Assignment of the Lowest Singlet and Triplet States of the Monoaldehyde of Durene

Abstract

The monoaldehyde of durene has been synthesized. It has been shown to be the impurity frequently encountered in spectral studies involving durene crystals. Both the polarized absorption and emission spectra of the protonated and deuterated aldehyde in crystals of durene^h-14 and durene^d-14 have been obtained. Although the lowest excited singlet and triplet states, separated by 2200 cm^?1, are shown to be nπ* a number of features in the phosphorescence spectrum are more characteristic of a ³π* state. The polarization of the absorption spectrum, in particular the 0-0 band and bands involving the excitation of totally symmetric vibrations, is inconsistent with the nπ* nature of the transition. A number of explanations is proposed.