Switchable Phase Helicity Independent of the Absolute Configuration of the Stereocenter: Anomalous Induction between Sergeants and Soldiers in Chiral Liquid-Crystalline Polymers
Cheng, Xiaoxiao1, Miao, Tengfei1, Zhang, Gong1, Guo, Jiaying1, Zhou, Zhenyang1, Zhang, Wei1,2* (张伟)
1State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
2School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu 241000, China
J. Am. Chem. Soc.2023, 145, 30, 16474–16487
Abstract：Controlling the secondary phase in chiral liquid-crystalline(LC)polymers is of great importance since it transfers and amplifies molecular information to the macroscopic properties. However, the chiral superstructures of the LC phase are determined exclusively by the inherent configuration of the parent chiral source. Here, we report the switchable supramolecular chirality of heteronuclear structures by the untraditional command between common chiral sergeant units and various achiral soldier units. Different chiral induction pathways between sergeants and soldiers were observed for copolymer assemblies with mesogenic and non-mesogenic soldier units, demonstrating the formation of a helical phase independent of the absolute configuration of the stereocenter. In the presence of non-mesogenic soldier units,the classical SaS (Sergeants and Soldiers) effect in the amorphous phase was observed; whereas in a full LC system, bidirectional command of sergeants was activated in response to the phase transition. Meanwhile,a full spectrum of morphological phase diagrams including spherical micelles, worms, nanowires, spindles, tadpoles, anisotropic ellipsoidal vesicles, and isotropic spherical vesicles were successfully achieved.Such spindles, tadpoles, and anisotropic ellipsoidal vesicles have rarely been obtained previously from chiral polymer systems.
链接：//pubs.acs.org/doi/10.1021/jacs.3c02999
