2H and 13C nuclear spin relaxation unravels dynamic heterogeneities in deep eutectic solvents of ethylene glycol, glycerol, or urea with choline chloride

Using deuteron spin-lattice and spin-spin relaxometry, the reorientational dynamics of ethaline (choline chloride/ethylene glycol) and reline (choline chloride/urea) are studied in a component-selective, isotope-edited manner over a wide temperature range, thereby complementing previous work on glyceline (choline chloride/glycerol). Differences in the hydrogen bond propensities effectuate that in reline and glyceline, the choline ions move faster than the hydrogen bond donors, glycerol and urea; in ethaline, the ethylene glycol molecules are reorienting faster. For glyceline and reline, the increase in the corresponding time scale ratio indicates a pronounced strengthening of the glycerol and urea networks upon cooling, while in ethaline, the time scale ratio remains essentially constant. For the three deep eutectic solvents, a comparison of the present component-selective results with the dielectric time constants shows that the latter are primarily sensitive to the dynamics of the respective hydrogen bond donors. In a Walden-type plot, the reorientation rates, selectively determined for the hydrogen bond donors and acceptors, are compared with their conductivity and fluidity, revealing that the dynamics of the choline ions relate most directly to the charge transport.