Excited state dipole moments and polarizabilities of some aromatic alkenes and alkynes

Abstract

Electric field induced changes in the optical absorption spectra (electrochromism) have been used to obtain the excited state dipole moments and polarizabilities of styrene, 2-vinylnaphthalene, 2-naphthylacetylene, and 9-vinylanthracene. Excited state dipole moments of the order of 4–6 debye have been obtained for all these molecules except for 9-vinylanthracene, for which the excited state dipole moment is zero within experimental error. These results support earlier proposals of the involvement of charge transfer excited states in the fast and efficient acid-catalysed photohydration reactions of this type of substrate. 9-Vinylanthracene, on the other hand, under similar conditions reacts differently to give a dimer as the major photoproduct, and its reaction is not subject to acid catalysis. These results shed light on the importance of charge transfer excited states on the efficiency of photohydration reactions. Keywords: electrochromism, excited state, dipole moments, polarizabilities.