Guo Yuquan, Cheng Xiaoxiao, He Zixiang, Zhou Zhenyang, Miao Tengfei, Zhang Wei
State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal Universitv, Huaian, 223300, China.
Angew Chem Int Ed Engl. 2023 Dec 21;62(52):e202312259. doi: 10.1002/anie.202312259. Epub 2023 Oct 9.
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.
通过非手性聚合物的自组装构建手性超结构通常依赖于多种非共价键的相互作用，这受到诱导手性记忆能力的显著限制。尽管引入共价交联无疑可以增强手性超结构的稳定性，但同时产生的强约束效应阻碍了手性智能材料的应用。为了解决这个问题，我们首次尝试通过将动态共价交联引入侧链聚合物的手性自组装中，实现超分子手性的可逆固定。在进行手性诱导后，聚合物链中肉桂酸酯基团的可逆[2+2]环加成反应可以通过光进一步控制，以操纵链间交联和解交联。基于这种光可编程和动态手性固定策略，首次建立了一种新型的手性聚合物材料图案嵌入存储机制。
