Modulating the Supramolecular Helicity of Poly(m-phenylenediamine) by Achiral Monomer Copolymerization

Abstract Designing artificial systems to mimic chiral superstructures and exploring how achiral molecules precisely modulate their chirality are crucial to understand the origin of homochirality in nature. Herein, we report that when using conventional supramolecular transcription methods to prepare chiral poly(m-phenylenediamine), simply introducing various small amounts of achiral diaminopyridines (DAPs) to copolymerize with m-phenylenediamine (MPD) enables the resulting chiral copolymers with adjustable helical configurations and chiroptical activities in an enantiopure template system. The strong hydrogen bonds between DAPs and the template molecules (L/D-PhgC16) proved to be the driving-force for guiding the chiral polymerization mode of MPD. Impressively, the exquisite self-sorting phenomenon is observed by tuning the stoichiometric ratio of DAP and D-PhgC16, where the as-prepared copolymers with opposite helicity can exist simultaneously to form a double network structure and their chiroptical activity could be well regulated. Furthermore, based on such a copolymerization strategy, we have built a conceptual library of helical functional copolymers with editable polymer types including conducting polymers and designable amine-aldehyde condensation-based polymers. This copolymerization-mediated synthetic protocol may facilitate the development of chiral polymers with controlled morphologies and dynamic compositions.