Tailored 2D Hierarchical Architectures via Interfacial Living Supramolecular Polymerization for Enhanced Exciton Migration

ABSTRACT The structural precision of living supramolecular polymerization processes is dictated by nucleation control, conventionally achieved through kinetic trapping of monomers in metastable aggregates or inactive molecular states. However, current strategies for living supramolecular polymerization, relying on bulk‐phase kinetic trapping of monomers, homogenize assembly pathways and hinder hierarchical control. By leveraging the interfacial adsorption of amphiphilic molecules at the liquid–liquid interface, we engineered a self‐limiting single‐molecule film from PDIOH 1 that elevates the nucleation energy barrier, suppressing premature polymerization while enabling pathway‐specific control over hierarchical self‐assembly. The dynamic monolayer drives surface‐catalyzed secondary nucleation at the liquid–liquid interface, programmably yielding epitaxially aligned 2D hierarchical architectures. Introducing interfacial seeds directs epitaxial growth of 2D hierarchical architectures with uniform shapes during living supramolecular polymerization. Remarkably, the excitation fluence–dependent transient absorption studies demonstrate that 2D hierarchical architectures exhibit a much larger exciton diffusion coefficient than that of disorganized fibers formed in the bulk solution. This work provides an interfacial strategy, enabling controllable assembly of 2D hierarchical materials via living supramolecular polymerization.