Photooxidation of 9,10-diethoxyanthracene: mechanistic dichotomies between homogeneous solution and reverse micelle photoprocesses

We have compared the photooxidation of the title compound, DEA, by diphenyliodonium salts in homogeneous acetonitrile (AN) and in heptane/AOT/water reverse micelle solutions. The reaction is efficient, which we attribute to rapid (ca. 10 ps) deethylation of the DEA radical cation, initially formed b...

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Bibliographic Details
Published in:Canadian journal of chemistry 1990-04, Vol.68 (4), p.612-619
Main Authors: DeVoe, R. J, Sahyun, M. R. V, Schmidt, E, Sharma, D. K
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
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Summary:We have compared the photooxidation of the title compound, DEA, by diphenyliodonium salts in homogeneous acetonitrile (AN) and in heptane/AOT/water reverse micelle solutions. The reaction is efficient, which we attribute to rapid (ca. 10 ps) deethylation of the DEA radical cation, initially formed by photoinduced electron transfer. In AN, the electron transfer occurs from singlet excited DEA, but in reverse micelles it is gated by intersystem crossing to triplet DEA. Under these conditions, DEA fluorescence quenching by the iodonium cation may still be observed; we infer operation of the external heavy atom effect as the primary mechanism. Keywords: anthracene, electron transfer, reverse micelle, photochemistry, picosecond.
ISSN:0008-4042
1480-3291
DOI:10.1139/v90-094