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Probing the Dynamics of Solvation and Structure of the OH- Ion in Aqueous Solution from Picosecond Transient Absorption Measurements

By Olivier Poizat and Guy Buntinx


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

Topics: transient absorption spectroscopy, hydroxide ion solvation, solvation dynamics, bipyridine, Organic chemistry, QD241-441, Chemistry, QD1-999, Science, Q, DOAJ:Organic Chemistry, DOAJ:Chemistry
Publisher: MDPI AG
Year: 2010
DOI identifier: 10.3390/molecules15053366
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