Excited-State Proton Transfer to H2O in Mixtures of CH3CN–H2O of a Superphotoacid, Chlorobenzoate Phenol Cyanine Picolinium (CBCyP)

Steady-state and time-resolved fluorescence techniques were employed to study a superphotoacid with a pKa* of ∼−7, the chlorobenzoate phenol cyanine picolinium salt (CBCyP) in acetonitrile–water mixtures. We found that the time-resolved fluorescence is bimodal. The amplitude of the short-time component depends on χwater; the larger χwater, the greater the amplitude. We found that the excited-state proton-transfer (ESPT) rate constant, kPT, is ≥5 × 1012 s–1 in mixtures of χwater ≥ 0.08, whereas in neat water, kPT = 6 × 1012 s–1. The long-time component has a lifetime of 50 ps at χwater = 0.75. We attribute this time component to the CBCyP molecules that are not hydrogen-bonded to H2O clusters. The results suggest that the ESPT rate constant to water in acetonitrile–water mixtures depends only slightly on the water cluster size and structure surrounding the CBCyP molecule. We attribute the independence of the ESPT rate on the average water-cluster size to the large photoacidity of CBCyP. QM TD-DFT calculati...