Abstract
AbstractNanosecond time‐resolved resonance Raman (ns‐TR3) spectroscopy was employed to investigate the triplet state of para‐hydroxybenzophenone (p‐hBP) in pure acetonitrile (MeCN) and its subsequent deprotonation reaction in a H2O/MeCN mixed solution. The TR3 results reveal that the deprotonation reaction occurred with the p‐hBP triplet state as the precursor species after 266 nm photolysis of p‐hBP in a H2O/MeCN mixed solution. The ground‐state p‐hBP anion species was observed to form about 20 ns after excitation in a 5% H2O/95% MeCN mixed solvent. Density functional theory (DFT) calculations were done to help obtain information about the structures and vibrational modes of the triplet p‐hBP and p‐hBP anion species. A reaction scheme is proposed for the photoreaction pathways of p‐hBP in pure MeCN and H2O/MeCN mixed solvents. Comparison of the results here for p‐hBP to the related para‐hydroxyacetophenone (HA) system indicates that substitution of the methyl group in HA with a phenyl group to form p‐hBP significantly alters the chemical reactivity of the triplet state so that both deprotonation and intersystem crossing (ISC) for the triplet state occur much faster in p‐hBP than in HA. Copyright © 2008 John Wiley & Sons, Ltd.
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