Hockey-Stick Polycatenars: Network formation and transition from one dimensional to three-dimensional liquid crystalline phases

Abstract

Photo switchable liquid crystalline (LC) materials are of great interest for optical and photonic applications. Herein we report the design, synthesis, and molecular self-assembly of the first examples of photosensitive hockey-stick (HS) polycatenars. Therefore, two new series of HSLCs derived from 4-cyanoresorcinol bent-core unit connected to a short azobenzene-based side arm with one variable alkoxy chain and a long ester-based wing terminated with two alkoxy chains at 3 and 5 positions of the terminal benzene ring are reported. They differ from each other in the length of the terminal chains connected to the long arm. The LC self-assembly of these HSLCs was investigated by polarized optical microscopy (POM), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and electro optical investigations. Depending on length of terminal chains a transition from one dimensional (1D) tilted and non-tilted smectic phases to three dimensional (3D) achiral bicontinuous cubic phases with Ia3¯d symmetry (Cubbi/Ia3¯d) upon chain elongation is observed. Moreover, achiral isotropic liquid networks were observed for medium and long chain homologues. Most of mesophases are room temperature LCs phases with wide ranges as observed in the cooling cycles, where once they are formed on heating, no sign of crystallization is detected down to ambient temperature. Finally, UV light irradiation results in fast and reversible photoinduced transformation between different types of LCs phases as well as between LC phase and isotropic liquid.