Time-resolved resonance Raman identification and structural characterization of a light absorbing transient intermediate in the photoinduced reaction of benzophenone in 2-propanol.
A nanosecond time-resolved resonance Raman (ns-TR3) spectroscopic study of the triplet state benzophenone reaction with the 2-propanol hydrogen-donor solvent and subsequent reactions is presented. The TR3 spectra show that the benzophenone triplet state (npi*) hydrogen-abstraction reaction with 2-propanol is very fast (about 10 to 20 ns) and forms a diphenylketyl radical and an associated 2-propanol radical partner. The temporal evolution of the TR3 spectra also indicates that recombination of these two radical species occurs with a time constant of about 1170 ns to produce a LAT (light absorbing transient) intermediate that is identified as the 2-[4-(hydroxylphenylmethylene)cyclohexa-2,5-dienyl]propan-2-ol (p-LAT) species. Comparison of the TR3 spectra with results obtained from density functional theory calculations for the species of interest was used to elucidate the identity, structure, properties, and major spectral features of the intermediates observed in the TR3 spectra. The structures and properties of the reaction intermediates observed (triplet benzophenone, diphenyl ketyl radical, and p-LAT) are briefly discussed.
Du
Yong
Y
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, People's Republic of China.
Ma
Chensheng
C
Kwok
Wai Ming
WM
Xue
Jiadan
J
Phillips
David Lee
DL