Water-induced fluorescence quenching of aniline and its derivatives in aqueous solution

Abstract

Nonradiative deactivation processes of excited aniline and its derivatives in aqueous solution were investigated by steady-state and time-resolved fluorescence measurements to reveal characteristic solvent effects of water on the relaxation processes of excited organic molecules. The magnitude of nonradiative rate (knr) of excited aniline derivatives increased significantly in water compared to that in organic solvents (cyclohexane, ethanol, and acetonitrile). The fluorescence lifetime measurements in organic solvent/H2O mixed solvents suggested that the fluorescence quenching in water was not due to exciplex formation but due to interactions with a water cluster. From temperature effect experiments on the fluorescence lifetime and quantum yield of aniline, N-methylaniline, and N,N-dimethylaniline, the apparent activation energies for the nonradiative deactivation rate in water were determined as 21, 30, and 41 kJ mol-1, respectively. Upon substitution of hydrogen atoms in the aromatic ring of aniline derivatives for deuterium atoms resulted in normal deuterium isotope effect in cyclohexane, i.e. knr decreased by deuterium substitution, while in water the same deuterium substitution led to an increase in knr (the inverse isotope effect). The inverse isotope effects implied that a direct internal conversion to vibrationally higher excited states in the electronically ground state is not a dominant mechanism but the transition to a close-lying energy level, e.g. the relaxation to charge transfer to solvent (ctts) state, would be associated with the quenching mechanism in water.