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Elucidation of Dynamics of Electron Transfer Process in Condensed Phases

Research Project

Project/Area Number 06640654
Research Category

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

Allocation TypeSingle-year Grants
Research Field Physical chemistry
Research InstitutionOsaka University

Principal Investigator

NOZAKI Koichi  Fac.of Sci., Dep.of Chem., Assistant, 理学部, 助手 (20212128)

Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1994: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsELECTRON TRANSFER / RUTHENIUM COMPLEX / PORPHYRIN / CHARGE RECOMBINATION / RHODIUM COMPLEX / ZINC CHLORIN / ENERGY TRANSFER / DISTANCE DEPENDENCE / 電荷分離反応 / 電荷再結合反応 / 距離依存性 / 溶媒依存性 / 内部変換
Research Abstract

To elucidate the effects of both intramolecular nuclear displacement and solvent dynamics on ET rates, intramolecular ET processes have been studied in the following donor-acceptor linked compounds.
(1) The dependencies of distance, solvent, temperature, and energy gap on the photoinduced and back ET rates in M (II) -Rh (III) (M=Ru and Os) dinuclear complexes have been examined. It is concluded that the large nuclear displacement in the rhodium complexes dominantly affected the ET rates.
(2) The high-density laser excitation of a Ru (II) dinuclear complex was used to produce a doubly excited state. A triplet-triplet annihilation between two MLCT states occurred to form a charge-separated state, [Ru (I) -Ru (III)], with 40% in a production yield. The distance dependence of the charge-separation and charge recombination have been examined.
(3) Rapid quenching of an Ru-MLCT excited state in the mixed-valent complexes, Ru (II) -M (III) (M=Ru and Os), was observed. The resulting product was the mixed-valence isomer state, Ru (III) -Os (II), which underwent back ET process to reproduce the ground state. Energy gap and temperature dependence of these ET rates have been studied.
(4) On the excitation of MMCT bands in mixed-valent complexes, Ru (II) -M (III) (M=Ru and Os), with a near-IR laser pulse, a back ET process from an optically generated mixed-valence isomer state was observed. However, the low quantum yield (-0.2) of the isomer state suggests that most of Franck-Condon states decayd to the ground state before they relaxd.
(5) The charge-separation and charge-recombination rates in Zinc chlorin-porphrin dyads have been measured in a variety of solvent. The variation of the charge-recombination rates with solvent was well understood in terms of current nonadiabatic ET theory. The intramolecular reorganization energy was estimated 0.175eV and the electronic interaction energy was 14meV.

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] Akio Yoshimura: "Temperature-Dependent Rates of Electron Transfers and Intersystem Crossing on the Laser Excitation of Ligand-Bridged Ru(II) and Co(III) compounds." J. Phys. Chem.100. 1630-1637 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Atsuhiro Osuka: "Intramolecular charge recombination in Carotemoid-porphyrin-pyromellitimide triads" Chem. Phys. Lett.238. 37-41 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichi Nozaki: "Reversible intramolecular electron transfer between Ru(II) complexes in the charge-transfer excited states" Supramolecular Photochemistry. 1(in press). (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akio Yoshimura: "Dependency of Phosphorescence Energy Transfer Rate on Distance between a Cationic Donor and a Cationic acceptor and on Temperature." (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichi Nozaki: "Solvent dependence of charge-sepa ration and darge-recombination in Zinc-porphyrin-porphyrin dyads." (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichi Nozaki: "Rh(III)(2,2′-bibyridine)_2(N-methyl-2-(2-pyridyl)benzimidazole)" (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akio Yoshimura, Koichi Nozaki, Noriaki Ikeda, and Takeshi Ohno: "Temperature Dependent Rates of Electron Transfers and Intersystem Crossing on the Laser-excitation of Ligand-bridged Ru (II) and Co (III) Compounds" J.Phys.Chem.100 (5). 1630-1637 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Atsuhiro Osuka, Hiroko Yamada, Satoshi Shinoda, Koichi Nozaki, and Takeshi Ohno: "Intramolecular charge recombination in carotenoid-porphyrin-pyromellitimide traids." Chem.Phys.Lett.238. 37-41 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichi Nozaki, Noriaki Ikeda, and Takeshi Ohno: "Reversible intramolecular electron transfer between Ru (II) complexes in the charge-transfer excited states." Supramolecular Photo-chemistry (New Joural of Chamistry). (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akio Yoshimura, Koichi Nozaki, Noriaki Ikeda, and Takeshi Ohno: "Dependency of Phosphorescence Energy Transfer Rate on Distance between a Cationic Donor and a Cationic Acceptor and on Temperature." (submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichi Nozaki, Takeshi Ohno, Shinji Marumo, and Atsuhiro Osuka.: "Solvent dependence of charge-separation and charge-recombination in Zinc-porphyrin-porphyrin dyads." (submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichi Nozaki, Takeshi Ohno: "Excited state relaxation in Rh (III) (2,2'-bibyridine)_2 (N-methyl-2- (2-pyridyl) benzimidazole)." (submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akio Yoshimura: "Temperature-Dependent Rates of Electron Tvansters and Intersystem Crossing on the Laser Excitation of Ligand-Bridged Ru (II) and Co (II) Compouads" J.Phys.Chem.100. 1630-1637 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Atsuhiro Osuka: "Intramolecular charge recombination in Carotenoid-porphyrin-pyromellitimide triads" Chem.Physics Lett.238. 37-41 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Koichi Nozaki: "Reversible intramolecular electron transter between Ru (II) complexes in the charge-tramster exited states" Supramolecular Photochemistry. 1(印刷中). (1997)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akio Yoshimura et al.: "Dependence of Metal-to-Ligand CT Excitation Energy Transter on Donor-Acceptor Distamce and on Tempera ture(77-300K)" J.Phys.Chem.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Atsahiro Osuka et al.: "In tramolecular Charge Recombination in Carotexoid-Porphyrin-Pyromellitide Triads" Chem.Phys.Lett.(印刷中).

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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