集積型金属錯体の化学的機能

2000 Fiscal Year Annual Research Report

• Project/Area Number: 10149102
• Research Institution: Tohoku University
• Principal Investigator: 伊藤 翼 東北大学, 大学院・理学研究科, 教授 (90007328)
• Co-Investigator(Kenkyū-buntansha): 芳賀 正明 中央大学, 理工学部, 教授 (70115723) ; 西原 寛 東京大学, 大学院・理学系研究科, 教授 (70156090) ; 佐々木 陽一 北海道大学, 大学院・理学研究科, 教授 (30004500)
• Keywords: 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

Research Abstract

○ 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.本年度は"非対称なポテンシャル面をもつ系"にこの手法を適用した.^<13>COや^<13>C^<18>Oを含む試料を用いることにより,平衡状態で存在する二つの混合原子価化学種それぞれにおける分子内電子移動速度定数の決定に成功した.また,供与型Pt-Ag結合生成を利用し,…Pt-Ag-Pt-Ag…型の一次元らせん構造の構築に成功した.
○ 佐々木は,次の系の酸化還元特性を研究した:一連のオキソ架橋クラスター系のクラスターユニットを介した配位子間相互作用,Ru三核錯体を金電極上へ3段階まで段階的に集積化した系,ジフォスフィンやポルフィリン配位子を含むレニウム6核錯体.更に,ルテニウムポルフィリンニ量体の混合原子価状態が特異な振電作用に基づく赤外スペクトルを与えることを初めて見い出した.
○ 西原は,光応答性アゾ共役遷移金属錯体の研究において,光定常状態におけるtrans体:cis体比がCo(II)とCo(III)で異なることを利用し酸化状態スイッチングと組み合わせて単一紫外光のみでのtrans-cis双方向の異性化を実現させた.またアゾフェロセン系において,MLCTバンドの可視光励起による,また,レドックスのみによるtrans-cis異性化の発現を見いだした.
○ 芳賀は,表面錯体集積体の構築を目指しジスルファイド基あるいはホスホン酸基を有するビス(ベンズイミダゾリル)ピリジン誘導体をもつルテニウム・オスミウム錯体を合成した.これらの錯体が金や酸化物の固体基板上に選択的吸着することを明らかにした.また,分子レベルでの整流素子の構築を目指し表面に自己組織化されたルテニウム/オスミウム二核錯体を合成し,溶液のpHにより電位勾配の逆転が起こる系を見いだした.

Research Products

• [Publications] 伊藤翼: "Unusual Redox State Dependent Fermi Resonances in the Infrared Spectra of Trinuclear Ruthenium Clusters with Isocyanide Ligands"Inorg.Chem.. 39. 2696-2698 (2000)
• [Publications] 伊藤翼: "A Strongly Coupled Mixed Valence State between Ru_3 Clusters. Intramolecular Electron Transfer on the Infrared Vibrational Time Scale in a Pyrazine (pz) Bridged dimer of Triruthenium Clusters, [{Ru_3 (μ-O)(μ-CH_3CO_2)_6(CO)(abco)}_2(μ-pz)](abco=l-azabicyclo[2,2,2]octane"Bull.Chem.Soc.Jpn.. 73. 1205-1212 (2000)
• [Publications] 伊藤翼: "A Graphite-Like Complex with Large Cavities Constructed with the Complex Ligand [Ni^<II>(bpca)_2]"Angew.Chem.Int.Ed.. 39. 3130-3132 (2000)
• [Publications] 伊藤翼: "A Novel Polymeric Ag^I Complex Consisting of Two Three-dimensional Networks Which are Enantiomeric and Interpenetrating"Chem.Commun.. 1953-1954 (2000)
• [Publications] 伊藤翼: "Mixed-Valent Heptairon Complex with a Ground-State Spin of S=12/2 Constructed from a Triiron Cluster Ligand"Angew.Chem.Int.Ed.. 39. 230-233 (2000)
• [Publications] 伊藤翼: "Superparamagnetic Behavior in an Alkoxo-Bridged Iron (II) Cube"J.Am.Chem.Soc.. 122. 12602-12603 (2000)
• [Publications] 伊藤翼: "Rational Construction of Chiral Octanuclear Metallacycles Consisting of Octahedral Co^<III>, Square-Planar Pd^<II>, and Linear Au^I or Ag^I Ions"Angew.Chem.Int.Ed.. 39. 4098-40101 (2000)
• [Publications] 伊藤翼: "A Helical Metal-Metal Bonded Chain via the Pt→Ag Dative Bond"J.Am.Chem.Soc.. 123. 743 (2001)
• [Publications] 佐々木陽一: "Reversibility in the Formation of Molybdenum Porphyrin Dioxygen Complexes"Bull.Chem.Soc.Jpn.. 73. 383-390 (2000)
• [Publications] 佐々木陽一: "Emission and Metal- and Ligand-Centered Redox Characteristics of the Hexarhenium (III) Clusters trans- and cis-[Re_6(μ_3-S)_8Cl_4(L)_2]_2^-, Where L is Pyridine Derivatives or Pyrazine"Inorg.Chem.. 38. 1765-1772 (2000)
• [Publications] 佐々木陽一: "Characterization of Novel Redox-Active Triruthenium (III) Complexes with a Disulfide-alkyl Ligand. Anion-Dependent Redox Behaviour of Monolayer Assemblies on Gold"J.Chem.Soc., Dalton Trans.. 2693-2701 (2000)
• [Publications] 佐々木陽一: "Steric Effects of Porphyrin Rings on Dioxygenation : Synthesis and Kinetic Studies of Molybdenum Porphyrin Dioxygen Complexes with Naphthyl Groups"Inorg.React.Mech.. 2. 85-91 (2000)
• [Publications] 佐々木陽一: "Luminescent Langmuir-Blodgett Films of Platinum (II) Complex [Pt(L18)Cl](PF_6)(L18=2,6-Bis (1-octadecylbenzimidazol-2-yl) pyridine)"Inorg.Chem.. 39. 4022-4028 (2000)
• [Publications] 佐々木陽一: "Coupling of Ground-State Molecular Vibrations to Low-Energy Electronic Transition of Ruthenium (III, II) Porphyrin Dimers"J.Am.Chem.Soc.. 122. 9032-9033 (2000)
• [Publications] 佐々木陽一: "Synthesis, Structure, and Properties of Sulfido-Bridged Dinuclear Tungsten (V) Complex of Dithilene, (Pr4N)_2[WV2(μ-S)_2{S_2C_2(CO_2Et)_2}_4]"J.Organomet.Chem.. 611. 370-375 (2000)
• [Publications] 佐々木陽一: "Chelate Formation around the Hexarhenium Cluster Center by a Diphosphane Ligand, Ph_2P(CH_2)_6PPh_2"Angew.Chem.Int.Ed.. 40. 239-242 (2001)
• [Publications] 西原寛: "Synthesis and Physical Properties of a π-Conjugated Ruthenium (II) Dinuclear Complex Involving an Azobenzene-Bridged Bis (terpyridine) Ligand"Mol.Cryst.Liq.Cryst.. 343. 193-198 (2000)
• [Publications] 西原寛: "Novel Photoisomerzation Behavior of Rh Binuclear Complexes Involving an Azobenzene-bridged Bis (terpyridine) Ligand-Strong Effects of Counterion and Solvent and the Induction of Redox Potential Shift"Inorg.Chem.. 39. 3438-3439 (2000)
• [Publications] 西原寛: "Novel Photo-isomerization of Azoferrocene with a Low-energy MLCT Band and Significant Change of the Redox Behavior between the Cis and Trans Isomers"J.Am.Chem.Soc.. 122. 12373-12374 (2000)
• [Publications] 西原寛: "Novel Protonation-Induced Structural Conversion of an Ethynylene-bridged Ferrocene-Anthraquinone Complex"Chem.Lett.. 1328-1329 (2000)
• [Publications] 西原寛: "Electron Transfer of Conjugated Polymeric Ferrocenes"Macromol.Symp.. 156. 21-27 (2000)
• [Publications] 西原寛: "Synthesis of a Vinylene-Bridged Ferrocene-Hydroquinone Complex and Its Unusual Structural Change Originated by Proton-Coupled Electron Transfer"Inorg.Chem.. 40. 4-5 (2001)
• [Publications] 西原寛: "Redox and Optical Properties of Conjugated Ferrocene Oligomers"Bull.Chem.Soc.Jpn.. (in press).
• [Publications] 西原寛: "Synthesis and Redox Properties of a π-Conjugated Cyclobutadienecobalt Polymer Containing Ferrocenyl Groups"J.Inorg.Organomet.Polym.. (in press).
• [Publications] 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 (2000)
• [Publications] 芳賀正明: "A Novel Rutnenium Surfactant : Electronic Spectra, ZINDO analysis and Langmuir-Blodgett Studies of Trans-dichloro (6,6'-bis (N-dodecylbenzimidazol-2-yl)-2,2'-bipyridine) ruthenium (II)"J.Chem.Soc.Dalton Trans.. 2357 (2000)
• [Publications] 芳賀正明: "Self-Organization of Au Nanoparticles Protected by 2,6-Bis (1'-(8-thiooctyl)-benzimidazol-2-yl) pyridine"J.Am.Chem.Soc.. 122. 4237 (2000)
• [Publications] 芳賀正明: "Chemical Transformation of Amphiphilic Ru Complexes Containing 2,6-Pyridinedicarboxylate at the Air-water Interface"Mol.Cryst.Lig.Cryst.. 342. 225 (2000)
• [Publications] 芳賀正明: "Synthesis and Proton-Coupled Electron Transfer Reaction of Self-Assembled Monolayers of Ruthenium (II) Complex Containing Tridentate 2,6-Bis (benzimidazol-2-yl)-pyridine on Gold Surface : Comparison of Acid/Base Chemistry With Bulk Solution"Inorg.Chem.. 39. 4566-4573 (2000)
• [Publications] 芳賀正明: "Luminescent Langmuir-Blodgett Films of Platinum (II) Complex,[Pt(L18)Cl](PF_6)(L18=2,6-Bis (1-octadecylbenzimidazol-2-yl) pyridine)"Inorg.Chem.. 39. 4022-4028 (2000)
• [Publications] 芳賀正明: "Matrix-assisted Laser Desorption/Ionization Time-of-flight Mass Spectrometry of Self-assembled Monolayers of Ruthenium Complexes on Glod"Rapid Commun.Mass Spectrom.. 14. 1301 (2000)
• [Publications] 芳賀正明: "Prospects and Problems of Single Molecule Infromation Devices"Jpn.J.Appl.Phys.. 39. 3835 (2000)