A Decoupled‐Motif Strategy Directs Supramolecular Charge‐Transfer Architectures Toward Efficient Photocatalytic H 2 Evolution

ABSTRACT 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 H 2 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.