Correlated Dynamics in Ionic Liquids by Means of NMR Relaxometry: Butyltriethylammonium bis(Trifluoromethanesulfonyl)imide as an Example

Int J Mol Sci. 2021 Aug 24;22(17):9117. doi: 10.3390/ijms22179117.

Abstract

1H and 19F spin-lattice relaxation experiments have been performed for butyltriethylammonium bis(trifluoromethanesulfonyl)imide in the temperature range from 258 to 298 K and the frequency range from 10 kHz to 10 MHz. The results have thoroughly been analysed in terms of a relaxation model taking into account relaxation pathways associated with 1H-1H, 19F-19F and 1H-19F dipole-dipole interactions, rendering relative translational diffusion coefficients for the pairs of ions: cation-cation, anion-anion and cation-anion, as well as the rotational correlation time of the cation. The relevance of the 1H-19F relaxation contribution to the 1H and 19F relaxation has been demonstrated. A comparison of the diffusion coefficients has revealed correlation effects in the relative cation-anion translational movement. It has also turned out that the translational movement of the anions is faster than of cations, especially at high temperatures. Moreover, the relative cation-cation diffusion coefficients have been compared with self-diffusion coefficients obtained by means of NMR (Nuclear Magnetic Resonance) gradient diffusometry. The comparison indicates correlation effects in the relative cation-cation translational dynamics-the effects become more pronounced with decreasing temperature.

Keywords: diffusion; dynamics; ionic liquids; nuclear magnetic resonance; relaxation.

MeSH terms

  • Hydrocarbons, Fluorinated / chemistry*
  • Imides / chemistry*
  • Ionic Liquids / chemistry*
  • Magnetic Resonance Spectroscopy / methods*

Substances

  • Hydrocarbons, Fluorinated
  • Imides
  • Ionic Liquids
  • bis(trifluoromethanesulfonyl)imide