Temperature Dependence of the Excited-State Proton-Transfer Reaction of Quinone-cyanine-7

Steady-state and time-resolved fluorescence techniques were used to study the temperature dependence of the photoprotolytic process of quinone-cyanine-7 (QCy7), a very strong photoacid, in H2O and D2O ice, over a wide temperature range, 85-270 K. We found that the excited-state proton-transfer (ESPT) rate to the solvent decreases as the temperature is lowered with a very low activation energy of 10.5 +/- 1 kJ/mol. The low activation energy is in accord with free-energy-correlation theories that predict correlation between Delta G of reaction and the activation energy. At very low temperatures (T < 150 K), we find that the emission band of the RO-*, the deprotonated form of QCy7, is blue-shifted by similar to 1000 cm(-1). We attributed this band to the RO-*center dot center dot center dot H3O+ ion pair that was suggested to be an intermediate in the photoprotolytic process but has not yet been identified spectroscopically.