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Controlling the Outcome of Electron Transfer Reactions in Ionic Liquids
Journal article   Peer reviewed

Controlling the Outcome of Electron Transfer Reactions in Ionic Liquids

Harsha V. R Annapureddy and Claudio J Margulis
The journal of physical chemistry. B, Vol.113(35), pp.12005-12012
09/03/2009
DOI: 10.1021/jp905144n
PMID: 19663446

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Abstract

In this article, we investigate the excited state intramolecular electron transfer (ET) reaction of crystal violet lactone (CVL) in the room temperature ionic liquid (RTIL) N-propyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Pr31 +][Tf2N−]. This system was chosen in light of recent experimental observations by Maroncelli and co-workers (J. Phys. Chem. B 2007, 111, 13473), in which the kinetics of electron transfer between S1 (commonly referred as LE) and S2 (commonly referred as CT) emission states and, therefore, the ratio of emitting populations were shown to be absorption-wavelength-dependent. Our computational studies indicate that the kinetics of the intramolecular ET between S1 and S2 states of CVL in [Pr31 +][Tf2N−] is local solvent-environment-dependent. Because emission time scales are smaller than solvent relaxation time scales, this behavior is characteristic of RTILs but uncommon in conventional solvents. Therefore, RTILs open a window of opportunity for manipulating the outcome of chemical reactions simply by tunning the initial excitation wavelength. Our studies show that when acetonitrile is used as a solvent instead of [Pr31 +][Tf2N−] the ratio of populations of emission states is independent of excitation wavelength, eliminating the opportunity for influencing the outcome of reactions.
 B: Statistical Mechanics, Thermodynamics, Medium Effects

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