Controlled Supramolecular Architecture Transformation from Homopolymer to Copolymer through Competitive Self-Sorting Method

Supramolecular copolymers can not only enrich the diversity of the polymer backbone but also exhibit certain special and improved properties compared with supramolecular homopolymers. However, the synthesis procedure of supramolecular copolymers is relatively complicated and time-consuming. Herein, a simple transformation from an AB₂-based supramolecular hyperbranched homopolymer to an AB₂+CD₂-based supramolecular hyperbranched alternating copolymer by the “competitive self-sorting” strategy is reported. After adding CD₂ monomer, which bears a competitive neutral guest moiety (TAPN) and two receptive benzo-21-crown-7 host moieties (B21C7), to the as-prepared AB₂-type supramolecular hyperbranched homopolymer constructed by the self-assembly of dialkylammonium salt (DAAS, A group)-functionalized pillar[5]arene (MeP5, B groups) monomers, the initial homopolymer structure is disrupted and then reassemble into a new supramolecular hyperbranched alternating copolymer based on the competitive self-sorting interaction between MeP5-TAPN and B21C7-DAAS. This study supplies a convenient approach to directly transform supramolecular homopolymers into supramolecular copolymers. (Figure presented.).