Giant Single-Crystal Shape Transformation with Wide Thermal Hysteresis Actuated by Synergistic Motions of Molecular Cations and Anions

Chemistry. 2020 May 26;26(30):6778-6783. doi: 10.1002/chem.202000845. Epub 2020 May 14.

Abstract

Manipulating the collective molecular movements to implement macroscopic mechanical response of bulk material is attractive and challenging. Here, an organic-inorganic hybrid single crystal is synthesized, which exhibits a giant macroscopic shape transformation with a remarkable thermal hysteretic feature. The colossal anisotropic shape change, which manifests as an abrupt elongation of ca. 9 % along the crystallographic c-axis and a concomitant contraction of ca. 9 % in a perpendicular direction, is induced by a significant reorientation of imidazolium, accompanied with a substantial configurational variation in CuBr4 2- complex anions. The synergistic motions of both the molecular cations and anions engender a remarkable large thermal hysteresis (>30 K) in the shape transformation of the single crystal, implying that this material may play a role in alternating memory media. Furthermore, due to the stable crystal lattice, a single crystal that demonstrates naked-eye detectable large shape transformation was used as a thermal actuator to spontaneously control an electric circuit by temperature variation.

Keywords: bistable materials; mechanical properties; molecular wheels; phase transitions; thermal hysteresis.