1998 Fiscal Year Annual Research Report

集積型金属錯体の次元構造の合理的制御

Research Project

Project/Area Number	10149104
Research Institution	Tokyo Institute of Technology
Principal Investigator	山本隆一東京工業大学, 資源化学研究所, 教授 (10016743)
Co-Investigator(Kenkyū-buntansha)	北川宏北陸先端科学技術大学院大学, 材料科学研究科, 助手 (90234244) 山下正廣名古屋大学, 大学院・人間情報学研究科, 教授 (60167707) 宗像恵近畿大学, 理工学部, 教授 (80090942)
Keywords	集積型金属錯体 / 次元構造 / ニッケル錯体 / パラジウム錯体 / 白金錯体 / 導電性 / 光機能 / 触媒作用
Research Abstract	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、パラジウム及び銀の金属錯体について、1,2,4,5-テトラシアノベンゼン、テトラチアフルバレン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、π-πの相互作用を評価し、ESR特性、導電性を明らかにした。さらに、ニッケル、パラジウム、白金の10族遷移金属のハロゲン架橋錯体を中心とす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-電荷-格子系の相互作用の大きさによる、電荷分離、電荷秩序、新電子相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Cl,Br,Iのハロゲン配位子の他に、CH_3S_2^-やジアミン配位子を用いた。たとえば、CH_3CS_2^-を配位子とする白金ヨウ素錯体については10-30cm^<-1>と室温で高い導電性を示し、また、ジアミンを配位子とするニッケル-パラジウムの混合金属臭素錯体については、ニッケルとパラジウムの元素組成比を変化させることにより、スピン密度波の状態が変化し、赤外吸収スペクトル及びラマンスペクトルが大きく変化することが分かった。また、本研究においては、ポリ(2,2'-ピリミジン-5,5'-ジイル)のようなπ共役高分子配位子を合成し、この高分子配位子についてルテニウム錯体等を合成し、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。すなわち、ポリ(2,2'-ピリミジン-5,5'-ジイル)を合成することができた。そして、この高分子配位子は繰り返し単位当り約1個のルテニウム、オスミウムを取り込み、主鎖π共役方向に沿った次元性に基づく電子の交換を行なっている系であることが、サイクリックボルタンメトリー及び紫外可視分光法により分かった。また、これらの金属錯体は水の光分解に対して活性を有することが分かった。

Research Products

(42 results)

All Other

All Publications (42 results)

[Publications] S.-B.Kim: "Preparation of Poly(diphenylamine-4,4'-diyl)and Related Random Copolymers by Organometallic Polycondensation.Electrical,Electrochemical,and Optical Properties" Macromolecules. 31. 988-993 (1998)
[Publications] T.Yamamoto.: "Extensive Studies on π-Stacking of Poly(3-alkylthiophene-2,5-diyl)s and Poly(4-alkylthiazole-2,5-diyl)s by Optical Spectroscopy,NMR Analysis,Light Scattering Analysis,and X-ray" J.Am.Chem.Soc.120. 2047-2058 (1998)
[Publications] T.Yamamoto: "Prepartion of π-Conjugated Poly(hydroquinone-2,5-diyl)and Poly(p-benzoquinone-2,5-diyl)and Their Electrochemical Behavior" Macromolecules. 31. 2683-2685 (1998)
[Publications] T.Shimizu: "Preparation of New Tetrathiafulvalene(TTF)Derivatives with Two Functional Groups at Positions,2,6-Diiodo-3,7-diphenyl,2,6-Bis[2-(trimethylsilyl)ethynyl]--3,7-diphenyl-TTF" Synthesis. 259-261 (1998)
[Publications] T.Yamamoto: "Electrically Conducting Properties of π-conjugated Polymers with Nitro Group Polymer" Macromol.Rapid.Commun.19. 263-266 (1998)
[Publications] H.Hayashi: "New π-Conjugated Polymers Derived from Benzimidazole Unit.Preparation,Solvatochromism and Oxidation of Poly(aryleneethynylene)s Comprised of 2-(3,5-Di-t-butyl-4-" Macromolecules. 31. 6063 (1998)
[Publications] T.Yamamoto: "Preparation of a New π-Conjugated Polymer Chelating Ligand,Poly(2,2-bipyridimidine-5,5'-diyl),and Its Metal Complexes"" Chem.Lett.1125-1126 (1998)
[Publications] T.Yamamoto: "Molecular Assembling of π-Conjugated Poly(pyrimido[5,4-d]pyrimidine-2,6-diyl)s Prepared by Organometallic Polycondensation" Chem.Lett.1163-1164 (1998)
[Publications] T.Yamamoto: "Preparation and Properties of π-Conjugated Poly(benzimidazole-4,7-diyl)s" Macromol.Chem.Phys.199. 1807-1813 (1998)
[Publications] T.Yamamoto: "Thermal Si-C Bond Cleavage of LRhH(SiAr_3)(μ-H)(μ-Cl)RhH(SiAr_3)L(Ar=C_6H_5,C_6H_4F-piL=P(i-Pr)_3)to Give RLhH(μ-SiAr_3)(μ-SiAr_2)(μ-Cl)RhHL Containing Symmetrically Bridging" Organometallics. 17. 5721-5727 (1998)
[Publications] M.Yamashita: "Charge Fluctuation in MMX Chain Compounds,R_4[Pt_2(pop)_4I].nH_2O" J.Am.Chem.Soc.(in press). (1999)
[Publications] K.Katsumata: "Field-Induced Long-Range-Ordering in an S=1 Quasi-One-Dimensional Antiferromagnet" J.Mag.Mag.Mat. 177. 626 (1998)
[Publications] M.Yamashita: "Tuning of Spin Density Wave Strengths of Quasi-One-Dimensional Halogen-Bridged Ni^<III> Complexes with Strong Electron-Correlation,Ni^<III>(chxn)_2XIY_2" Inorg.Chem.(in press). (1999)
[Publications] H.Okamoto: "Conversion of Excitons to Spin-Soliton Pairs in Quasi-One-Dimensional Halogen Bridged Metal Complexes" Phys.Rev.Lett.80. 861 (1998)
[Publications] S.Sato: "Nuclear Magnetic Relaxation of Proton in an S=1 Haldane Gap Linear Chain System Ni(C_3H_<14>N_2)_2N_3(ClO_4)" J.Mag.Mag.Mat.177. 689 (1998)
[Publications] S.Onaka: "Construction of a Crystalline Tetramer and Infinite Network through the Dual Use of Au(I)...Au(I)and π-π Interaction" Chem.Lett.525 (1998)
[Publications] S.Onaka: "The Synthesis of [AuCo(CO)_4]_2(μ-dppfe)(dppfe=1,1'-bis(diphenylphosphino)ferroccne)and the P-Au-Co-CO(axial)skeletal pair formation between neighboring molecules in the crystal" J.Org.Met.564. 249 (1998)
[Publications] M.Yamashita: "Pressure Effect on Haldane Gap System" Synth.Met.(in press). (1999)
[Publications] H.Okamoto: "Solitons,Polarons,and Excitons in Quasi-One-Dimensional Halogen-Bridged Mixed-Valence Compounds" Bull.Chem.Soc.Jpn.71. 2023 (1998)
[Publications] K.Marumoto: "Low-temperature ESR properties of halogen-bridged mixed-metal complexes Ni_<1-x>Pd_x(chxn)_2Br_3(x<0.5)" Synth.Met.(in press). (1999)
[Publications] S.Kuroda: "ESR studies of halogen-bridged mixed-metal compounds Ni_<1-x>Pd_x(chxn)_2Br_3" Synth.Met.(in press). (1999)
[Publications] M.Munakata: "Towards the Construction of Functional Solid-State Supramolecular Metal Complexes Containing Copper(I)and Silver(I)." Adv.Inorg.Chem.46. 173-303 (1999)
[Publications] M.Munakata: "Construction of Copper(I)Coordination Polymers of 1,2,4,5-Tetracyanobenzene with Zigzag Sheet and Porous." Inorg.Chem.37. 5651-5656 (1998)
[Publications] L.P.Wu: "S...S Contact-assembled Tetrathiafulvalene Derivatives of Copper and Siver(I)Coordination Polymers and Organic Radical Cation Salt." J.Chem.Soc.,Dalton Trans.3255-3261 (1998)
[Publications] M.Munakata: "Dicopper Complexes Derived from 4-Amino-2,1,3-benzothiadiazole with Versatile Coordination Number and Geometry." J.Chem.Soc.,Dalton Trans.1499-1502 (1998)
[Publications] Y.Suenaga: "Self-assembly of Copper(I)and Silver(I)Complexes with Square Grid and Channel Structures." J.Chem.Soc.,Dalton Trans.1121-1125 (1998)
[Publications] M.Munakata: "Supramolecular Silver(I)Complexes with Highly Strained Polycyclic Aromatic Compounds." J.Am.Chem.Soc.8610-8618 (1998)
[Publications] T.Kuroda-Sowa: "A Novel Two-Dimensional Copper(I) Coordination Polymer with Bridging TTF." Chem.Lett.449-500 (1998)
[Publications] M.Maekawa: "Synthesis and Crystal Structure of Dinuclear Palladium(I)dppm Complex with 4-Mercaptopyridine." Inorg.Chim.Acta. 281. 116-119 (1998)
[Publications] M.Munakata: "Synthesis and Structure of a Novel Bis(μ-η2-thianthrene)disilver(I)bis(perchlorate)." Inorg.Chim.Acta. 271. 145-150 (1998)
[Publications] M.Maekawa: "Synthesis and Crystal Structure of Two Ternary Dicopper(I)Complexes Having the Unsymmetrical Coordination Arrangement Bridged by 1.8-Naphthyridine." Inorg.Chim.Acta. 271. 129-136 (1998)
[Publications] M.Munakata: "Assembly of Mixed-Valence Copper Complex by Multiple Hydrogen Bonds of Tetrahydoxybenzoquinone" Inorg.Chim.Acta. 268. 317-321 (1998)
[Publications] M.Maekawa: "Synthesis and Crystal Structure of Dinuclear and Tetranuclear Palladium dppm Complexes." Polyhedron. 17. 3657-3663 (1998)
[Publications] Y.Suenaga: "Synthesis and Structure of a Two-dimensinal Copper(II)Coordination Polymer with 3,4,9,10-Perylenetera carboxylic Acid and Ethylenediamine." Polyhedron. 17. 2207-2211 (1998)
[Publications] M.Maekawa: "Crystal Structure of Bis(diphenylphosphino)methane Dipalladium(I)Nitrate Complex,[Pd_2(m-dppm)_2(NO_3)_2]." Anal.Sci.14. 447-449 (1998)
[Publications] M.Maekawa: "Crystal Structure of Tetranuclear Palladium(I)Complex Bridged by Bis(diphenylphosphino)methane(bpe),[ Pd_4(μ-dppm)_4(μ-Cl)_2](ClO_4)_2・bpe" Anal.Sci.14. 451-453 (1998)
[Publications] J.Dai: "Synthesis,Structure and Characterization of Trinitratotri(N-Butylcaprolactam)Samarium(III)" Coord.Chem.43. 13-20 (1998)
[Publications] Y.Suenaga: "A Linear-Chain Copper(I)Coordination Polymer with Hexakis(methylthio)benzene." Acta Cryst.C54. 1566-1569 (1998)
[Publications] Hiroshi Kitagawa: "The Charge Ordering with Lattice Distrotions in a Conductive MMX-Chain Complex." Coordination Chemistry Review. (in press). (1999)
[Publications] Hiroshi Kitagawa: "The Valence Transoition in a Conductive MMX-Chain System,Pt_2(dta)_4I." Synthetic Metals. (in press). (1999)
[Publications] Hiroshi Kitagawa: "^<129>I Mossbauer Spcctroscopic Study in a MMX-Chain System,M_2(dta)_4I(M=Ni,Pt,dta=CH_3CS_2)" Synthetic Metals. (in press). (1999)
[Publications] 三谷洋興: "水素結合と電子状態,水素結合における構造物性と機能" 日本結晶学会誌. 40. 83-89 (1998)

1998 Fiscal Year Annual Research Report

集積型金属錯体の次元構造の合理的制御

Principal Investigator

山本 隆一 東京工業大学, 資源化学研究所, 教授 (10016743)

Research Products

[Publications] S.-B.Kim: "Preparation of Poly(diphenylamine-4,4'-diyl)and Related Random Copolymers by Organometallic Polycondensation.Electrical,Electrochemical,and Optical Properties" Macromolecules. 31. 988-993 (1998)

[Publications] T.Yamamoto.: "Extensive Studies on π-Stacking of Poly(3-alkylthiophene-2,5-diyl)s and Poly(4-alkylthiazole-2,5-diyl)s by Optical Spectroscopy,NMR Analysis,Light Scattering Analysis,and X-ray" J.Am.Chem.Soc.120. 2047-2058 (1998)

[Publications] T.Yamamoto: "Prepartion of π-Conjugated Poly(hydroquinone-2,5-diyl)and Poly(p-benzoquinone-2,5-diyl)and Their Electrochemical Behavior" Macromolecules. 31. 2683-2685 (1998)

[Publications] T.Shimizu: "Preparation of New Tetrathiafulvalene(TTF)Derivatives with Two Functional Groups at Positions,2,6-Diiodo-3,7-diphenyl,2,6-Bis[2-(trimethylsilyl)ethynyl]--3,7-diphenyl-TTF" Synthesis. 259-261 (1998)

[Publications] T.Yamamoto: "Electrically Conducting Properties of π-conjugated Polymers with Nitro Group Polymer" Macromol.Rapid.Commun.19. 263-266 (1998)

[Publications] H.Hayashi: "New π-Conjugated Polymers Derived from Benzimidazole Unit.Preparation,Solvatochromism and Oxidation of Poly(aryleneethynylene)s Comprised of 2-(3,5-Di-t-butyl-4-" Macromolecules. 31. 6063 (1998)

[Publications] T.Yamamoto: "Preparation of a New π-Conjugated Polymer Chelating Ligand,Poly(2,2-bipyridimidine-5,5'-diyl),and Its Metal Complexes"" Chem.Lett.1125-1126 (1998)

[Publications] T.Yamamoto: "Molecular Assembling of π-Conjugated Poly(pyrimido[5,4-d]pyrimidine-2,6-diyl)s Prepared by Organometallic Polycondensation" Chem.Lett.1163-1164 (1998)

[Publications] T.Yamamoto: "Preparation and Properties of π-Conjugated Poly(benzimidazole-4,7-diyl)s" Macromol.Chem.Phys.199. 1807-1813 (1998)

[Publications] T.Yamamoto: "Thermal Si-C Bond Cleavage of LRhH(SiAr_3)(μ-H)(μ-Cl)RhH(SiAr_3)L(Ar=C_6H_5,C_6H_4F-piL=P(i-Pr)_3)to Give RLhH(μ-SiAr_3)(μ-SiAr_2)(μ-Cl)RhHL Containing Symmetrically Bridging" Organometallics. 17. 5721-5727 (1998)

[Publications] M.Yamashita: "Charge Fluctuation in MMX Chain Compounds,R_4[Pt_2(pop)_4I].nH_2O" J.Am.Chem.Soc.(in press). (1999)

[Publications] K.Katsumata: "Field-Induced Long-Range-Ordering in an S=1 Quasi-One-Dimensional Antiferromagnet" J.Mag.Mag.Mat. 177. 626 (1998)

[Publications] M.Yamashita: "Tuning of Spin Density Wave Strengths of Quasi-One-Dimensional Halogen-Bridged Ni^<III> Complexes with Strong Electron-Correlation,Ni^<III>(chxn)_2XIY_2" Inorg.Chem.(in press). (1999)

[Publications] H.Okamoto: "Conversion of Excitons to Spin-Soliton Pairs in Quasi-One-Dimensional Halogen Bridged Metal Complexes" Phys.Rev.Lett.80. 861 (1998)

[Publications] S.Sato: "Nuclear Magnetic Relaxation of Proton in an S=1 Haldane Gap Linear Chain System Ni(C_3H_<14>N_2)_2N_3(ClO_4)" J.Mag.Mag.Mat.177. 689 (1998)

[Publications] S.Onaka: "Construction of a Crystalline Tetramer and Infinite Network through the Dual Use of Au(I)...Au(I)and π-π Interaction" Chem.Lett.525 (1998)

[Publications] S.Onaka: "The Synthesis of [AuCo(CO)_4]_2(μ-dppfe)(dppfe=1,1'-bis(diphenylphosphino)ferroccne)and the P-Au-Co-CO(axial)skeletal pair formation between neighboring molecules in the crystal" J.Org.Met.564. 249 (1998)

[Publications] M.Yamashita: "Pressure Effect on Haldane Gap System" Synth.Met.(in press). (1999)

[Publications] H.Okamoto: "Solitons,Polarons,and Excitons in Quasi-One-Dimensional Halogen-Bridged Mixed-Valence Compounds" Bull.Chem.Soc.Jpn.71. 2023 (1998)

[Publications] K.Marumoto: "Low-temperature ESR properties of halogen-bridged mixed-metal complexes Ni_<1-x>Pd_x(chxn)_2Br_3(x<0.5)" Synth.Met.(in press). (1999)

[Publications] S.Kuroda: "ESR studies of halogen-bridged mixed-metal compounds Ni_<1-x>Pd_x(chxn)_2Br_3" Synth.Met.(in press). (1999)

[Publications] M.Munakata: "Towards the Construction of Functional Solid-State Supramolecular Metal Complexes Containing Copper(I)and Silver(I)." Adv.Inorg.Chem.46. 173-303 (1999)

[Publications] M.Munakata: "Construction of Copper(I)Coordination Polymers of 1,2,4,5-Tetracyanobenzene with Zigzag Sheet and Porous." Inorg.Chem.37. 5651-5656 (1998)

[Publications] L.P.Wu: "S...S Contact-assembled Tetrathiafulvalene Derivatives of Copper and Siver(I)Coordination Polymers and Organic Radical Cation Salt." J.Chem.Soc.,Dalton Trans.3255-3261 (1998)

[Publications] M.Munakata: "Dicopper Complexes Derived from 4-Amino-2,1,3-benzothiadiazole with Versatile Coordination Number and Geometry." J.Chem.Soc.,Dalton Trans.1499-1502 (1998)

[Publications] Y.Suenaga: "Self-assembly of Copper(I)and Silver(I)Complexes with Square Grid and Channel Structures." J.Chem.Soc.,Dalton Trans.1121-1125 (1998)

[Publications] M.Munakata: "Supramolecular Silver(I)Complexes with Highly Strained Polycyclic Aromatic Compounds." J.Am.Chem.Soc.8610-8618 (1998)

[Publications] T.Kuroda-Sowa: "A Novel Two-Dimensional Copper(I) Coordination Polymer with Bridging TTF." Chem.Lett.449-500 (1998)

[Publications] M.Maekawa: "Synthesis and Crystal Structure of Dinuclear Palladium(I)dppm Complex with 4-Mercaptopyridine." Inorg.Chim.Acta. 281. 116-119 (1998)

[Publications] M.Munakata: "Synthesis and Structure of a Novel Bis(μ-η2-thianthrene)disilver(I)bis(perchlorate)." Inorg.Chim.Acta. 271. 145-150 (1998)

[Publications] M.Maekawa: "Synthesis and Crystal Structure of Two Ternary Dicopper(I)Complexes Having the Unsymmetrical Coordination Arrangement Bridged by 1.8-Naphthyridine." Inorg.Chim.Acta. 271. 129-136 (1998)

[Publications] M.Munakata: "Assembly of Mixed-Valence Copper Complex by Multiple Hydrogen Bonds of Tetrahydoxybenzoquinone" Inorg.Chim.Acta. 268. 317-321 (1998)

[Publications] M.Maekawa: "Synthesis and Crystal Structure of Dinuclear and Tetranuclear Palladium dppm Complexes." Polyhedron. 17. 3657-3663 (1998)

[Publications] Y.Suenaga: "Synthesis and Structure of a Two-dimensinal Copper(II)Coordination Polymer with 3,4,9,10-Perylenetera carboxylic Acid and Ethylenediamine." Polyhedron. 17. 2207-2211 (1998)

[Publications] M.Maekawa: "Crystal Structure of Bis(diphenylphosphino)methane Dipalladium(I)Nitrate Complex,[Pd_2(m-dppm)_2(NO_3)_2]." Anal.Sci.14. 447-449 (1998)

[Publications] M.Maekawa: "Crystal Structure of Tetranuclear Palladium(I)Complex Bridged by Bis(diphenylphosphino)methane(bpe),[ Pd_4(μ-dppm)_4(μ-Cl)_2](ClO_4)_2・bpe" Anal.Sci.14. 451-453 (1998)

[Publications] J.Dai: "Synthesis,Structure and Characterization of Trinitratotri(N-Butylcaprolactam)Samarium(III)" Coord.Chem.43. 13-20 (1998)

[Publications] Y.Suenaga: "A Linear-Chain Copper(I)Coordination Polymer with Hexakis(methylthio)benzene." Acta Cryst.C54. 1566-1569 (1998)

[Publications] Hiroshi Kitagawa: "The Charge Ordering with Lattice Distrotions in a Conductive MMX-Chain Complex." Coordination Chemistry Review. (in press). (1999)

[Publications] Hiroshi Kitagawa: "The Valence Transoition in a Conductive MMX-Chain System,Pt_2(dta)_4I." Synthetic Metals. (in press). (1999)

[Publications] Hiroshi Kitagawa: "^<129>I Mossbauer Spcctroscopic Study in a MMX-Chain System,M_2(dta)_4I(M=Ni,Pt,dta=CH_3CS_2)" Synthetic Metals. (in press). (1999)

[Publications] 三谷洋興: "水素結合と電子状態,水素結合における構造物性と機能" 日本結晶学会誌. 40. 83-89 (1998)

山本隆一東京工業大学, 資源化学研究所, 教授 (10016743)