Cheng Xiaoxiao, 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.
School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu, 241000, China.
Angew Chem Int Ed Engl. 2024 Dec 20;63(52):e202414332. doi: 10.1002/anie.202414332. Epub 2024 Oct 29.
In the polymerization-induced chiral self-assembly (PICSA) process, chiral functional monomers undergo spontaneous supramolecular self-assembly and asymmetric stacking during living polymerization, leading to the in situ generation of chiroptical polymer assemblies characterized by diverse morphologies. The PICSA strategy facilitates precise control and manipulation of both non-covalent supramolecular helices and covalent macromolecular helices within aggregated cores, thereby driving significant advancements in fields such as chiral recognition materials, asymmetric catalysts, nonlinear optical materials, and ferroelectric liquid crystals (LC). This minireview summarizes recent developments in the in situ chiroptical construction and modulation associated with the PICSA methodology. Furthermore, it seeks to elucidate emerging PICSA systems founded on various living polymerization mechanisms, exploring hierarchical chirality transfer processes and the pathway complexities in both equilibrium and non-equilibrium conditions. This minireview also presents several illustrative examples that demonstrate the practical applications of chiral polymer materials synthesized through the PICSA approach, thereby illuminating future opportunities in this innovative field.
在聚合诱导的手性自组装(PICSA)过程中,手性功能单体在活性聚合过程中经历自发的超分子自组装和不对称堆积,导致原位生成具有多种形态特征的手性光学聚合物组装体。PICSA策略有助于精确控制和操纵聚集核内的非共价超分子螺旋和共价大分子螺旋,从而推动手性识别材料、不对称催化剂、非线性光学材料和铁电液晶(LC)等领域的重大进展。本综述总结了与PICSA方法相关的原位手性光学构建和调制的最新进展。此外,它试图阐明基于各种活性聚合机制的新兴PICSA系统,探索分级手性转移过程以及平衡和非平衡条件下的途径复杂性。本综述还给出了几个示例,展示了通过PICSA方法合成的手性聚合物材料的实际应用,从而阐明了这一创新领域的未来机遇。