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Synthesis and Molecular-assembling of Metal Polynuclear Complexes as a Switching Molecular Devices by Proton Transfer

Research Project

Project/Area Number 04453045
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionMie University

Principal Investigator

HAGA Masa-aki  Mie University, Fac.of Educ., Dept.of Chem., Professor, 教育学部, 教授 (70115723)

Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥7,900,000 (Direct Cost: ¥7,900,000)
Fiscal Year 1993: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1992: ¥6,100,000 (Direct Cost: ¥6,100,000)
KeywordsProton-transfer / Polynuclear complex / Ru complex / Switching MolecularDevice / Benzimidazole Derivatives / Electron transfer / Molecular Electronic Devices / ルテニウム多核錯体 / 混合原子価錯体
Research Abstract

In the Ru complexes containing the proton dissociable LH, the thermodynamic relations between electron transfer, proton transfer and photoexcitation can be summarized by a three-dimensional cubic scheme(Fig.1). In this scheme, the thermodynamic quantities such as pK_a and redox potential E_<1/2> are correlated each other. This thermodynamic scheme inspires us to design the supramolecular complexes which can possess a proton-induced switching activity. The proton dissociation in Ru complexes leads to the changes of redox potentials and donor poperty of the ligand, which induces the switching of redox and photochemical properties in the complexes. To elucidate this phenomenon, new dinuclear Ru complexes containing proton dissociable benzimidazole derivatives have been prepared. As a bridging ligand, several new ligands were introduced ; i.e., 2,2'-bis(2-benzimidazolyl)-4,4'-bipyridine(bbbpyH_2) and 2,2'-bis(2-pyridyl)-bibenzimidazole(bpbimH_2). A series of mono-, di-, tri-and tetranuclear Ru complexes bridged by these benzimidazole derivatives have been synthezized. Proton transfer in these complexes can functionas an external perturbation for (1) the change of the metal-metal interaction through bnridging ligand ; (2) the change of the localized position for the excited electron ; (3) the change of the pathway for the electron transfer ; (4) the change of the multielectron transfer pocesses ; for example, the change from the two-electron process to two one-electron processes. The complexes exhibit different switching modes on the redox behaviors, emission, or metal-metal interaction.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (33 results)

All Other

All Publications (33 results)

  • [Publications] T.Ohno,K.Nozaki,and: "A Metal-to-Ligand Charge-Transfer Excited States of a Biruthenium(II)Compound Bridged by 2,6-Bis(2-pyridyl)benzodiimidazole" Inorg.Chem. 31. 4256-4261 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Ohno,K.Nozaki,and: "Photoexcited States of Bi-Ruthenium(II)Compounds Bridged by Bis-2,2'-(2-Pyridyl)-Bibenzimidazole or Bi-(2-Pyridyl-2'-Benzimidazole)ethane" Inorg.Chem. 31. 546-555 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Nozaki,T.Ohno: "Intramolecular Electron Transfer in Photoexcited Ru(II)-Rh(III)Binuclear Compounds" J.Phys.Chem.96. 10880-10888 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Xiao Xiaoming,M.Haga,T.Matsumura-Inoue et al: "Synthesis and Proton Transfer-linked Redox Tuning of Ru(II)Complexes with 2,6-Bis(benzimidazol-2-yl)pyridine Ligands" J.Chem.Soc.Dalton Trans. 2477-2484 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 芳賀正明: "多重モード(電子,光,プロトン)でのスイッチング機能を目指した金属錯体" PETROTECH(ペトロテック). 16巻. 805-811 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Nagashima,H.Yamaguchi,Y.Kato,et: "Facile Cleavage of Carbon-Palladium Bonds in C60Pdn with Phosphines and Phosphites.An Altemative Route to (h2-C60)PdL2 and Discovery of Fluxionarity" Chem.Lett.2153-2156 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Haga,T.Ano,T.: "Synthesis and Proton-coupled Redox Properties of Mononuclear or Asymmetric Dinuclear Complexes of Ruthenium,Rhodium and/or Osmium containing2,2'-Bis(2-pyridyl)-6,6'-Bibenzimidazole" J.Chem.Soc.Dalton Trans.263-272 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Haga,Md.Meser Ali: "Photoexcited states of dinuclear Ru complexes bridged by proton-dissociable benzimidazole derivatives" Coord.Chem.Rev. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] R.Arakawa,T.Matsuo,et al: "Multiply Charged Ions of Ruthenium Tetranuclear Complexes in Electrospray Ionization Mass Spectrometry" Submitted.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] R.Arakawa,T.Matsuo,H.Ito,I.Katakuse,et al: "Observation of Multiply Charged Ions in Electrospray Ionization Mass Spectrometry.Ruthenium(II),Rhodium(III),and Cobalt(III)Complexes" Submitted.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Haga,M.M.Ali,S.Koseki et al.: "Proton-induced Tuning of Electrochemical and Photochemical Properties in Ru Mononuclear and Dinuclear Complexes Containing 2,2'-Bis(benzimidazolyl)-4,4'-hipyridine Synthesis,Molecular Structure,and Excitedstate Properties" To be submitted.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Haga,M.M.Ali,et al.: "Synthesis,Electrochemistry,and Photoexcited-state Properties of Dinuclear Ru Complexes Bridged by 2,2'-Bis(2-pyridyl)-2,2'-thiazolo[5,6-d]-benzothiazole" Submitted.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Ohno, K.Nozaki, and M.Haga: ""A Metal-to-Ligand Charge-Transfer Excited States of a Biruthenium(II) Compound Bridged by 2,6-Bis(2-pyridyl)benzodiimidazole"" Inorg.Chem.31. 4256-4261 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Ohno, K.Nozaki, and M.Haga: ""Photoexcited States of Bi-Ruthenium(II) Compounds Bridged by Bis-2,2'-(2-Pyridyl)-Bibenzimidazole or Bi-(2-Pyridyl-2'-Benzimidazole)ethane"." Inorg.Chem.31. 546-555 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Nozaki, T.Ohno, and M.Haga: ""Intramolecular Electron Transfer in Photoexcited Ru(II)-Rh(III) Binuclear Compounds"" J.Phys.Chem.96. 10880-10888 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Xiao Xiaomig, M.Haga, T.Matsumura-Inoue, Yu Ru, A.W.Addison, K.Kano: "Synthesis and Proton Transfer-linked Redox Tuning of Ruthenium(II) Complexes with 2,6-Bis(benzimidazol-2-yl)pyridine Ligands"." J.Chem.Soc.Dalton Trans.2477-2484 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Masa-aki Haga: ""Metal Complexes Towards Multi-mode Switching Molecular Devices"(In Japanese)" PETROTECH. 16. (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hideo Nagashima, H.Yamaguchi, Y.Kato, Y.Saito, M.Haga, K.Itoh: ""Facile Cleavage of Carbon-Palladium Bonds in C60Pdn with Phosphines and Phosphites. An Alternative Route to (h^2-C60)PdL2 and Discovery of Fluxionarity"." Chem.Lett.2153-2156 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Haga, T.Ano, T.Ishizaki, K.Kano, K.Nozaki, T.Ohno: ""Synthesis and Proton-coupled Redox Properties of Mononuclear or Asymmetric Dinuclear Complexes of Ruthenium, Rhodium and/or Osmium containing 2,2'-Bis(2-pyridyl)-6,6'-Bibenzimidazole"" J.Chem.Soc.Dalton.Trans.263-272 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Haga, Md.Meser Ali, H.Maegawa, K.Nozaki, A.Yoshimura, T.Ohno: ""Photoexcited states of dinuclear Ru Complexes bridged by proton-dissociable benzimidazole derivatives"" Coord.Chem.Rev.(in press). (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] R.Arakawa, T.Matsuo, K.Nozaki, T.Ohno, M.Haga: ""Multiply Charged Ions of Ruthenium Tetranuclear complexes in Electrospray Ionization Mass Spectrometry"" (submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] R.Arakawa, T.Matsuo, H.Ito, I.Katakuse, K.Nozaki, T.Ohno, M.Haga: ""Observation of Multiply Charged Ions in Electrospray Ionization Mass Spectrometry. Ruthenium(II), Rhodium(III) and Cobalt(III) Complexes"." (submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Haga, M.M.Ali, S.Koseki, K.Fujimori, A.Yoshimura, K.Nozaki, T.Ohno, K.Nakajima: ""Proton-induced Tuning of Electrochemical and Photochemical Properties in Ru Mononuclear and Dinuclear Complexes Containing 2,2'-Bis(benzimidazolyl)-4,4'-bipyridine : Synthesis, Molecular Structure, and Excited-state Properties."" (To be submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Haga, M.M.Ali, S.Koseki, A.Yoshimura, K.Nozaki, T.Ohno: ""Synthesis, Electrochemistry, and Photoexcited-state Properties of Dinuclear Ru Complexes Bridged by 2,2'-Bis(2-pyridyl)-2,2'-thiazolo[5,6-d]-benzothiazole"." (to be submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 芳賀正明: "多重モード(電子,光,プロトン)でのスイッチング機能を目指した金属錯体" PETROTECH(ペトロテック). 16巻. 805-811 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Xiao Xiaoming,Masa-aki Haga他: "Synthesis and Proton Transfer-linked Redox Tuning of Ruthenium(II)Complexes with Tridentate 2,6-Bis(benzimidazol-2-yl)pyridine Ligands" J.Chem.Soc.Dalton Trans.2477-2484 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Masa-aki Haga,Tomo-aki Ano他: "Synthesis and Proton-coupled Redox Properties of Mononuclear or Asymmetric Dinuclear Complexes of Ruthenium,Rhodium,and/or Osmium contaiing 2,2'-Bis(2-pyrdyl)(-6,6'-Bibenzimidazole" J.Chem.Soc.Dalton Trans.263-272 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Masa-aki Haga,Md.Meser Ali,Hatsuko Maegawa他: "Photoexcited states of dinuclear Ru complexes bridged by proton-dissociable benzimidazole derivatives" Coord.Chem.Rev. (印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takeshi Ohno: "Photo excited States of Biruthienium(2)Compounds Bridged by 2.2'-Bis(2-pyridyl)bibenzimidazole or1.2-Bis(2-(2-pyridyl)benzimidazclyl)ethane" Inorg.Chem. 31. 548-555 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Takeshi Ohno: "A Metal-to-Ligand Charge Transfer Excited State of a Biruthenium(2)Compound Bridged by 2.6-Bis(2-pyridyl)benzodiimidazole" Inorg.Chem. 31. 4256-4261 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Koichi Nozaki: "Intramolecular Electron Transfer in Photoxcited Ru(2)-Rh(3)Binuclear Compounds" J.Phys.Chem. 96. 10880-10888 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Xiao Xiaoming: "Synthesis and Proton Transfer Linked Redox Tuning of Ruthenium(2)Complexes with Tridentate 2.6-Bis(benzimidazol-2-yl)pyridine" J.Chem.Soc.Dulton Truns. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] K.Nozaki(分担): "Dynamics and Mechanisms of Photoinduced Transfer and Related Phenomena" Elsevier Science Publishers, 11 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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