Why are viscosities lower for ionic liquids with - CH 2Si(CH 3) 3 vs -CH 2C(CH 3)3 substitutions on the imidazolium cations?

Hideaki Shirota, Edward W. Castner

Research output: Contribution to journalArticle

148 Citations (Scopus)

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 °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.

Original languageEnglish
Pages (from-to)21576-21585
Number of pages10
JournalJournal of Physical Chemistry B
Volume109
Issue number46
DOIs
Publication statusPublished - Nov 24 2005

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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