Solvent Effects on the Phosphorescent State of Some Aromatic Carbonyls

Abstract

Triplet state properties of chromone, 4-chromanone, acetophenone, and several alkyl derivatives of acetophenone were studied in a variety of solvent systems. The phosphorescence excitation method was used to monitor the energies and relative intensities of singlet–triplet absorption bands in the presence and absence of heavy atom solvents. The results, combined with earlier optical and magnetic resonance studies of such systems, illustrate the importance of solvent environment in determining fundamental properties of these excited states. Observed trends are interpreted in terms of contrasting effects of changing solvent polarity on proximate n,π* and π.π* triplet states. To describe the relative contribution of each orbital type to the phosphorescent state, the coefficients of each wavefunction must change with solvent. Correspondingly, the solvent environment should be specified whenever orbital designations are made.