Picosecond laser photolysis studies on the photoreduction of excited benzophenone by diphenylamine in solutions

Article abstract of DOI:10.1246/bcsj.63.131

The mechanism of photoreduction of benzophenone (BP) by diphenylamine (DPA) in isooctane as well as acetonitrile and other polar solvents has been investigated by means of picosecond laser photolysis and time-resolved transient absorption spectral measurements. The results of measurements have demonstrated clearly that the hydrogen abstraction and charge transfer (CT) or ion pair (IP) state formation by electron transfer are competing at encounter between triplet benzophenone (³BP*) and DPA both in nonpolar and polar solvent, and the CT or IP state relaxed with respect to the donor acceptor configurations and solvation does not contribute to the ketyl radical formation. It has been concluded that the very short-lived CT state at encounter between ³BP* and DPA plays a crucial role in the hydrogen abstraction reaction, i.e. the mutual orientation of ³BP* and DPA in this very short-lived CT state at encounter will determine the successive process, the formation of the ketyl radical or relaxed CT or IP state.