title: Temperature dependence of the excited-state proton-transfer reaction of quinone-cyanine-7.
abstract: 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 ΔG 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 ~1000 cm(-1). We attributed this band to the RO(-)*···H3O(+) ion pair that was suggested to be an intermediate in the photoprotolytic process but has not yet been identified spectroscopically.
authors.affiliation: Raymond and Beverly Sackler Faculty of Exact Sciences, School of Chemistry, Tel Aviv University, Tel Aviv 69978, Israel.
authors.forename: Ron
authors.initials: R
authors.lastname: Simkovitch
authors.forename: Shay
authors.initials: S
authors.lastname: Shomer
authors.forename: Rinat
authors.initials: R
authors.lastname: Gepshtein
authors.forename: Doron
authors.initials: D
authors.lastname: Shabat
authors.forename: Dan
authors.initials: D
authors.lastname: Huppert