Singlet and triplet reactivity in the photoinduced electron transfer from aromatic amines to chlorobenzenes

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 las...

Full description

Saved in:
Bibliographic Details
Published in:Journal of photochemistry and photobiology. A, Chemistry. Chemistry., 1991-11, Vol.62 (1), p.83-91
Main Authors: Avila, V., Cosa, J.J., Chesta, C.A., Previtali, C.M.
Format: Article
Language:English
Subjects:
Atomic and molecular physics
Exact sciences and technology
Molecular properties and interactions with photons
Physics
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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.
ISSN:1010-6030
1873-2666
DOI:10.1016/1010-6030(91)85107-R