The formation mechanism of ketyl radicals and several other selective photoreactions of benzophenone and its derivatives are initiated by the protonation of their triplet state and have been investigated using nanosecond time-resolved resonance Raman spectroscopy (ns-TR(3)) in solutions of varying conditions. Evidence is found that the ketyl radical is generated by the combined action of a ketone protonation and a subsequent electron transfer based on the results from previous studies on the photochemistry and photophysics of benzophenone and the ns-TR(3) results reported here for benzophenone, 1,4-dibenzoylbenzene, 3-(hydroxymethyl)benzophenone, and ketoprofen in neutral and acidic solution. In order to better understand the role of the protonated ketone, results are summarized for some selective photochemical reactions of benzophenone and its derivatives induced by protonation in acidic solutions. For the parent benzophenone, the protonation of the ketone leads to the photohydration reactions at the ortho- and meta-positions of the benzene ring in acidic aqueous solutions. For 3-(hydroxymethyl)benzophenone, the protonation promotes an interesting photoredox reaction to become very efficient and the predominant reaction in a pH = 2 aqueous solution. While for ketoprofen, the protonation can initiate a solvent-mediated excited-state intramolecular proton transfer (ESIPT) from the carboxyl group to the carbonyl group that then leads to a decarboxylation reaction in a pH = 0 acidic aqueous solution. We briefly discuss the key role of the protonation of the ketone in the photochemistry of these aromatic ketones.
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