π–hole forces enabled programmable supramolecular chirality based on a chiral benzimidazole pincer

Employing noncovalent forces to fabricate self-assembled nanoarchitectures composed of multiple constituents regulates the expression of chirality across hierarchical levels. Here we report a programmed hierarchical chiral assembly through π-hole interactions synchronized with hydrogen bonding. A chiral molecular pincer composed of benzimidazole and cholesteryl moieties capable of forming complementary hydrogen bonds with carboxylic acids, coassembles with achiral organic acids to generate one-dimensional helical superstructures, enhancing the expression of supramolecular chirality and chiroptical activities. The multicomponent coassembly system accommodates structurally diverse acids-including aliphatic, aromatic, and polymeric acids-exhibiting pronounced substrate-dependent induction of supramolecular chirality. Further incorporating fluorinated or chlorinated components introduced π-hole forces that realize modulation of the macroscopic chirality, affording well-defined chiral microarchitectures with tunable topology and chirality. The resulting materials display complex yet highly ordered chiral nanostructures, with the potential for anisotropic growth toward macroscopic scales. This study establishes a modular platform for the high-throughput fabrication of chiroptical materials with tunable supramolecular chirality, offering insights into the rational design of functional soft materials through π-hole interaction driven hierarchical self-assembly.