Multivariate statistical treatment of solvent effects in the photoreduction of CoIII(En)2(Br)(RC6H4NH2)2+ complexes in aqua-organic solvent media

Multivariate statistical treatment of solvent effects in the photoreduction of... Ultraviolet photolysis (λ = 254 nm) studies were carried out for a series of cobalt(III) complexes, CoIII(En)2(Br)(RC6H4NH2)2+, where R = m-OMe, p-F, H, m-Me, p-Me, p-OEt, and p-OMe, in various compositions of water-methanol/1,4-dioxane mixtures (0, 5, 10, 15, 20, 25, and 30 vol % organic cosolvent) at two different temperatures (287 and 300 K). The ligand-to-metal charge-transfer excited state produced in the excitation of the complex initially generated a solvent-caged {CoII; ligand radical} pair, which eventually undergoes recombination/separation into products. The quantum yield sharply increased from a mixture containing a lower mole fraction of organic cosolvent (x org) to higher one. In other words, when x org in the mixture increases, a steady increase in the quantum yield is observed. The quantum yield of CoIII(En)2(Br)(RC6H4NH2)2+ in various solvent mixtures is found to exhibit a linear (logΦCo(II) − 1/εr) dependence. This is consistent with solvation or solvent cage effect, which may be nonspecific, specific, or both. In order to throw light on these effects, a phenomenological model of solvent effects was applied. Therefore, the quantum yield values have been correlated statistically with some success containing different solvent parameters. The solvent parameters considered in this work are Grunwald-Winstein’s Y, Krygowski-Fawcett’s E T N and DN N along with Kamlet-Taft’s α, β, π* parameters. The regression model proposed is Y S = Y 0 + Σ i = 1 n a i X i , where YS is the solvent-dependent property (here logΦCo(II)) in a given solvent; Y 0 is the statistical quantity corresponding to the value of property in the reference solvent; X 1, X 2, X 3 … are explanatory variables, the solvent parameters, which can explain the various solvation effects on reactants/{CoII; ligand radical} pair, and a 1, a 2, a 3… etc., are the regression coefficients. The coefficient values can be quantified to measure the relative importance of solvent effects on the physicochemical quantity, that is, the photoreduction yields in the present investigation. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Russian Journal of Coordination Chemistry Springer Journals

Multivariate statistical treatment of solvent effects in the photoreduction of CoIII(En)2(Br)(RC6H4NH2)2+ complexes in aqua-organic solvent media

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Publisher
Nauka/Interperiodica
Copyright
Copyright © 2006 by Pleiades Publishing, Inc.
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry
ISSN
1070-3284
eISSN
1608-3318
D.O.I.
10.1134/S1070328406050095
Publisher site
See Article on Publisher Site

Abstract

Ultraviolet photolysis (λ = 254 nm) studies were carried out for a series of cobalt(III) complexes, CoIII(En)2(Br)(RC6H4NH2)2+, where R = m-OMe, p-F, H, m-Me, p-Me, p-OEt, and p-OMe, in various compositions of water-methanol/1,4-dioxane mixtures (0, 5, 10, 15, 20, 25, and 30 vol % organic cosolvent) at two different temperatures (287 and 300 K). The ligand-to-metal charge-transfer excited state produced in the excitation of the complex initially generated a solvent-caged {CoII; ligand radical} pair, which eventually undergoes recombination/separation into products. The quantum yield sharply increased from a mixture containing a lower mole fraction of organic cosolvent (x org) to higher one. In other words, when x org in the mixture increases, a steady increase in the quantum yield is observed. The quantum yield of CoIII(En)2(Br)(RC6H4NH2)2+ in various solvent mixtures is found to exhibit a linear (logΦCo(II) − 1/εr) dependence. This is consistent with solvation or solvent cage effect, which may be nonspecific, specific, or both. In order to throw light on these effects, a phenomenological model of solvent effects was applied. Therefore, the quantum yield values have been correlated statistically with some success containing different solvent parameters. The solvent parameters considered in this work are Grunwald-Winstein’s Y, Krygowski-Fawcett’s E T N and DN N along with Kamlet-Taft’s α, β, π* parameters. The regression model proposed is Y S = Y 0 + Σ i = 1 n a i X i , where YS is the solvent-dependent property (here logΦCo(II)) in a given solvent; Y 0 is the statistical quantity corresponding to the value of property in the reference solvent; X 1, X 2, X 3 … are explanatory variables, the solvent parameters, which can explain the various solvation effects on reactants/{CoII; ligand radical} pair, and a 1, a 2, a 3… etc., are the regression coefficients. The coefficient values can be quantified to measure the relative importance of solvent effects on the physicochemical quantity, that is, the photoreduction yields in the present investigation.

Journal

Russian Journal of Coordination ChemistrySpringer Journals

Published: May 13, 2006

References

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