The effect of added salts on electron transfer reactions involving exciplexes: the N,N-dimethylaniline-photosensitized dechlorination of 4-chlorobiphenyl

Journal of Photochemistry Pub Date : 1987-08-01 Epub Date: 2002-01-30 DOI:10.1016/0047-2670(87)80036-9

C.A. Chesta, J.J. Cosa, C.M. Previtali

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引用次数: 17

Abstract

The dechlorination of 4-chlorobiphenyl (ClBi) photosensitized by N,N-dimenthylaniline (DMA) was studied in methanolic and ethyl acetate solutions by means of continuous photolysis at 313 nm. The hydrogen chloride quantum yield was measured as a function of ClBi concentration. The reaction proceeds mainly via DMA singlet state sensitization.

Excited singlet deactivation of DMA by ClBi was investigated by fluorescence quenching. In low polarity solvents such as cyclohexane and ethyl acetate, the fluorescence quenching was accompanied by the appearance of the fluorescence band of an exciplex. The fluorescence quenching of the DMAClBi exciplex by tetrabutylammonium perchlorate and lithium perchlorate was also studied. Both salts enhanced the sensitized dechlorination of ClBi and an electrostatic interaction between undissociated perchlorates and the exciplexes is postulated to be responsible for the enhanced dechlorination.

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添加盐对杂络合物电子转移反应的影响:N,N-二甲基苯胺光敏脱氯

研究了N,N-维苯胺(DMA)光敏的4-氯联苯(ClBi)在甲醇和乙酸乙酯溶液中313 nm连续光解的脱氯反应。测定了氯化氢量子产率与ClBi浓度的关系。反应主要通过DMA单线态敏化进行。用荧光猝灭法研究了ClBi对DMA的激发单线态失活。在低极性溶剂中，如环己烷和乙酸乙酯，荧光猝灭伴随着荧光带的出现。研究了高氯酸四丁基铵和高氯酸锂对DMAClBi外络合物的荧光猝灭作用。这两种盐都增强了ClBi的敏化脱氯作用，而未解离的高氯酸盐和络合物之间的静电相互作用被认为是增强脱氯作用的原因。

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Journal of Photochemistry

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