Abstract: | It is shown that azulenium cations in the first electronically excited state S1 are stronger acids than in the ground state S0. Their apparent pK″*, obtained from the H0-dependence of the quenching of the azulenium cation S1 → S0 fluorescence does not correspond to a true acid-base equilibrium in the electronically excited state S1. The pK″* values are kinetically controlled, the rate of reprotonation of azulene in the S1 state being too low to compete with the internal conversion to S0. |