Donor-Acceptor Engineering Enables Kinetic Control of Chirality Transfer in Side Chain Polymers.

Chirality transfer across hierarchical architectures represents a pivotal and underexplored challenge in the design of functional chiral materials. Through molecular engineering integrating chiral α-terminal groups with electronically tunable azobenzene (Azo) side chains, we demonstrate that in kinetically trapped aggregates of side chain Azo polymers, the dipole moment of the chromophore, modulated by terminal electron-donating (Donor, D) or withdrawing (Acceptor, A) substituents, dictates the absolute inversion of the resulting supramolecular helix. The substituent-dependent dipole reorientation cascades into long-range helical reorganization via π-π and van der Waals cooperativity, ultimately governing whether chirality transfer follows thermodynamic preference, undergoes inversion, or exhibits multiplexed behavior. This electronically driven chirality inversion transcends classical steric models and establishes a transformative framework for designing adaptive chiral materials with programmable handedness, offering promising applications in photonic circuits, enantioselective nanosensors, and bioinspired metamaterials.