| Project/Area Number |
05453118
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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 |
工業物理化学
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| Research Institution | SHIZUOKA UNIVERSITY |
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Principal Investigator |
NAGAMURA Toshihiko SHIZUOKA UNIVERSITY,RESEARCH INSTITUTE OF ELECTRONICS,PROFESSOR, 電子工学研究所, 教授 (90117200)
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| Co-Investigator(Kenkyū-buntansha) |
SAKAGUCHI Hirochi SHIZUOKA UNIVERSITY,RESEARCH INSTITUTE OF ELECTRONICS,PROFESSOR, 電子工学研究所, 助手 (30211931)
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| Project Period (FY) |
1993 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1994: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1993: ¥4,700,000 (Direct Cost: ¥4,700,000)
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| Keywords | Ion-pair charge-transfer complex / Photoinduced electron transfer reaction / Radicals / Charge-resonance spectrum / Styrylpyridinium / Molecular interaction / ESR / Photochromism / スチリルビリジニウム |
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| Research Abstract |
1) Tetraphenyl salts of styrylpyridinium ions with strong electron-withdrawing groups such as nitro and dicyanovinyl groups were prepared.They formed ion-pair charge-transfer (IPCT) complexes in less polar organic solvents like 1,2-dimethoxyethane (DME).Upon excitation of an IPCT band in degassed conditions, electron transfer reaction occurred resulting in the formation of styrylpyridinyl radical with an absorption spectrum in the visible region. At the same time a broad absorption spectrum was observed in the near infrared region, which was assigned to the charge-resonance (CR) band due to the electronic interaction between a photogenerated styrylpyridinyl radical with a parent styrylpyridinium cation. The CR-band spectrum depended on the substituents and the stabilization energy was slightly higher in nitro-derivative than dicyanavinyl-derivative.
2) The Electron Spin Resonance (ESR) spectrum of photoinduced radicals in dicyanovinyl-derivative was a broad singlet due to exchange broad
… More
ening. Hyperfine structure appeared upon mixing it with unirradiated DME solution of dicyanovinyl-derivateve, which was assigned to dimer radical cations formed by interaction of photogenerated styrylpyridinyl radicals with parent styrylpyridinium cations.
3) Kinetic studies were made on these salts using a nano-second (ns) pulsed laser. The CR-band absorption rose within a ns pulse in a similar manner as the visible absorption of styrylpyridinyl radicals, strongly suggested diffusionlness formation of dimer radical cations.
4) A mixture of amphipathic nitrostyrylpyridinium tetraphenylborate and arachidic acid showed a solid condensed phase at the air-water interface. Y-type Langmuir-Blodgett films were deposited on a quartz plate with deposition ratio of unity. Microcrystalline films were also prepared by evaporation. Photoexcitation of these solid films at the same condition as in solutions caused some spectral chantes. It was, however, not possible to observe the formation of styrylpyridinyl radicals and dimer radical cations in these solid films. Less
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