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1999 Fiscal Year Final Research Report Summary

Dynamics of Electron Transfer and Energy Transfer by New Chiral Photosensitizers

Research Project

Project/Area Number 09044096
Research Category

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

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionKumamoto University

Principal Investigator

SAKAKI Shigeyoshi  Fac. of Eng., Kumamoto University, Professor, 工学部, 教授 (20094013)

Co-Investigator(Kenkyū-buntansha) MUSASHI Yasuo  Data Processing Center, Kumamoto University, Assistant Professor, 総合情報処理センター, 講師 (10271131)
HAMADA Taisuke  Fac. of Eng., Kumamoto University, Associate Professor, 工学部, 助手 (10253717)
SUGIMOTO Manabu  Graduate School of Science and Technology, Kumamoto University, Associate Professor, 大学院・自然科学研究科, 講師 (80284735)
Project Period (FY) 1997 – 1999
KeywordsChiral ruthenium (II) bipyridine complex / Chiral Copper (I) complex / Pulse radiolysis / Laser Flash Photolysis / Photoasymmetric reduction / Photoasymmetric synthesis / Molecular / Mechanics Study / Marcus theory
Research Abstract

(1)Chiral photosensitizers, Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 (menbpy=4,4'-bis(1R,2S,5R)-(-)menthoxycarbonyl}-2,2'-bipyridine), Δ-[Ru(phenebpy)ィイD23ィエD2]ィイD12+ィエD1 (phenebpy=4,4'-bis(1-phenethylaminocarbonyl)-2,2'-bipyridine), [Cu(tmdcbpy)(PRィイD23ィエD2)ィイD22ィエD2]ィイD12+ィエD1(tmdcbpy=4,4'-6,6'-tetramethyl-5,5'-bis(S)-(-)-1-phenylcarbamoyl-2,2'-bipyridine) were newly synthesized here. (2) Pulse radiolysis of Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 in ethanol yields one-electron reduced species in which ruthenium(I) is not involved but anion radical of menbpy ligand is involved. Reduction of [Co(acac)ィイD23ィエD2] by this Δ-[Ru(menbpy)ィイD23ィエD2]ィイD1+ィエD1 occurs stereoselectively with selectivity of 2.7. (3) [Cu(tmdcbpy)(PPhィイD23ィエD2)]ィイD1+ィエD1 perfomrs stereoselective photoreduction of [Co(edta)]ィイD1-ィエD1 with significantly large enantiomer excess (60% at 10% conversion), under near-UV light irradiation, while [Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 cannot perform stereoselective photoreduction of [Co(edta)] … More ィイD1-ィエD1. (4) Photoreductions of cationic methylviologen and anionic 4,4'-bis(3-carboxyethyl)-1,1'-bipyridinium (dcbpy) by [Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 were investigated with laser flash photolysis. The reaction rate significantly depend on the electrostatic interaction; both photoinduced electron transfer from ィイD1*ィエD1[Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 to MVィイD12+ィエD1 and the reverse electron transfer from MVィイD1+ィエD1 to [Ru(bpy)ィイD23ィエD2]ィイD13+ィエD1 occur more slowly than those of dcbpy. (5) Analysis based on Marcus theory showed that the electronic coupling term HィイD2rpィエD2 significantly depends on the electrostatic interaction, suggesting that the electrostatic interaction is important to the stereoselectivity in electron transfer reaction. (5) Photoderacemization of [Co(acac)ィイD23ィエD2] was carried out with Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 in acetonitrile-water under visible light irradiation. Quenching reactions and model reaction indicate that this reaction takes place through the oxidative quenching of Δ-ィイD1*ィエD1[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 by[Co(acac)ィイD23ィエD2]. (6) Electron transfer reaction was investigated with molecular mechanics, which shows that [Co(acac)ィイD23ィエD2] approaches [Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 along the CィイD23vィエD2 axis. Less

  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] S. Sakaki, H. Ishikura, K. Kuraki, T. Satoh, T. Arai, H. Hamada: "Synthesis of a new chiral Copper(I) complex and its application to Stereoselective Photoreduction of [Co(edta)]^-(H_4edt=ethylenedinitrilotetraacetic acid)"J. Chem. Soc., Dalton Trans.. 1815-1820 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y. Musashi and S. Sakaki: "Insertion of Crbon dioxide into a Rhodiun(III)-Hbond: A theoretical study"J. Chem. Soc., Dalton Trans.. 577-583 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S. Sakaki, R. Horita, K. Kuraki, and T. Hamada: "Photoasymmetric Synthesis of [Co(edta)]^- from Co(II) Salt and L_4edta (L=H^+ or Na^+), Using a Chiral Cu(I) Complex"Chemistry Letters. 827-828 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hamada, M. Tsukamoto, H. Ohtsuka, and S.Sakai: "Charge Effects in Photoinduecd Electron-transfer Reactions between [Ru(bpy)_3]^<2+> and Viologen Derivatives"Bull. Chem. Soc. Jpn.. 2281-2291 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Sakanoue, M. Motoda, M. Sugimoto, and S. Sakaki: "A Molecular Orbital Study on the Hole Transport Property of Organic Amine Compounds"J. Phys. Chem. A. 5551-5556 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. hamada, B. S. Brunschwig, K. Eifuku, E. fujita, M. Korner, S. Sakaki, R. Eldik, and J. Wishart: "Enantiselectivities in Electron-Transfer and Excited State Quenching Reactions of a Chiral Ruthenium Complex possessing a Helical Structure"J. Phys. Chem. A.. 5645-5654 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S. Sakaki: The Transition State.

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S. Sakaki: The Basic Organometallic Chemistry (in Japanese).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shigeyoshi Sakaki, Hiroyuki Ishikura, Koichi Kuraki, Takasi Satoh, Toru Arai, and Taisuke. Hamada: "Synthesis of a new chiral Copper(I) complex and its application to Stereoselective Photoreduction of [Co(edta)]ィイD1-ィエD1(HィイD24ィエD2edt=ethylenedinitrilotetraacetic acid)"J. Chem. Soc., Dalton Trans.. No.3. 1815-1820 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yasuo Musashi and Shigeyoshi Sakaki: "Insertion of Carbon dioxide into a Rhodium(III)-H Bond: A theoretical study"J. Chem. Soc., Dalton Trans.. No.2. 577-583 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shigeyoshi Sakaki, Rikihisa Horita, Koichi Kuraki, and Taisuke Hamada: "Photoasymmetric Synthesis of [Co(edta)] ィイD1-ィエD1from Co(II) Salt and LィイD24ィエD2edta (L=HィイD1+ィエD1 or NaィイD1+ィエD1), Using a Chiral Cu(I) Complex"Chemistry Letters. No.8. 827-828 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Taisuke Hamada, Masaya Tsukamoto, Hiroshi Ohtsuka, and Shigeyoshi Sakaki: "Charge Effects in Photoinduced Electron-transfer Reactions between [Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 and viologen Derivatives"Bull., Chem. Soc. Jpn.. 71, No.10. 2281-2291 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kei Sakanoue, Midori Motoda, Manabu Sugimoto, and Shigeyoshi Sakaki: "A Molecular Orbital Study on the Hole Transport Property of Organic Amine Compounds"J. Phys. Chem. A. 103, No.28. 5551-5556 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Taisuke Hamada, B. S. Brunschwig, Kenji Eifuku, Etsuko Fujita, Manuela Korner, Shigeyoshi Sakaki, R. Eldik, and James Wishart: "Enantioselectivities in Electron-Transfer and Excited State Quenching Reactions of a Chiral Ruthenium Complex possessing a Helical Structure"J. Phys. Chem. A. 103, No.29. 5645-5654 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shigeyoshi Sakaki: ""The Transition State", (Ed. By Takayuki Fueno)"Kodansha, Gordon and Breach Science Publishers. 328 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shigeyoshi Sakaki: ""The Basic Organometallic Chemistry (in Japanese)", (Ed. By Akira Nakamura)"Asakura. 197 (1999)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2001-10-23  

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