title: Why are viscosities lower for ionic liquids with -CH2Si(CH3)3 vs -CH2C(CH3)3 substitutions on the imidazolium cations?
abstract: 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 (BF(4)(-)) and bis(trifluoromethylsulfonyl)imide (NTf(2)(-)) 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 ILs for the NTf(2)(-) and BF(4)(-) 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.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road, Piscataway, New Jersey 08854-8087, USA. shirota@rutchem.rutgers.edu
authors.forename: Hideaki
authors.initials: H
authors.lastname: Shirota
authors.forename: Edward W
authors.initials: EW
authors.lastname: Castner
mesh_terms: D002412:Cations / Q000737:chemistry; D007093:Imidazoles / Q000737:chemistry*; D052578:Ionic Liquids / Q000138:chemical synthesis / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D010420:Pentanes / Q000737:chemistry*; D012680:Sensitivity and Specificity; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013696:Temperature; D014297:Trimethylsilyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014783:Viscosity
chemical_list: D002412:Cations; D007093:Imidazoles; D052578:Ionic Liquids; D010420:Pentanes; D014297:Trimethylsilyl Compounds; C039752:neopentane