Photoionization of perylene in polar solvents

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Abstract
The photoionization of perylene in two common polar solvents (acetonitrile and dimethylformamide) is reported. The transient absorption spectra differ significantly from one solvent to the other: Positive and negative ion absorption intensities invert as also do ion decay times. These differences are attributed to solute–solvent interactions in the excited state. The mechanism for the photoionization process is posited to involve electron injection from perylene to the electrophilic solvent (i.e., acetonitrile) and hole injection from perylene to the nucleophilic solvent (i.e., dimethylformamide).