As the development of the work (J. Phys. Chem. B 2019, 123 (10), 2362−2372), we have investigated the translational mobility in the same set of dried imidazoliumbased ionic liquids (ILs) [bmim]A (A = BF 4− , NO 3 − , TfO − , I − , Br − , and Cl − ) in a wide temperature range using the NMR technique. It is shown that for the [bmim] + cation, the temperature dependencies of product Dη do not follow the Stokes−Einstein relation for most systems studied, that is, the so-called "diffusion−viscosity decoupling" was realized. The correlation between local and translational mobility in pure IL of the [bmim][A] type was investigated using the data on NMR relaxation rates and diffusion coefficients. The most recent hypothesis of "water pockets" in mixtures of IL with water is critically discussed. Considering the totality of data in the literature and obtained here, we propose a specific model of the microstructure which may be applied up to water concentrations of 80−90 mol % (the structure of water-rich solutions is out of our current consideration). To confirm the model, molecular dynamics simulations of "IL−water" mixtures were also carried out.

The detailed investigation of the local mobility in a set of dried imidazolium-based ionic liquids (1-butyl-3-methylimidazolium) in a wide temperature range and varying anions (BF4 –, I–, Cl–, Br–, NO3 –, TfO–) is presented. The measurements of temperature dependencies of the spin–lattice relaxation times of 1H and 13C nuclei are motivated by the need to obtain a fundamental characterization of molecular mobility of the substances under study, namely, to estimate the correlation times, τc, for the motion of individual molecular groups. In particular, it follows from obtained results that the mobility of the hydrocarbon “tail” is higher (smaller τc) than that of the imidazole ring, and this expected tendency is quantified. The effect of the influence of an anion type on the cation mobility is also analyzed.