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 sterically demanding, highly emissive diphenylanthracene derivatives, previously considered aggregation-incompetent, can be programmed to form highly ordered supramolecular nanotubes through conformational preorganization via scissor-shaped dimerization. Stepwise π-core expansion from terphenylene to diphenylnaphthalene 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. Structural analyses and all-atom molecular dynamics simulations of nanotubes reveal a herringbone-like chromophore wall that reconciles dense π-stacking with curvature. Strikingly, time-resolved fluorescence anisotropy measurements demonstrate exciton migration along the tube axis (≈55 nm) and around the circumference (≈11 nm). These findings demonstrate that intramolecular folding preorganizes the spatial arrangement of intermolecular interaction sites, thereby directing curved supramolecular assembly and enabling the emergence of complex nanostructures with advanced optoelectronic function in π-systems.
Aizawa et al. (2026) studied this question.