Switchable Phase Helicity Independent of the Absolute Configuration of the Stereocenter: Anomalous Induction between Sergeants and Soldiers in Chiral Liquid-Crystalline Polymers

Controlling the secondary phase in chiral liquid-crystalline(LC)polymers is of great importance since it transfers and amplifies molecularinformation to the macroscopic properties. However, the chiral superstructuresof the LC phase are determined exclusively by the inherent configurationof the parent chiral source. Here, we report the switchable supramolecularchirality of heteronuclear structures by the untraditional commandbetween common chiral "sergeant" units and various achiral"soldier" units. Different chiral induction pathwaysbetween sergeants and soldiers were observed for copolymer assemblieswith mesogenic and non-mesogenic soldier units, demonstrating theformation of a helical phase independent of the absolute configurationof the stereocenter. In the presence of non-mesogenic soldier units,the classical SaS (Sergeants and Soldiers) effect in the amorphousphase was observed; whereas in a full LC system, bidirectional commandof sergeants was activated in response to the phase transition. Meanwhile,a full spectrum of morphological phase diagrams including sphericalmicelles, worms, nanowires, spindles, tadpoles, anisotropic ellipsoidalvesicles, and isotropic spherical vesicles were successfully achieved.Such spindles, tadpoles, and anisotropic ellipsoidal vesicles haverarely been obtained previously from chiral polymer systems.