Associative return electron transfer. A bond-coupled electron transfer in the photoreactions of cyclopropylamines

Yingsheng Wang, David K. Luttrull, Joseph P. Dinnocenzo, Joshua L. Goodman, Samir Farid, Ian Gould

Research output: Contribution to journalArticle

12 Scopus citations

Abstract

The dynamics of the geminate radical-ion pairs formed by electron transfer to the excited states of cyanoanthracenes from 2-phenylcyclopropylamines are dominated by exothermic bond cleavage of the amine radical cations. Quantitative studies of product formation as a function of the energetics of the photochemical and corresponding thermal reactions provide support for a novel mechanism in which return electron transfer in the geminate pair occurs in concert with bond formation from the ring-opened radical cations. This bond-coupled electron transfer process is referred to as an associative return electron transfer reaction. The important features of the associative electron transfer process that explain the experimental observations are described in terms of potential energy surfaces and competition between adiabatic and non-adiabatic deactivation paths.

Original languageEnglish (US)
Pages (from-to)1169-1176
Number of pages8
JournalPhotochemical and Photobiological Sciences
Volume2
Issue number11
DOIs
StatePublished - Nov 2003

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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