Proton-coupled electron-transfer reactions play an important role in essential biochemical processes and in many redox reactions, notably those related to solutions to global energy challenges, as for example the splitting of water. In this presentation, we describe the photoinduced electron-transfer processes from water and alcohols to quinolinium cations, which result in fluorescence quenching of this species. Analysis of steady-state and time-resolved fluorescence data in acetonitrile solutions are consistent with the existence of a proton-coupled electron transfer between pairs of the hydroxylic molecules and the excited quinolinium ion. The structure of the intermediate complex with two water molecules in the ground and first-excited singlet states was determined by geometry optimization using ab-initio DFT(B3LYP) quantum mechanical calculations.We thank the Spanish Government and EU ERDF (Grants CTQ2010-17835, CTQ2010-17026, and CTQ2011-29311-C02-01) and the Xunta de Galicia (Grants CN 2012/314, EM2012/091, and GPC 2013/052) for financial support of our work.

Photoinduced proton-coupled electron transfer involving quinolinium cations

248th National Meeting (2014)

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