Spectroscopic Evidence for Doubly Hydrogen-Bonded Cationic Dimers in the Solid, Liquid, and Gaseous Phases of...

Intermolecular interactions determine whether matter sticks together, gases condense into liquids, or liquids freeze into solids. The most prominent example is hydrogen bonding in water, responsible for the anomalous properties in the liquid phase and polymorphism in ice. The physical properties are also exceptional for ionic liquids (ILs), wherein a delicate balance of Coulomb interactions, hydrogen bonds, and dispersion interactions results in a broad liquid range and the vaporization of ILs as ion pairs. In this study, we show that strong, local, and directional hydrogen bonds govern the structures and arrangements in the solid, liquid, and gaseous phases of carboxyl-functionalized ILs. For that purpose, we explored the H-bonded motifs by X-ray diffraction and attenuated total reflection (ATR) infrared (IR) spectroscopy in the solid state, by ATR and transmission IR spectroscopy in the liquid phase, and by cryogenic ion vibrational predissociation spectroscopy (CIVPS) in the gaseous phase at low temperature. The analysis of the CO stretching bands reveals doubly hydrogen-bonded cationic dimers (c═c), resembling the archetype H-bond motif known for carboxylic acids. The like-charge doubly hydrogen-bonded ion pairs are present in the crystal structure of the IL, survive phase transition into the liquid state, and are still present in the gaseous phase even in (2,1) complexes wherein one counterion is removed and repulsive Coulomb interaction increased. The interpretation of the vibrational spectra is supported by quantum chemical methods. These observations have implications for the fundamental nature of the hydrogen bond between ions of like charge.