An investigation of the solvent dependence on the ultrafast intersystem crossing kinetics of xanthone

The photophysics of xanthone in solution are measured using femtosecond pump-probe techniques. A kinetic model which includes intersystem crossing from both the 1ππ∗ and 1nπ∗ electronic states accurately represents the non-single exponential growth of the triplet-triplet absorption after excitation into the 1ππ∗ state at 310 nm. The intersystem crossing rate constants are consistent with an ‘inverse’ gap effect due to solvent polarity induced shifts in the electronic states. The branching between intersystem crossing from the 1ππ∗ and 1nπ∗ electronic states is also solvent dependent and is determined by the rate constant for internal conversion in the singlet electronic state.