The photochemistry and photophysics of some styrenes

Brentnall, Roger Leslie (1981) The photochemistry and photophysics of some styrenes. University of Southampton, Doctoral Thesis.

Abstract

A range of styrenes have been shown to form fluorescent exciplexes on irradiation in the presence of tertiary amines. The results of a mechanistic study of the photochemical and photophysical consequences of these bimolecular interactions are presented here. The systems which have been examined in the greatest detail in this context are those involving interaction of triethylamine (Et3N) with Styrene itself, trans-l-phenylprop-l-ene and Indene. Using principally the techniques of Single Photon Counting and Fluorescence Spectroscopy, under a variety of conditions of solvent and temperature, a detailed kinetic analysis of the processes of exciplex formation and decay has been carried out for these systems. Due to the polar nature of the exciplexes, strong correlations of various experimental parameters with the electron accepting ability of the initially excited styrenes have been observed. Over the range of systems studied, the exciplex emission maxima, free energy for complex formation and the various individual rate parameters (including apparently the rate constant for photoproduct formation) were all found to vary systematically in this way. In the case of the trans-lphenylprop-1-ene/Et3N system, the fact that photoproduct formation (and geometric isomerisation) may occur via the exciplex intermediate was demonstrated using the technique of exciplex quenching. As a background to the study of the styrene/amine interactions, the unimolecular photophysics of a range of compounds containing the styryl group, was examined. The results obtained support the view that the relative orientation of the phenyl and olefinic moieties is of particular importance in determining the photophysical characteristics of these compounds.

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