Comparison of the blue-shifted C-D stretching vibrations for DMSO-d(6) in imidazolium-based room temperature ionic liquids and in water.
Comparison of the blue-shifted C-D stretching vibrations for DMSO-d(6) in imidazolium-based room temperature ionic liquids and in water.
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DOI：
10.1021/jp900139z
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发表时间：
2009-04
期刊：
影响因子：
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通讯作者：
Liqun Zhang;Yong Wang;Zhengtian Xu;Haoran Li
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文献类型：
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作者：
Liqun Zhang;Yong Wang;Zhengtian Xu;Haoran Li
仔细研究了DMSO-d(6)/离子液体1-丁基-3-甲基咪唑鎓四氟硼酸盐([Bmim][BF(4)])混合物中氘代二甲亚砜(DMSO-d(6))的蓝移C-D伸缩振动(nu(CD))，并与DMSO-d(6)/水进行了比较。 FTIR 研究结果表明，DMSO-d(6) 和阴离子 [BF(4)(-)] 之间 C-D...F 的直接相互作用对 DMSO-d(6)/IL 混合物中 nu(CD) 蓝移的影响较小。他们还表明，附近官能团SO与阳离子C(2)-H形成的氢键的间接影响对nu(CD)的蓝移有显着影响，这可以从[Bmim][BF(4)]和1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐([Bm(2)im][BF(4)])蓝移的显着差异推断出来。相反，在 DMSO-d(6)/水混合物的情况下，DMSO-d(6) 的甲基与水的氧原子之间的 C-H...O 直接水合是造成 nu(CD) 蓝移的主要原因。此外，理论计算表明，电荷迁移和再杂化对两种混合物的蓝移具有主导作用。
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.