1999 年度実績報告書

集積型金属錯体の化学的機能

研究課題

研究課題/領域番号	10149102
研究機関	東北大学
研究代表者	伊藤翼東北大学, 大学院・理学研究科, 教授 (90007328)
研究分担者	鈴木正樹金沢大学, 理学部, 教授 (20091390) 芳賀正明中央大学, 理工学部, 教授 (70115723) 佐々木陽一北海道大学, 大学院・理学研究科, 教授 (30004500)
キーワード	酸化還元挙動 / 混合原子価 / 多サイト反応場 / 表面錯体 / プロトン共役電子移動 / 多段階電子移動 / 集積型金属錯体
研究概要	○伊藤は,「Ru三核クラスターユニット間の混合原子価状態」における分子内電子移動速度を赤外吸収線形から決定する手法の開発研究を継続して行った.従来に比べ最も大きなpKa値をもつキヌクリジンを含むピラジン架橋三核ルテニウムクラスター二量体にこの手法を適用した結果,最も大きな速度定数1x10^<12>s^<-1>(-18℃)が得られた. ○佐々木は,プロトン共役電子移動反応を示すオキソ架橋ルテニウムおよび鉄錯体を金電極上に自己集積化することに成功し,水溶液との界面でプロトン共役電子移動反応を実現した.また,八面体型レニウム六核錯体にピリジン型配位子を数および幾何構造を制御して導入し、それらの酸化還元挙動を系統的に調べた他,レニウム六核錯体が発光性であることを初めて見い出し,一連の錯体の光物性を明らかにした. ○「多サイト反応場の構築とその利用」に向け,鈴木は,三脚型四座配位子(Me3-tpa=tris(6-methyl-2-pyridyl-methyl)amine)を含む高原子価ニ核ニッケル(III)オキソ錯体([Ni_2(μ-O_2)_2(Me_3-tpa)_2]^<2+>)の構造と酸素活性化機構を詳細に見当した.その結果,bis(μ-oxo)dinickel(III)錯体のオキソ基は配位子に組み込んだメチル基の水素原子を引き抜き,水酸化あるいはカルボン酸イオンにまで酸化することを見だした.さらにこの水素原子の引き抜きには,オキソ基と水素原子の間の近接効果が重要であることを明らかにした. ○芳賀は,2,6-ビス(オクタデシルベンズイミダゾリル)ビリジン(L18)を有し,かつ配位能をもつ一連のルテニウム錯体[Ru(L18)(L)]^<n+>(L=4,4'-ビピリジンあるいはシアノ基)を新規に合成し,下層液中の金属イオンとの界面での錯形成が起こることを明らかにした.また,ジスルフィド基あるいはホスホン酸基をもつビス(2-ベンズイミダゾリル)ピリジン基を有するルテニウム錯体を合成し,金あるいは酸化物表面への自己集積化を行った.表面でのプロトン共役電子移動が起こることならびに接触角の変化を観測した.

研究成果
(17件)

すべてその他

すべて文献書誌 (17件)

[文献書誌] 伊藤翼: "A Short Platinum to Silver Bond and its Application in the Construction of Extended Structures : Syntheses and Structures of Ag_2[Pt(ox)_2]・2H_2O and [Ag_2(H_2O)]_2[Ag_2CF_2SO_3)_4][Pt(acac)_2]_2"J. Chem. Soc., Dalton Trans.. 273-274 (1999)
[文献書誌] 伊藤翼: "Electron Transfer on the Infrational Time Scale in the Mixed Valence State of 1,4-Pyrazine and 4,4'-Bipyridine Bridged Ruthenium Cluster Complexes"J. Am. Chem. Soc.. 121. 4625-4632 (1999)
[文献書誌] 伊藤翼: "The First Examples of Platinum(II)-Cadmium(II) Bonds : The Role of Strong Field Ligands in Making Dative Pt-M bonds"J. Am. Chem. Soc.. 121. 7405-7406 (1999)
[文献書誌] 伊藤翼: "Syntheses and Properties of a Series of Oxo-Centered Triruthenium Complexes and Their Bridged Dimers with Isocyanide Ligands at Terminal and Bridging Positions"Inorg. Chem.. 38. 4070-4078 (1999)
[文献書誌] 伊藤翼: "Syntheses and Structures of Bridge and Chelate Isomers of Tetraplatinum(II) Cluster Complex with Diethydithiophosphate ion (Et_2dtp) at In-planc Sites. [Pt_4(CH_3COO)_4(Et_2dtp)_4]. And Their Mutual Isomerization via Cluster Core Rotation"J. Am. Chem. Soc.. 121. 10738-10742 (1999)
[文献書誌] 伊藤翼: "Cyanide-Bridged Iron-Copper Molecular Squares with Doublet and Quintet Spin Ground States"Inorg. Chem.. 38. 5686-5689 (1999)
[文献書誌] 芳賀正明: "Highly Ordered LB Films of a Novel Ferric Schiff Base Complex"Mol. Crys. Liq. Crys.. 337. 133-136 (1999)
[文献書誌] 芳賀正明: "Absorption and Emission Behavior of Bis(2,2'-bipyridine)(2-(2-Pyridyl)benzimidazole)Ruthenium(II) Doped to Silica Gel Matrix"J. Mater. Chem.. 9. 3041-3444 (1999)
[文献書誌] 芳賀正明: "Synthesis and Tuning of Chemical Properties of Protonation/Deprotonation of Novel Dinuclear Rutehnium Complexes Containing 2,6,2',6'-tetra(4,5-dimethylbenzimidazol-2-yl)-4,4'-bipyridine"Inorg. Chem. Commun.. 3. 35-38 (1999)
[文献書誌] 鈴木正樹: "Synthesis, Structures, and Properties of Bis(μ-oxo)nickel(III) and Bis(μ-superoxo)nickel(II) Complexes : An Unusual Conversion of a Ni(III)_2(μ-O)_2 Core by H_2O_2 and Oxygenation of Ligand"J. Am. Chem. Soc.. 122. 254-263 (1999)
[文献書誌] 鈴木正樹: "Bimetallic Dioxygen Complexes Derived from End-off Compartmental Ligands"Coord. Chem. Rev.. in press. (1999)
[文献書誌] 佐々木陽一: "Interaction of Some Lewis Acids with the Oxo-bridge of (μ-Oxo)di(-acetato)diruthenium(III, III) Complexes and Their Electrochemical Consequence"Electrochem. 67. 427-430 (1999)
[文献書誌] 佐々木陽一: "Hexarhenium(III) Clusters [Re_6(μ3-S)_8X_6]^2-(X=Cl, Br, I) are Luminescent at Room Temperature"Chem. Lett.. 7. 697-698 (1999)
[文献書誌] 佐々木陽一: "Enhaced Kinetic Lability of Ru(III) Centers in Oxo-Centered Mixed-Metal Ru_2M Trinuclear Complexes(M=Z and Mg)"Inorg. Chem.. 38. 4146-4148 (1999)
[文献書誌] 佐々木陽一: "Synthesis and Electochemical Characterization of Self-Assembled Monolayers of Redox-Active Oxidged Triruthenium(III) Clusters on Au(III)"J. Electroanal. Chem.. 473. 93-98 (1999)
[文献書誌] 佐々木陽一: "Synthesis, tructures and Redox Properties of Octa(μ_3-sulfido)hexarhenium(III) Complexes Having Terminal Pyridine Ligands"Inorg. Chem.. 38. 5557-5564 (1999)
[文献書誌] 芳賀正明: "Electrochemical Properties of Dinuclear Ru Complex Langmuir-Blodgett Films Towards Molecular Electronics"Mol. Crys. Liq. Crys.. 337. 89-92 (1999)

1999 年度 実績報告書

集積型金属錯体の化学的機能

研究代表者

伊藤 翼 東北大学, 大学院・理学研究科, 教授 (90007328)

研究成果

[文献書誌] 伊藤 翼: "A Short Platinum to Silver Bond and its Application in the Construction of Extended Structures : Syntheses and Structures of Ag_2[Pt(ox)_2]・2H_2O and [Ag_2(H_2O)]_2[Ag_2CF_2SO_3)_4][Pt(acac)_2]_2"J. Chem. Soc., Dalton Trans.. 273-274 (1999)

[文献書誌] 伊藤 翼: "Electron Transfer on the Infrational Time Scale in the Mixed Valence State of 1,4-Pyrazine and 4,4'-Bipyridine Bridged Ruthenium Cluster Complexes"J. Am. Chem. Soc.. 121. 4625-4632 (1999)

[文献書誌] 伊藤 翼: "The First Examples of Platinum(II)-Cadmium(II) Bonds : The Role of Strong Field Ligands in Making Dative Pt-M bonds"J. Am. Chem. Soc.. 121. 7405-7406 (1999)

[文献書誌] 伊藤 翼: "Syntheses and Properties of a Series of Oxo-Centered Triruthenium Complexes and Their Bridged Dimers with Isocyanide Ligands at Terminal and Bridging Positions"Inorg. Chem.. 38. 4070-4078 (1999)

[文献書誌] 伊藤 翼: "Cyanide-Bridged Iron-Copper Molecular Squares with Doublet and Quintet Spin Ground States"Inorg. Chem.. 38. 5686-5689 (1999)

[文献書誌] 芳賀 正明: "Highly Ordered LB Films of a Novel Ferric Schiff Base Complex"Mol. Crys. Liq. Crys.. 337. 133-136 (1999)

[文献書誌] 芳賀 正明: "Absorption and Emission Behavior of Bis(2,2'-bipyridine)(2-(2-Pyridyl)benzimidazole)Ruthenium(II) Doped to Silica Gel Matrix"J. Mater. Chem.. 9. 3041-3444 (1999)

[文献書誌] 芳賀 正明: "Synthesis and Tuning of Chemical Properties of Protonation/Deprotonation of Novel Dinuclear Rutehnium Complexes Containing 2,6,2',6'-tetra(4,5-dimethylbenzimidazol-2-yl)-4,4'-bipyridine"Inorg. Chem. Commun.. 3. 35-38 (1999)

[文献書誌] 鈴木 正樹: "Synthesis, Structures, and Properties of Bis(μ-oxo)nickel(III) and Bis(μ-superoxo)nickel(II) Complexes : An Unusual Conversion of a Ni(III)_2(μ-O)_2 Core by H_2O_2 and Oxygenation of Ligand"J. Am. Chem. Soc.. 122. 254-263 (1999)

[文献書誌] 鈴木 正樹: "Bimetallic Dioxygen Complexes Derived from End-off Compartmental Ligands"Coord. Chem. Rev.. in press. (1999)

[文献書誌] 佐々木 陽一: "Interaction of Some Lewis Acids with the Oxo-bridge of (μ-Oxo)di(-acetato)diruthenium(III, III) Complexes and Their Electrochemical Consequence"Electrochem. 67. 427-430 (1999)

[文献書誌] 佐々木 陽一: "Hexarhenium(III) Clusters [Re_6(μ3-S)_8X_6]^2-(X=Cl, Br, I) are Luminescent at Room Temperature"Chem. Lett.. 7. 697-698 (1999)

[文献書誌] 佐々木 陽一: "Enhaced Kinetic Lability of Ru(III) Centers in Oxo-Centered Mixed-Metal Ru_2M Trinuclear Complexes(M=Z and Mg)"Inorg. Chem.. 38. 4146-4148 (1999)

[文献書誌] 佐々木 陽一: "Synthesis and Electochemical Characterization of Self-Assembled Monolayers of Redox-Active Oxidged Triruthenium(III) Clusters on Au(III)"J. Electroanal. Chem.. 473. 93-98 (1999)

[文献書誌] 佐々木 陽一: "Synthesis, tructures and Redox Properties of Octa(μ_3-sulfido)hexarhenium(III) Complexes Having Terminal Pyridine Ligands"Inorg. Chem.. 38. 5557-5564 (1999)

[文献書誌] 芳賀 正明: "Electrochemical Properties of Dinuclear Ru Complex Langmuir-Blodgett Films Towards Molecular Electronics"Mol. Crys. Liq. Crys.. 337. 89-92 (1999)

1999 年度実績報告書

伊藤翼東北大学, 大学院・理学研究科, 教授 (90007328)

[文献書誌] 伊藤翼: "A Short Platinum to Silver Bond and its Application in the Construction of Extended Structures : Syntheses and Structures of Ag_2[Pt(ox)_2]・2H_2O and [Ag_2(H_2O)]_2[Ag_2CF_2SO_3)_4][Pt(acac)_2]_2"J. Chem. Soc., Dalton Trans.. 273-274 (1999)

[文献書誌] 伊藤翼: "Electron Transfer on the Infrational Time Scale in the Mixed Valence State of 1,4-Pyrazine and 4,4'-Bipyridine Bridged Ruthenium Cluster Complexes"J. Am. Chem. Soc.. 121. 4625-4632 (1999)

[文献書誌] 伊藤翼: "The First Examples of Platinum(II)-Cadmium(II) Bonds : The Role of Strong Field Ligands in Making Dative Pt-M bonds"J. Am. Chem. Soc.. 121. 7405-7406 (1999)

[文献書誌] 伊藤翼: "Syntheses and Properties of a Series of Oxo-Centered Triruthenium Complexes and Their Bridged Dimers with Isocyanide Ligands at Terminal and Bridging Positions"Inorg. Chem.. 38. 4070-4078 (1999)

[文献書誌] 伊藤翼: "Cyanide-Bridged Iron-Copper Molecular Squares with Doublet and Quintet Spin Ground States"Inorg. Chem.. 38. 5686-5689 (1999)

[文献書誌] 芳賀正明: "Highly Ordered LB Films of a Novel Ferric Schiff Base Complex"Mol. Crys. Liq. Crys.. 337. 133-136 (1999)

[文献書誌] 芳賀正明: "Absorption and Emission Behavior of Bis(2,2'-bipyridine)(2-(2-Pyridyl)benzimidazole)Ruthenium(II) Doped to Silica Gel Matrix"J. Mater. Chem.. 9. 3041-3444 (1999)

[文献書誌] 芳賀正明: "Synthesis and Tuning of Chemical Properties of Protonation/Deprotonation of Novel Dinuclear Rutehnium Complexes Containing 2,6,2',6'-tetra(4,5-dimethylbenzimidazol-2-yl)-4,4'-bipyridine"Inorg. Chem. Commun.. 3. 35-38 (1999)

[文献書誌] 鈴木正樹: "Synthesis, Structures, and Properties of Bis(μ-oxo)nickel(III) and Bis(μ-superoxo)nickel(II) Complexes : An Unusual Conversion of a Ni(III)_2(μ-O)_2 Core by H_2O_2 and Oxygenation of Ligand"J. Am. Chem. Soc.. 122. 254-263 (1999)

[文献書誌] 鈴木正樹: "Bimetallic Dioxygen Complexes Derived from End-off Compartmental Ligands"Coord. Chem. Rev.. in press. (1999)

[文献書誌] 佐々木陽一: "Interaction of Some Lewis Acids with the Oxo-bridge of (μ-Oxo)di(-acetato)diruthenium(III, III) Complexes and Their Electrochemical Consequence"Electrochem. 67. 427-430 (1999)

[文献書誌] 佐々木陽一: "Hexarhenium(III) Clusters [Re_6(μ3-S)_8X_6]^2-(X=Cl, Br, I) are Luminescent at Room Temperature"Chem. Lett.. 7. 697-698 (1999)

[文献書誌] 佐々木陽一: "Enhaced Kinetic Lability of Ru(III) Centers in Oxo-Centered Mixed-Metal Ru_2M Trinuclear Complexes(M=Z and Mg)"Inorg. Chem.. 38. 4146-4148 (1999)

[文献書誌] 佐々木陽一: "Synthesis and Electochemical Characterization of Self-Assembled Monolayers of Redox-Active Oxidged Triruthenium(III) Clusters on Au(III)"J. Electroanal. Chem.. 473. 93-98 (1999)

[文献書誌] 佐々木陽一: "Synthesis, tructures and Redox Properties of Octa(μ_3-sulfido)hexarhenium(III) Complexes Having Terminal Pyridine Ligands"Inorg. Chem.. 38. 5557-5564 (1999)

[文献書誌] 芳賀正明: "Electrochemical Properties of Dinuclear Ru Complex Langmuir-Blodgett Films Towards Molecular Electronics"Mol. Crys. Liq. Crys.. 337. 89-92 (1999)