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Photochemical Reaction of Charge-transfer Complexes

电荷转移配合物的光化学反应

基本信息

批准号：
08640696
负责人：
TAKAYANAGI Hiroaki
金额：
$ 1.34万
依托单位：
Kitasato University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1998
项目状态：
已结题

项目摘要

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.

本文研究了苊烯（CAN）与一系列电子受体如腈、酸酐和1，4-苯醌的电荷转移（CT）络合物的激发态反应活性与离子对基态和自由基间的净能量差-ΔG Δ D_2BET ′ Δ D_2的关系。在二氯乙烷中，用546.1 nm光选择性激发CT络合物以测定反应的量子产率，用Φ λ D2 R、Φ λ D2或>500 nm光选择性激发CT络合物以研究反应产物。Φ λ D2 R λ D2与-ΔG λ D2 BET λ D2的关系图表明，具有大的-ΔG λ D2 BET λ D2值的CT络合物产生净反应产物;然而，随着-ΔG λ D2 BET λ D2的降低，Φ λ D2 R λ D2趋于降低，当-ΔG λ D2 BET λ D2低于1.7 Ev时，Φ λ D2 R λ D2最终达到零。当-ΔG Δ D_2BET Δ D_2低于阈值时，CAN与受体的CT复合物激发不产生任何反应产物。结果表明，-ΔG β D2 BET β D2通过影响自由基离子的后向电子转移速率，明显地控制了激发态CT复合物的反应活性。