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Photo-induced Electron-relay Reaction Utilizing Electrostatic Field of Polymers

Research Project

Project/Area Number 63470072
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionNagoya University

Principal Investigator

SAWAKI Yasuhiko  Nagoya University, Dept. of Appl. Chem., Professor, 工学部, 教授 (30023120)

Co-Investigator(Kenkyū-buntansha) TAKAGI Katsuhiko  Nagoya University, Dept. of Appl. Chem., Assoc. Professor, 工学部, 助教授 (60023264)
Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥5,100,000 (Direct Cost: ¥5,100,000)
Fiscal Year 1989: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1988: ¥4,400,000 (Direct Cost: ¥4,400,000)
KeywordsElectron-relay / Photochemistry / Cis-trans isomerization / Stylbazole radical / スチルバゾ-ルラジカル / 光増感電子リレー / 高分子電解質のクラスター形成 / 吸着分子の光化学反応 / 光二量化反応
Research Abstract

Molecular aggregates are formed between polystyrenesulfonate anions (PSS^-) and stilbazolium cations (Stz^+) by means of their electrostatic interactions. A co-adsorbed sensitizer, Ru(bpy)_3^<2+> 2+ transfers, on irradiation, its electron into stilbazolium cation resulting in the formation of stylbazole radical. An efficient electron relay takes place among the olefin aggregates, and highly efficient cis to trans isomerization of the olefins occurs, quantum yields being as high as 100. Firstly, we could show that the thousands of Stz^+ ions bound to PSS^- are divided into small aggregates of micelle-like clusters and that their aggregation numbers are constant in the range of 80-90, irrespective of the degree of polymerization of PSS^-. The electron-relay chain isomerization proceeds within one micellar cluster. Secondly, we could succeed in detecting directly stylbazole radical, as an unstable transient intermediate in the cis-trans isomerization. Photolysis of a mixture of p-dicyanobenzene (DCB) and naphthalene in the presence of stilbazolium cation yielded a transient species, (^<lambda>max 420 nm) at the expense of anion radical of DCB (^<lambda>max 340 nm). The transient spectrum is that of stylbazole radical, and decays satisfying a second-order kinetics. The decay rate constant has been found to be heavily increased by the addition of polystyrenesulfonate anions, which implies that an electron is rapidly relayed among the adsorbed stilbazolium ion aggregates.

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] K.Takagi,H.Fukaya and Y.Sawaki: "Does a Stilbazolium Cation Adsorbing Poly(styrenesulfonate)Anion Form Micelle-like Clusters?" Journal of American Chemical Society. 110. 7469-7473 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Takagi,N.Miyake,E.Nakamura,Y.Sawaki,N.Koga: "ZuTPPS-Sensitized Photodibromination of 2,3-Dibromo-3-phenyl-propionic Acids.Electron Transfer Initiated Chain Debromination." Journal of Organic Chemistry. 53. 1703-1708 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Takagi,N.Miyake,E.Nakamura,H.Usami,Y.Sawaki,H.Iwamura: "Micellar Effect on the Photosensitized Debromination of 2,3-Dibromo-3-phenylpropionic Acid" J.Chem.Soc.,Faraday Trnasaction 1. 84. 3475-3486 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 高木克彦、沢木泰彦: "新・光機能性高分子の応用、“バイオ関連材料"" シ-エムシ-, 14 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 高木克彦、沢木泰彦: "表面、“イオン性界面を利用した光増感電子移動反応"" 広信社, 8 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Takagi, H. Fukaya, and Y. Sawaki: "Does a Stilbazolium Cation Adsorbing Poly(styrenesulfonate) Anion Form Micellar-like Clusters?" Journal of American Chemical Society, 110, 7469-7473, (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Takagi, N. Miyake, E. Nakamura, Y. Sawaki, N. Koga, and H. Iwamura: "ZnTPPS-Sensitized Photodibromination of 3-Dibromo-3-phenylpropionic Acids. Electron Transfer Initiated Chain Debromination." Journal of Organic Chemistry, 53, 1703-1709, (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Takagi, N. Miyake, E. Nakamura, H. Usami, Y. Sawaki, and H. Iwamura: "Micellar Effect on the Photosensitized Debromination of 2, 3-Dibromo-3-phenylpropionic Acids." Journal of Chemical Society, Faraday Transaction 1, 84, 3475-3486, (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Takagi,N.Maiyake,E.Nakamura,Y.Sawaki,N.Koga,H.Iwamura: "ZnTPPS-Sensitized Photodibrodimination of 2,3-Dibromo-3-phenyl-propionic Acids.Electron Transfer Initiated Chain Debromination." Journal of Organic Chemistry. 53. 1703-1708 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Takagi,N.Maiyake,E.Nakamura,H.Usami,Y.Sawaki: "Micellar Effect on the Photosensitized Debromination of 2,3-Dibromo-3-pheylpropionic Acid" J.Chem.Soc.,Faraday Transaction 1. 84. 3475-3486 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] Katsuhiko Takagi: Journal of the American Chemical Society. 110. 7469-7472 (1988)

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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