Photo-induced Electron-relay Reaction Utilizing Electrostatic Field of Polymers
| Project/Area Number | 63470072 |
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Nagoya University |
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Principal Investigator |
SAWAKI Yasuhiko Nagoya University, Dept. of Appl. Chem., Professor, 工学部, 教授 (30023120)
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| Co-Investigator(Kenkyū-buntansha) |
TAKAGI Katsuhiko Nagoya University, Dept. of Appl. Chem., Assoc. Professor, 工学部, 助教授 (60023264)
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| Project Period (FY) |
1988 – 1989
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| Project Status |
Completed(Fiscal Year 1989)
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| 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)
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| Keywords | Electron-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 |
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| 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.
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Report
(3results)
Research Products
(11results)
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[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).
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