Deuteron magnetic resonance study of glyceline deep eutectic solvents: Selective detection of choline and glycerol dynamics

Glyceline, a green solvent considered for various electrochemical applications, represents a multi-component glass former. Viewed from this perspective, the choline cation and the hydrogen bond donor glycerol, the two major constituents forming this deep eutectic solvent, were studied using nuclear magnetic resonance in a selective manner by means of suitably deuteron-labeled isotopologues. Carried out from far above to far below the glass transition temperature, measurements and analyses of the spin-lattice and spin-spin relaxation times reveal that the reorientational dynamics of the components, i.e., of glycerol as well as of chain deuterated choline chloride are slightly different. Possible implications of this finding regarding the hydrogen-bonding pattern in glyceline are discussed. Furthermore, the deuterated methyl groups in choline chloride are exploited as sensitive probes of glyceline's supercooled and glassy states. Apart from spin relaxometry, a detailed line shape analysis of the CD₃ spectra yields valuable insights into the broad intermolecular and intramolecular energy barrier distributions present in this binary mixture.