• • Post-polymerization modification enabled synthesis of a series of helical PPAs with identical degrees of polymerization and distribution, but with alkyl side chain lengths varied to induce asymmetry; this approach avoids time-consuming direct polymerization of diverse monomers.
• • Increasing side chain asymmetry transformed regular 2D hexagonal sheets (aspect ratio ~1) into anisotropic hexagonal platelets with progressively higher aspect ratios; the largest asymmetry produced chiral vortices, demonstrating a critical asymmetry threshold for pathway shift.
• • Computational simulations revealed that vortex-like assemblies are kinetically stabilized rather than thermodynamically stable, indicating that assembly conditions and kinetic control are essential for achieving chiral vortex structures.
• • All 2D assemblies exhibited significantly enhanced circularly polarized luminescence (CPL) compared to discrete polymer solutions, with dissymmetry factors (g_lum) as high as 0.1, which is among the highest reported for helical polymer assemblies and is critical for chiroptical device applications.