Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 109, Issue 46, Pages 21576-21585Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp053930j
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We have prepared novel room temperature ionic liquids (RTILs) with trimethylsilylmethyl (TMSiM)-substituted imidazolium cations and compared the properties of these liquids with those for which the TMSiM group is replaced by the analogous neopentyl group. The ionic liquids are prepared with both tetrafluoroborate (BF4_) and bis(trifluoromethylsulfonyl)imide (NTf2-) anions paired with the imidazolium cations. At 22 degrees C, the TMSiM-substituted imidazolium ILs have shear viscosities that are reduced by a factor of 1.6 and 7.4 relative to the alkylimidazolium lLs for the NTf2- and BF4- anions, respectively. To understand the effect of silicon substitution on the viscosity, the charge densities have been calculated by using density functional theory electronic structure calculations. The ultrafast intermolecular, vibrational, and orientational dynamics of these RTILs have been measured by using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). The intermolecular dynamical spectrum provides an estimate of the strength of interactions between the ions in the RTILs, and provides a qualitative explanation for the observed reduction in viscosity for the silicon -substituted RTILs.
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