Photochemical Reaction of Charge-transfer Complexes
| Project/Area Number |
08640696
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Kitasato University |
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Principal Investigator |
TAKAYANAGI Hiroaki School of Pharmaceutical Sciences, Kitasato University Professor, 薬学部, 教授 (00050477)
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| Co-Investigator(Kenkyū-buntansha) |
HAGA Naoki School of Pharmaceutical Sciences, Kitasato University Assistance Professor, 薬学部, 助手 (80245422)
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| Project Period (FY) |
1996 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1998: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1997: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1996: ¥1,100,000 (Direct Cost: ¥1,100,000)
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| Keywords | Charge-transfer complex / Charge-transfer excitation / Photochemical Reaction / Contact radical ion pair / Quantum yield / Energy gap for backward electron transfer / 溶液 / 結晶 / 溶媒和ラジカルイオン対 / 電荷移動(CT)錯体 / 電荷移動(CT)励起 / 電子移動 / ラジカルイオン対 |
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| Research Abstract |
We have investigated dependence of the net energy deference, -ΔGィイD2BET'ィエD2, between the ground state and radical ion pairs on reactivity of the excited state of the charge-transfer (CT) complexes between acenaphthylene (CAN) and a series of electron acceptors such as nitriles, acid anhydrides and 1,4-benzoquinones. The CT complexes were selectively excited in dichloroethane with 546.1 nm light to determine quantum yield of reaction, ΦィイD2R,ィエD2, or >500 nm light to investigate the reaction products. Plots of ΦィイD2RィエD2 against -ΔGィイD2BETィエD2 shows that CT complexes with large -ΔGィイD2BETィエD2 values give net reaction products; however, with lowering of -ΔGィイD2BETィエD2, ΦィイD2RィエD2 tends to decrease and finally reaches zero when -ΔGィイD2BETィエD2 is lower than 1.7 Ev. When -ΔGィイD2BETィエD2 is lower than the threshold, excitation of the CT complexes of CAN with acceptors did not result in any reaction products. It was concluded that -ΔGィイD2BETィエD2 clearly controls the reactivity of excited CT complexes by affecting the backward electron transfer rate from the resulting radical ions.
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Report
(4 results)
Research Products
(8 results)
