Excited-state hydroxide ion transfer from a model xanthenol photobase.
2015
This article reports a study of excited-state hydroxide ion release from a model xanthenol photobase, XanOH. The driving force for the reaction was tuned using solvent mixtures with varying water/acetonitrile ratios, and the kinetics of the reaction was monitored using ultrafast pump–probe spectroscopy. The intrinsic barrier for the heterolysis was evaluated using Marcus and bond-energy bond-order (BEBO) models. The obtained value (ΔGo# = 10.17–10.80 kcal/mol) is significantly higher than the intrinsic barriers found for the proton release from previously studied photoacids. These results were discussed in terms of the difference in structures of solvated H+ and OH– ions.
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