Cold Crystallization and the Molecular Structure of Imidazolium-Based Ionic Liquid Crystals with a <i>p</i>-Nitroazobenzene Moiety
Katsuma Ishino, Hajime Shingai, Yasuyuki Hikita, Isao Yoshikawa, Hirohiko Houjou, Katsunori Iwase
Abstract
-imidazol-3-ium tetrafluoroborate ionic liquid crystal was investigated based on thermal analysis, structural analysis, infrared spectroscopy, and quantum chemical calculations. By conducting thorough structural characterization, we found that the prerequisite for cold crystallization is the irreversible molecular conformational alteration induced by the initial heating of the as-grown crystal into a smectic liquid crystal. The originally linear cation molecule bends and forms a step-stair conformation that persists throughout the subsequent heating and cooling processes as phase transition occurs from the crystal phase to the liquid crystal phase and then to the isotropic liquid phase. The formation of cold crystal occurs because of the choice of molecular stability over crystalline stability. Given the exothermic anomaly exhibited upon heating generic crystals to cold crystals, these findings demonstrate the promising potential of this ionic liquid crystal for thermal energy storage applications.