Systematic Dielectric and NMR Study of the Ionic Liquid 1‐Alkyl‐3‐Methyl Imidazolium

Abstract

The dynamic behaviors of ionic liquid samples consisting of a series of 1-alkyl-3-methylimidazolium cations and various counteranionic species are investigated systematically over a wide frequency range from 1 MHz to 20 GHz at room temperature using dielectric relaxation (DR) and nuclear magnetic resonance (NMR) spectroscopies. DR spectra for the ionic liquids are reasonably deconvoluted into two or three relaxation modes. The slowest relaxation times are strongly dependent upon sample viscosity and cation size, whereas the relaxation times of other modes are almost independent of these factors. We attribute the two slower relaxation modes to the rotational relaxation modes of the dipolar cations because the correlation times of the cations evaluated using longitudinal relaxation time (T(1) (13)C NMR) measurements corresponded to the dielectric relaxation times. On the other hand, the fastest relaxation mode is presumably related to the inter-ion motions of ion-pairs formed between cationic and anionic species. In the case of the ionic liquid bis(trifluoromethanesulfonyl)imide, the system shows marked dielectric relaxation behavior due to rotational motion of dipolar anionic species in addition to the relaxation modes attributed to the dipolar cations.