Polymerization‐induced Chiral Self‐assembly for the In situ Construction, Modulation, Amplification and Applications of Asymmetric Suprastructures

Abstract 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.