Polarization of Phosphorescence and Symmetry of the Lowest Triplet State in Phenoxide Ion

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Abstract
Phosphorescence from rigid-glass solutions of phenoxide ion was subjected to a careful polarization study. The 0, 0 region of the emission is polarized mainly along the short (in-plane) and perpendicular (normal-to-the-plane) axes of the molecule. The presence of a short-axis component in the 0, 0 region of phosphorescence leads directly to a 3A1(3La) assignment for the lowest triplet state of this molecule and, by extrapolation, to a 3B1 u assignment in benzene. The solvent effects on the lifetime and polarization of phosphorescence demonstrate the importance of vibronic spin—orbit coupling in inducing dipole-allowed character into the phosphorescence of the phenoxide ion.