Journal of Physical Chemistry p. 678 - 683 (1989)
Update date:2022-08-25
Topics:
Bruni, Maria Cristina
Ponterini, Glauco
Scoponi, Marco
An extensive analysis of the S1 deactivation pathways of diphenyl sulfone (DPS) in alcohols and some other solvents is presented.The combined results of steady-state photolysis, time-resolved fluorescence, and steady-state fluorescence measurements at variable temperature and of S1 <*> -> T1 intersystem crossing quantum yield determinations enable a complete characterization of the S1 photophysics and photochemistry of DPS to be obtained.The main S1 decay channel appears to be an activated S1 <*> -> Tn intersystem crossing (Ea ca. 2 kcal/mol), other than S1 <*> -> T1.Although the fluorescence emission and S1 <*> -> T1 quantum yields show some solvent dependence, they play minor roles in the solvents studied.The state eventually reached in the S1 <*> -> Tn activated intersystem crossing is proposed to be a dissociative 3??* state localized on a C-S bond, on the basis of experimental evidence and of some preliminary theoretical data.A simple rationalization of the observations is provided by a model potential energy diagram obtained as an extension of the one previously proposed to account for the results concerning the T1 decay of the same molecule.Two hypotheses on the mechanisms of the above-mentioned S1 <*> -> Tn activated intersystem crossing are put forward and briefly discussed.
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