Bonded exciplex formation: Electronic and stereoelectronic effects

Yingsheng Wang, Olesya Haze, Joseph P. Dinnoeenzo, Samir Farid, Ramy S. Farid, Ian Gould

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Abstract

As recently proposed, the singlet-excited states of several cyanoaromatics react with pyridine via bonded-exciplex formation, a novel concept in photochemical charge transfer reactions. Presented here are electronic and steric effects on the quenching rate constants, which provide valuable support for the model. Additionally, excited-state quenching in poly(vinylpyridine) is strongly inhibited both relative to that in neat pyridine and also to conventional exciplex formation in polymers, consistent with a restrictive orientational requirement for the formation of bonded exciplexes. Examples of competing reactions to form both conventional and bonded exciplexes are presented, which illustrate the delicate balance between these two processes when their reaction energetics are similar. Experimental and computational evidence is provided for the formation of a bonded exciplex in the reaction of the singlet excited state of 2, 6, 9, 10-tetracyanoanthracene (TCA) with an oxygen-substituted donor, dioxane, thus expanding the scope of bonded exciplexes.

Original languageEnglish (US)
Pages (from-to)13088-13094
Number of pages7
JournalJournal of Physical Chemistry A
Volume112
Issue number50
DOIs
StatePublished - Dec 18 2008

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Wang, Y., Haze, O., Dinnoeenzo, J. P., Farid, S., Farid, R. S., & Gould, I. (2008). Bonded exciplex formation: Electronic and stereoelectronic effects. Journal of Physical Chemistry A, 112(50), 13088-13094. https://doi.org/10.1021/jp8041445