Folding-mediated self-assembly of sterically demanding π-luminophore dyads into nanotubes exhibiting multidirectional exciton transport

The hierarchical self-assembly of folded proteins into functional nanostructures has long served as a conceptual foundation for designing synthetic polymer systems. However, the efficacy of folding-based strategies in small-molecule assemblies remains largely unproven. Here, we show that highly emissive diphenylanthracene derivatives, previously considered aggregation-incompetent, can be directed to form highly ordered nanotubular structures through conformational preorganization via scissor-shaped dimerization. Stepwise π-core expansion from terphenylene to diphenylanthracene in the foldable supramolecular synthons induces a morphological progression from twisted ribbons to helical coils and, ultimately, to hollow nanotubes. This structural evolution is driven by folding-assisted directional π–π stacking and cooperative hydrogen bonding. The diphenylanthracene-based nanotubes exhibit multidirectional exciton transport enabled by a herringbone-like arrangement of chromophores. These findings demonstrate that folding-mediated self-assembly offers a viable design strategy for integrating hierarchical order and advanced optoelectronic function into π-systems.