. Murakami: "Ni-Promoted Syntheses of New 3,3'-Dichloro-5,5'-bipyrzoles and Poly (Bipyraxole-5,5'-diyl)s"Bull. Chem. Soc. Jpn.. 72. 1629-1635 (1999)
[文献書誌] Y. Muramatsu: "Preparation of Main-chain Type Poly (anthraquinone)s Having Alkoxy Groups"Polymer. 40. 6607-6609 (1999)
[文献書誌] M. Yamashita: "Tuning of Charge Density Wave Strengths by Competition between Electron-Correlation of Ni^<III>"Inorg. Chem.. 38. 5124-5130 (1999)
[文献書誌] M. Munakata: "A Novel Double-Starand Helical Motif in a Two-dimensional Polymeric Complex of Silver (I)"Chem. Commun.. 1545-1546 (1999)
[文献書誌] K. Sugimoto: "A Novel Eight-emebered Cu_4I_4 Ring Supported by Sulfur Atoms of an M (mnt)_2 Moiety"Chem. Commun.. 455-456 (1999)
[文献書誌] M. Maekawa: "Syntheses, Crystal Structures and Autoreduction Behavior of Antiferromagnetically Coupled"Inorg. Chim. Acta. 293. 20-29 (1999)
[文献書誌] L.P. Wu: "Silver (I) Tetraiodoethylene Complexes with Twisted Olefin Moiety"Inorg. Chim. Acta. 290. 251-255 (1999)
[文献書誌] M. Maekawa: "Synthesis and Crystal Structure of Tetranuclear Copper (I) and Silver Complexes"Inorg. Chim. Acta. 290. 153-158 (1999)
[文献書誌] T. Yamamoto: "Temperature dependent electrical conductivity of p-doped poly (3,4-ethylenedioxythiophene)"Polym. Bull.. 42. 321-327 (1999)
[文献書誌] T. Shimizu: "Rh-complex promoted synthesis of poly (aryl-acetylene) with pendant TTF units"Inorg. Chim. Acta. 296. 278-280 (1999)
[文献書誌] T. Sakano: "Preparation and characterization of various N-substituted-2-aza-3- ferrocenophanes"Inorg. Chim. Acta. 296. 176-182 (1999)
[文献書誌] T. Morikita: "Preparation of poly (aryleneethynulene) type pi-conjugated polymers constituted of 2-alkylbenzim"Inorg. Chim. Acta. 296. 254-260 (1999)
[文献書誌] Y. Suenanga: "Two-dimnsional Supramolecular Coordination Compounds of Silver (I) with Box Structures"J. Chem. Soc., Dalton Trans.. 2737-2742 (1999)
[文献書誌] G.L. Ning: "Construction of 2-D Multilayer Structures : Silver (I) Complexes with Linear Aromatic Compounds"J. Chem. Soc., Dalton Trans.. 2527-2536 (1999)
[文献書誌] M. Munakata: "Open Dimeric and Closed Polymeric Container Molecules : Calixarene Complexes of Ag (I)"J. Chem. Soc., Dalton Trans.. 373-378 (1999)
[文献書誌] G.L. Ning: "Mobility of Silver (I) Ions Around the Propeller Ligand, Hexaphenylbenezene in Silver (I)"Inorg. Chem.. 38. 5674-5680 (1999)
[文献書誌] T. Yamamoto: "Preparation of π-Conjuated Polymers Composed of hydroquinone, p-Benzoquinone, and p-Diacetoxyphen"Macromolecules. 32. 8886-8896 (1999)
[文献書誌] G.L. Ning: "Cationic Tetrasilver Complex Hexaphenylbenzene"G.L. Ning. 38. 1376-1477 (1999)
[文献書誌] M. Munakata: "Construction of Metal Sandwich System Derived from Assembly of Silver (I) Complexes"J. Am. Chem. Soc.. 121. 4968-4976 (1999)
[文献書誌] M. Maekawa: "Synthesis and Structures of Dinuclear Rhodium (I) Complexes and 1-D Zigzg Chain Rhodium (I)"J. Chem. Soc., Dalton Trans.. 4357-4362 (1999)
[文献書誌] A.S. Batsanov: "The Role of Hydrogen-Bonding Interactions in Stabilizing Trigonal Planar Copper (I)"J. Chem. Soc., Dalton Trans.. 4251-4259 (1999)
[文献書誌] K. Saito: "Thermodynamic Metal-Insulator Transition in a Hydroge-Bonded Organic-Inorganic Hybrid Conductor"J. Phys. Chem. Soc. Jpn.. 68. 3592-3599 (1999)
[文献書誌] M. Yamashita: "Electronic Structures of Quasi-One-dimensional Hlogen-Bridged Ni^<III> Complexes"Coord. Chem. Rev.. 190. 309-330 (1999)
[文献書誌] X. Chen: "Temperature Dependence of Raman Scattering in K_3Ba_3C_<60>"J. Phys. Condens. Matter.. 11. 8329-8340 (1999)
[文献書誌] M. Kato: "Luminescence Properties and Crystal Structures of Dicyano (diimine) Platinum (II) Complexes"Inorg. Chem.. 38. 1638-1641 (1999)
[文献書誌] T. Kawamoto: "Raman Investigation of the One-Dimensional Organic Conductor with Half-Filled Band, (TTF-TTP) I_3"68. 3748-3749 (1999)
[文献書誌] M. Munakata: "Silver (I) Complex Assemblies with Non-planar Aromatic Compounds"Inorg. Chem.. 38. 5668-5673 (1999)
[文献書誌] T. Yamamoto: "π-Conjugated Polymers Bearing Electronic and Optical Functionalities"Bull. Chem. Soc. Jpn.. 72. 621-638 (1999)
[文献書誌] T. Yamamoto: "Charge Flucturaiton in MMX Chain Compounds, A_4 [Pt_2 (pop)_4] nH_2O"J. Am. Chem. Soc.. 121. 2321-2322 (1999)
[文献書誌] M. Yamashita: "Tuning of Spin Density Wave Strength of Quasi-One-Dimensional Halogen-Bridges Ni^<III>"Inorg. Chem.. 38. 1894-1899 (1999)
[文献書誌] K. Marumoto: "Induced spin moments in quasi-one-dimensional halogen-bridged mixed-metal complexes of nickel"Phys. Rev. B. 60. 7699-7702 (1999)
[文献書誌] H. Kitagawa: "Charge Ordering with Lattice Distortions in a Conductive MMX-Chain Complex, Pt_2 (dta)_4 I"J. Am. Chem. Soc.. 121. 10068-10080 (1999)
[文献書誌] T. Kawamoto: "Raman and Optical Investigation on Charge Localization in One-dimensional Organic Conductors"Phys. Rev. B. 60. 4635-4645 (1999)

1999 年度 実績報告書

集積型金属錯体の次元構造の合理的制御

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)

研究成果

[文献書誌] N. Hayashida: "Synthesis of Ru- and Os-Complexes of π-Conjuated Oligomers of 2,2'-Bipyridine and 5,5'-Bipyrimidine"Bull. Chem. Soc. Jpn.. 72. 1153-1162 (1999)

[文献書誌] B.-L. Lee: "Synthesis of New Alternating CT-Type Copolymers of Thiophene and Pyrido 3,4-b pyazine Units"Macromolecules. 32. 1375-1382 (1999)

[文献書誌] T. Yamamoto: "Redox Behavior of Poly (diphenylamine-4,4'-diyl) in Acidic Media and Electonic Properties"Jpn. J. Appl. Phys.. 38. L273-L276 (1999)

[文献書誌] Y. Murakami: "Ni-Promoted Syntheses of New 3,3'-Dichloro-5,5'-bipyrzoles and Poly (Bipyraxole-5,5'-diyl)s"Bull. Chem. Soc. Jpn.. 72. 1629-1635 (1999)

[文献書誌] Y. Muramatsu: "Preparation of Main-chain Type Poly (anthraquinone)s Having Alkoxy Groups"Polymer. 40. 6607-6609 (1999)

[文献書誌] M. Yamashita: "Tuning of Charge Density Wave Strengths by Competition between Electron-Correlation of Ni^<III>"Inorg. Chem.. 38. 5124-5130 (1999)

[文献書誌] M. Munakata: "A Novel Double-Starand Helical Motif in a Two-dimensional Polymeric Complex of Silver (I)"Chem. Commun.. 1545-1546 (1999)

[文献書誌] K. Sugimoto: "A Novel Eight-emebered Cu_4I_4 Ring Supported by Sulfur Atoms of an M (mnt)_2 Moiety"Chem. Commun.. 455-456 (1999)

[文献書誌] M. Maekawa: "Syntheses, Crystal Structures and Autoreduction Behavior of Antiferromagnetically Coupled"Inorg. Chim. Acta. 293. 20-29 (1999)

[文献書誌] L.P. Wu: "Silver (I) Tetraiodoethylene Complexes with Twisted Olefin Moiety"Inorg. Chim. Acta. 290. 251-255 (1999)

[文献書誌] M. Maekawa: "Synthesis and Crystal Structure of Tetranuclear Copper (I) and Silver Complexes"Inorg. Chim. Acta. 290. 153-158 (1999)

[文献書誌] T. Yamamoto: "Temperature dependent electrical conductivity of p-doped poly (3,4-ethylenedioxythiophene)"Polym. Bull.. 42. 321-327 (1999)

[文献書誌] T. Shimizu: "Rh-complex promoted synthesis of poly (aryl-acetylene) with pendant TTF units"Inorg. Chim. Acta. 296. 278-280 (1999)

[文献書誌] T. Sakano: "Preparation and characterization of various N-substituted-2-aza-3- ferrocenophanes"Inorg. Chim. Acta. 296. 176-182 (1999)

[文献書誌] T. Morikita: "Preparation of poly (aryleneethynulene) type pi-conjugated polymers constituted of 2-alkylbenzim"Inorg. Chim. Acta. 296. 254-260 (1999)

[文献書誌] Y. Suenanga: "Two-dimnsional Supramolecular Coordination Compounds of Silver (I) with Box Structures"J. Chem. Soc., Dalton Trans.. 2737-2742 (1999)

[文献書誌] G.L. Ning: "Construction of 2-D Multilayer Structures : Silver (I) Complexes with Linear Aromatic Compounds"J. Chem. Soc., Dalton Trans.. 2527-2536 (1999)

[文献書誌] M. Munakata: "Open Dimeric and Closed Polymeric Container Molecules : Calixarene Complexes of Ag (I)"J. Chem. Soc., Dalton Trans.. 373-378 (1999)

[文献書誌] G.L. Ning: "Mobility of Silver (I) Ions Around the Propeller Ligand, Hexaphenylbenezene in Silver (I)"Inorg. Chem.. 38. 5674-5680 (1999)

[文献書誌] T. Yamamoto: "Preparation of π-Conjuated Polymers Composed of hydroquinone, p-Benzoquinone, and p-Diacetoxyphen"Macromolecules. 32. 8886-8896 (1999)

[文献書誌] G.L. Ning: "Cationic Tetrasilver Complex Hexaphenylbenzene"G.L. Ning. 38. 1376-1477 (1999)

[文献書誌] M. Munakata: "Construction of Metal Sandwich System Derived from Assembly of Silver (I) Complexes"J. Am. Chem. Soc.. 121. 4968-4976 (1999)

[文献書誌] M. Maekawa: "Synthesis and Structures of Dinuclear Rhodium (I) Complexes and 1-D Zigzg Chain Rhodium (I)"J. Chem. Soc., Dalton Trans.. 4357-4362 (1999)

[文献書誌] A.S. Batsanov: "The Role of Hydrogen-Bonding Interactions in Stabilizing Trigonal Planar Copper (I)"J. Chem. Soc., Dalton Trans.. 4251-4259 (1999)

[文献書誌] K. Saito: "Thermodynamic Metal-Insulator Transition in a Hydroge-Bonded Organic-Inorganic Hybrid Conductor"J. Phys. Chem. Soc. Jpn.. 68. 3592-3599 (1999)

[文献書誌] M. Yamashita: "Electronic Structures of Quasi-One-dimensional Hlogen-Bridged Ni^<III> Complexes"Coord. Chem. Rev.. 190. 309-330 (1999)

[文献書誌] X. Chen: "Temperature Dependence of Raman Scattering in K_3Ba_3C_<60>"J. Phys. Condens. Matter.. 11. 8329-8340 (1999)

[文献書誌] M. Kato: "Luminescence Properties and Crystal Structures of Dicyano (diimine) Platinum (II) Complexes"Inorg. Chem.. 38. 1638-1641 (1999)

[文献書誌] T. Kawamoto: "Raman Investigation of the One-Dimensional Organic Conductor with Half-Filled Band, (TTF-TTP) I_3"68. 3748-3749 (1999)

[文献書誌] M. Munakata: "Silver (I) Complex Assemblies with Non-planar Aromatic Compounds"Inorg. Chem.. 38. 5668-5673 (1999)

[文献書誌] T. Yamamoto: "π-Conjugated Polymers Bearing Electronic and Optical Functionalities"Bull. Chem. Soc. Jpn.. 72. 621-638 (1999)

[文献書誌] T. Yamamoto: "Charge Flucturaiton in MMX Chain Compounds, A_4 [Pt_2 (pop)_4] nH_2O"J. Am. Chem. Soc.. 121. 2321-2322 (1999)

[文献書誌] M. Yamashita: "Tuning of Spin Density Wave Strength of Quasi-One-Dimensional Halogen-Bridges Ni^<III>"Inorg. Chem.. 38. 1894-1899 (1999)

[文献書誌] K. Marumoto: "Induced spin moments in quasi-one-dimensional halogen-bridged mixed-metal complexes of nickel"Phys. Rev. B. 60. 7699-7702 (1999)

[文献書誌] H. Kitagawa: "Charge Ordering with Lattice Distortions in a Conductive MMX-Chain Complex, Pt_2 (dta)_4 I"J. Am. Chem. Soc.. 121. 10068-10080 (1999)

[文献書誌] T. Kawamoto: "Raman and Optical Investigation on Charge Localization in One-dimensional Organic Conductors"Phys. Rev. B. 60. 4635-4645 (1999)

1999 年度実績報告書

山本隆一東京工業大学, 資源化学研究所, 教授 (10016743)