Ultrafast Time-Resolved Spectroscopic Study on the Photophysical and Photochemical Reaction Mechanisms of ortho-Methylbenzophenone in Selected Solutions.

The photophysical and photochemical reaction pathways of ortho-methylbenzophenone (o-MeBP) in different solutions were investigated by employing femtosecond to nanosecond transient absorption and nanosecond time-resolved resonance Raman spectroscopy methods. In pure acetonitrile, neutral or pH 1 aqueous solutions, o-MeBP exhibit similar excited-state evolutions upon excitation in which o-MeBP will experience excitation to an excited state then undergo intersystem crossing and solvent arrangement followed by 1,5 hydrogen atom transfer processes to form the first singlet excited state, triplet state (n, π*), biradical intermediates, and enol form transients, respectively. However, in a pH 0 acidic solution, the protonation of o-MeBP will form the cation biradical intermediate that facilitates radical coupling to generate a benzocyclobutanol product, which causes a dramatic reduction of the lifetime of the enol form transients. In contrast, in sodium bicarbonate solution, the biradical intermediate may be quenched by the bicarbonate ion to construct a C-C bond and form the carboxylic acid that causes a fast decay of biradical intermediate. These results demonstrate that the photophysical and photochemical reaction pathways of o-MeBP are pH-dependent in aqueous solution which may be very useful for the capture of CO2 capture by photoexcitation of aromatic ketones.