Picosecond and Nanosecond Studies of the Photoreduction of Benzophenone by N,N-Diethylaniline and Triethylamine

Article abstract of DOI:10.1021/j100172a030

The photoreduction of benzophenone by N,N-diethylaniline and trimethylamine has been examined in a number of solvents by both nano- and picosecond laser photolysis.With diethylaniline, electron transfer is the primary step and the spectrum of the ion pair has been detected even in nonpolar solvents such as benzene and cyclohexane.Rapid proton transfer then takes place to form a high yield of the ketyl radical.The lifetime of the ion pair in benzene is about 900 ps.In acetonitrile the ion pair dissociates into individual ions which then decay by back electron transfer and proton transfer.A spectral shift to the red occurs over 100 ps as the contact ion pair dissociates.In acidic alcohols such as methanol and trifluoroethanol proton transfer from the alcohol occurs to produce the ketyl radical.In the case of triethylamine, no distinct absorption band for benzophenone anion was seen in picosecond experiments but difference spectra, which removed much of the spectrum of benzophenone triplet, clearly showed some contribution from the anion.For this compound, it is likely that electron transfer occurs first followed by very fast proton transfer.