The reaction of intracomplex proton transfer (44BPY-....HO-H) ® 44BPYH. + OH- that follows the photoreduction of 4,4’-bipyridine (44BPY) into its anion radical 44BPY- in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) is investigated in acetonitrile-water mixtures by using picosecond transient absorption. The dependence of the appearance kinetics of the 44BPYH. radical on the water content reveals a highly diffusional proton transfer process that is controlled by the dynamics of solvation of the released hydroxide ion. The results are interpreted on the basis of a two-step mechanism where an intermediate solvation complex (44BPYH.)OH-(H2O)3 is formed first before evolving toward a final four-water hydration structure OH-(H2O)4
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