Study of preferential solvation in binary mixtures by means of frequency-domain fluorescence spectroscopy

The preferential solvation of 8-N,N-(dimethylamino)-11H-indeno[2,1-a]pyrene, Py(S)DMA, in its transient charge transfer (CT) state in binary solvents such as toluene/DMSO liquid mixtures was studied by means of frequency-domain fluorometry. The data obtained were considered within the following kinetic scheme: the preferential solvation was described by the system of consecutive reversible reactions of which each step is associated with the absorption of one DMSO molecule in the first solvation shell of the fluoresent Py(S)DMA dipolar CT molecule. The rate constants of the first two reversible elementary processes (i.e., the decay of solvation complexes of Py(S)DMA with one and two polar molecules, k(-1) = 1.1 10(9) s(-1) and k(-2) = 1.4 10(9) s(-1)) were deter-mined.