{"title":"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","authors":"C.A. Chesta, J.J. Cosa, C.M. Previtali","doi":"10.1016/0047-2670(87)80036-9","DOIUrl":null,"url":null,"abstract":"<div><p>The dechlorination of 4-chlorobiphenyl (ClBi) photosensitized by <em>N,N</em>-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.</p><p>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 DMAClBi 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.</p></div>","PeriodicalId":16771,"journal":{"name":"Journal of Photochemistry","volume":"39 2","pages":"Pages 251-261"},"PeriodicalIF":0.0000,"publicationDate":"1987-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0047-2670(87)80036-9","citationCount":"17","resultStr":"{\"title\":\"The effect of added salts on electron transfer reactions involving exciplexes: the N,N-dimethylaniline-photosensitized dechlorination of 4-chlorobiphenyl\",\"authors\":\"C.A. Chesta, J.J. Cosa, C.M. Previtali\",\"doi\":\"10.1016/0047-2670(87)80036-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The dechlorination of 4-chlorobiphenyl (ClBi) photosensitized by <em>N,N</em>-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.</p><p>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 DMAClBi 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.</p></div>\",\"PeriodicalId\":16771,\"journal\":{\"name\":\"Journal of Photochemistry\",\"volume\":\"39 2\",\"pages\":\"Pages 251-261\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1987-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/0047-2670(87)80036-9\",\"citationCount\":\"17\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Photochemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/0047267087800369\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Photochemistry","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/0047267087800369","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
The effect of added salts on electron transfer reactions involving exciplexes: the N,N-dimethylaniline-photosensitized dechlorination of 4-chlorobiphenyl
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 DMAClBi 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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