SINGLET AND TRIPLET REACTIVITY IN THE PHOTOINDUCED ELECTRON-TRANSFER FROM AROMATIC-AMINES TO CHLOROBENZENES

被引:13
作者
AVILA, V
COSA, JJ
CHESTA, CA
PREVITALI, CM
机构
[1] Departamento de Quimica y Fisica, Universidad Nacional de Rio Cuarto
关键词
D O I
10.1016/1010-6030(91)85107-R
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The electron transfer quenching from the excited singlet state of several aromatic amines and 9-methylcarbazole to chlorobenzenes and chlorobiphenyls was studied by fluorescence quenching in methanolic solutions. The triplet quenching of N,N-dimethylaniline and 9-methylcarbazole was measured by laser flash photolysis. It was found that the singlet rate constants do not follow the same free-energy correlation as the triplet state. The reactivity of the excited singlet is lower than that of the triplet for a given overall free-energy change. It is proposed that this effect is due to a contribution from an inner-sphere reorganization to the intrinsic energy barrier, which would be higher in the case of the singlet reaction.
引用
收藏
页码:83 / 91
页数:9
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