On the coupling between ionic conduction and dipolar relaxation in deep eutectic solvents: Influence of hydration and glassy dynamics.

We have studied the ionic conductivity and the dipolar reorientational dynamics of aqueous solutions of a prototypical deep eutectic solvent (DES), ethaline, by dielectric spectroscopy in a broad range of frequencies (MHz-Hz) and for temperatures ranging from 128 to 283 K. The fraction of water in the DES was varied systematically to cover different regimes, starting from the pure DES and its water-in-DES mixtures to the diluted electrolyte solutions. Depending on these parameters, different physical states were examined, including low viscosity liquid, supercooled viscous liquid, amorphous solid, and freeze-concentrated solution. Both the ionic conductivity and the reorientational relaxation exhibited characteristic features of glassy dynamics that could be quantified from the deviation from the Arrhenius temperature dependence and non-exponential decay of the relaxation function. A transition occurred between the water-in-DES regime (<40 wt. %), where the dipolar relaxation and ionic conductivity remained inversely proportional to each other, and the DES-in-water regime (>40 wt. %), where a clear rotation-translation decoupling was observed. This suggests that for a low water content, on the timescale covered by this study (∼10 to 1 s), the rotational and transport properties of ethaline aqueous solutions obey classical hydrodynamic scaling despite these systems being presumably spatially microheterogeneous. A fractional scaling is observed in the DES-in-water regime due to the formation of a maximally freeze-concentrated DES aqueous solution coexisting with frozen water domains at sub-ambient temperature.