Programming supramolecular polymer network topology via homochiral self-sorting

While stereochemistry has a strong influence on polymer structure and assembly, its use as a design handle to regulate polymer network topology remains unexplored. Here we demonstrate that homochiral self-sorting can be harnessed to suppress primary loops in end-linked polymer networks. We synthesized linear polymers terminated with heterochiral bi-2-naphthol-based ligands that cross-link via palladium(II)-mediated Pd₂L₄ metal-organic cage (MOC) assembly. This design exploits a thermodynamic preference for homochiral MOCs, enforcing a bias against intramolecular cyclization. Compared with networks formed from homochiral polymers, which can form primary loops through MOC formation, networks formed from heterochiral polymers exhibit lower primary loop densities and enhanced mechanical properties. The presence of sacrificial loops at low concentrations also enables topology editing by adding functionalized free ligands with minimal impact on network integrity. This work establishes chiral self-sorting as a versatile approach to controlling polymer topology and provides a generalizable strategy for designing robust and functional polymer networks.