Dynamically Switchable Global Chirality in Racemic PolymerSystems
Zixiang He, Jiaying Guo, Yuqing Wang, Haotian Ma, Xiaoxiao Cheng（程笑笑）,* and Wei Zhang（张伟）*
State and Local Joint Engineering Laboratory for Novel FunctionalPolymeric Materials, Jiangsu Engineering Laboratory of NovelFunctional Polymeric Materials, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, College of Chemistry,Chemical Engineering and Materials Science, Soochow University Suzhou, 215123 (China)
Angew. Chem. Int. Ed.2025, 64, e202417495
Abstract: Any polymers composed of racemic segmentsare obviously optically inactive and lack any chiropticalapplications. Here, we present an intriguing method forprecisely generating global chirality in racemic copolymer assemblies without any external asymmetricalintervention via step-wise polymerization-induced chiralself-assembly (PICSA). Global supramolecular chiralityof the nanoaggregates could be dynamically switched bythe two diametrically opposed chiral conflict effects:“first come, first serve” effect and “late-comer livesabove” effect, which can be controlled by the preciselyspecified the number and sequence of enantiomericsegments. Significantly, the supramolecular stackingmanners of the racemic mesogenic building units as wellas the liquid crystallinity of the solvophobic core play acrucial role for the chiral communication pathway ofenantiomeric mesogens. Furthermore, such switchableglobal chirality in racemic polymers is broadly applicableand well regulable. We propose that this research maychallenge the notion that racemic systems lack opticalactivity while highlighting their potential applications infunctional racemic polymer materials and providinginsights into the evolution of racemates towards homochirality on early Earth.
Article information: //doi.org/10.1002/anie.202417495
