title: Comparison of the blue-shifted C-D stretching vibrations for DMSO-d(6) in imidazolium-based room temperature ionic liquids and in water.
abstract: The blue-shifted C-D stretching vibrations (nu(CD)) of deuteriated dimethyl sulfoxide (DMSO-d(6)) in mixtures of DMSO-d(6)/ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) were carefully investigated and compared with those in DMSO-d(6)/water. Results from FTIR studies indicate that the direct interaction of C-D...F between DMSO-d(6) and the anion [BF(4)(-)] plays a minor role in the blue-shift of nu(CD) in the mixtures of DMSO-d(6)/IL. They also show that the indirect influence of the hydrogen bond formed by the nearby functional group SO with C(2)-H of the cation significantly contributes to the blue-shift of nu(CD), as can be inferred from the significant differences of the blue-shift in [Bmim][BF(4)] and 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([Bm(2)im][BF(4)]). In contrast, in the case of DMSO-d(6)/water mixtures, direct hydration of C-H...O between the methyl groups of DMSO-d(6) with the oxygen atom of water is mainly responsible for the blue shift of nu(CD). Furthermore, theoretical calculations revealed that charge migrations as well as rehybridization have a dominant effect on the blue-shift in both mixtures.
authors.affiliation: Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China.
authors.forename: Liqun
authors.initials: L
authors.lastname: Zhang
authors.forename: Yong
authors.initials: Y
authors.lastname: Wang
authors.forename: Zheng
authors.initials: Z
authors.lastname: Xu
authors.forename: Haoran
authors.initials: H
authors.lastname: Li