Simultaneous Chiral Fixation and Chiral Regulation Endowed by Dynamic Covalent Bonds
Guo, Yuquan1, Cheng, Xiaoxiao1, He, Zixiang1, Zhou, Zhenyang1, Miao, Tengfei1,3*（缪腾飞）, Zhang, Wei1,2*(张伟)
1Stateand Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, Suzhou Key Laboratory of Macro-molecular Design and Precision Synthesis,College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123(China)
2School of Chemical and Environmental Engineering, Anhui Poly-technic University, Wuhu, 241000(China)
3Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal Universitv, Huaian223300(China)
Angew. Chem. Ed. In. 2023, e202312259
Abstract：The construction of chiral superstructures through the self-assembly of non-chiral polymers usually relies on the interplay of multiple non-covalent bonds, which is significantly limited by the memory ability of induced chirality. Although the introduction of covalent crosslinking can undoubtedly enhance the stability of chiral superstructures, the concurrent strong constraining effect hinders the application of chirality-smart materials. To address this issue, we have made a first attempt at the reversible fixation of supramolecular chirality by introducing dynamic covalent crosslinking into the chiral self-assembly of side-chain polymers. After chiral induction, the reversible [2+2] cycloaddition reaction of the cinnamate group in the polymer chains can be further controlled by light to manipulate inter-chain crosslinking and decrosslinking. Based on this photo-programmable and dynamic chiral fixation strategy, a novel pattern-embedded storage mechanism of chiral polymeric materials was established for the first time.