Anion dynamics and motional decoupling in a glycerol–choline chloride deep eutectic solvent studied by one- and two-dimensional 35Cl NMR

Abstract

Chlorine-35 is among the few nuclides that provide an experimental handle on the anion dynamics in choline based deep eutectic solvents. By combining several nuclear magnetic resonance (NMR) techniques, the present work examines the Cl⁻ motions within glyceline, a glycerol : choline chloride 2 : 1 solution, in a large temperature range down to the glass transition temperature T_g. The applied methods include spin relaxometry, second-order line shape analysis, as well as two-dimensional central-transition exchange and stimulated-echo spectroscopy. The finding of unstructured central-transition NMR spectra characterized by a relatively small average quadrupolar coupling attests to a highly disordered, essentially nondirectional anionic coordination in glyceline. For temperatures larger than about 1.3T_g the chlorine motions are well coupled to those of the glycerol and the choline moieties. At lower temperatures the local translational anion dynamics become Arrhenian and increasingly faster than the motion of glyceline's matrix molecules. Upon further cooling, the overall ionic conductivity continues to display a super-Arrhenius behavior, implying that the choline cations rather than the Cl anions dominate the long-range charge transport also near T_g.