We present deuteron quadrupole coupling constants (DQCC) for hydroxyl-functionalized ionic liquids (ILs) in the crystalline or glassy states characterizing two types of hydrogen bonding: The regular Coulomb-enhanced hydrogen bonds between cation and anion (c-a), and the unusual hydrogen bonds between cation and cation (c-c), which are present despite repulsive Coulomb forces. We measure these sensitive probes of hydrogen bonding by means of solid-state NMR spectroscopy. The DQCCs of (c-a) ion pairs and (c-c) H-bonds are compared to those of salt bridges in supramolecular complexes and those present in molecular liquids. At low temperatures, the (c-c) species successfully compete with the (c-a) ion pairs and dominate the cluster populations. Equilibrium constants obtained from molecular-dynamics (MD) simulations show van't Hoff behavior with small transition enthalpies between the differently H-bonded species. We show that cationic-cluster formation prevents these ILs from crystallizing. With cooling, the (c-c) hydrogen bonds persist, resulting in supercooling and glass formation.
Keywords: DFT calculations; hydrogen bonding; ionic liquids; molecular-dynamics simulations; solid-state NMR.
© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.