Supramolecular topology dictates the fate of charge-transfer (CT) excitons in donor-acceptor assemblies. By tailoring the geometric connectivity of NDI-pyrene conjugates (NPCs), we control whether CT channels remain confined or segregate into parallel pathways. Confined topologies localize electron-hole pairs to form emissive CT states, while segregated double-cable architectures facilitate long-range charge migration for visible-light-driven H2 evolution. Comprehensive structural and photophysical analyses collectively reveal how topology transforms excited-state dynamics into distinct photochemical outcomes. This study highlights the design principle of using geometric confinement to link supramolecular assembly with photocatalytic function.
Lo et al. (Thu,) studied this question.