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J Phys Chem A. 2013 May 16;117(19):3925-34. doi: 10.1021/jp3128669. Epub 2013 May 6.

Temperature dependence of the excited-state proton-transfer reaction of quinone-cyanine-7.

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Raymond and Beverly Sackler Faculty of Exact Sciences, School of Chemistry, Tel Aviv University, Tel Aviv 69978, Israel.


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.

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