Helical Ladder Bottlebrush Polymers With Tunable Helicity and Circularly Polarized Luminescence

Abstract

ABSTRACT Helical ladder polymers possess rigid, helically fused backbones that confer distinctive chiroptical properties, yet their integration into polymer brush architectures remains highly challenging. Here, we report the first synthesis of bottlebrush polymers with a helically fused ladder backbone, achieved through acid‐catalyzed intramolecular cyclization followed by controlled ATRP grafting‐from polymerization. By integrating a single‐handed ladder scaffold with flexible, water‐soluble PNIPAM side chains, the resulting architecture markedly enhances the processability and structural tunability of helical ladder polymers. Moreover, the traditional helical ladder, long regarded as completely rigid and static, has been found to exhibit dynamic transition properties. This change was caused by conformational triggering of the thermally driven binaphthyl dihedral angles, which was quantitatively confirmed by the thermodynamic dynamics and molecular dynamics simulations, demonstrating the hierarchy of the transition from axial chirality to helical chirality. Overall, this work establishes a promising synthetic method for helical ladder bottlebrush polymers and demonstrates their potential as versatile platforms for designing dynamic chiral materials.