Chiral Binaphthyl[n]arene Gel: Controlled Gelation Ability and Stepwise Amplification of Circularly Polarized Luminescence

Abstract The construction of circularly polarized luminescence (CPL) materials through self‐assembly of chiral macrocycles has garnered significant attention. However, controlling their nanostructure morphology and understanding chirality amplification mechanisms remain challenging. Here, a series of chiral macrocyclic homologs containing varying numbers of binaphthyl units (binaphthyl[n]arene, denoted as n , n = 2–5) are synthesized in a single‐step reaction. All macrocycles exhibited CPL, with stronger chiral amplification observed in smaller homologs, 2 and 3 , showing dissymmetry factors (| g _lum |) of sixfold and 2.75‐fold, respectively, compared to the monomer. These smaller homologs form supramolecular gels in various solvents, while larger ones yield amorphous precipitates. Further enhanced CPL is observed in the gels of 2 and 3 , with | g _lum | reaching up to 3.3 × 10 ⁻³ , 8.25‐fold and 5.5‐fold, respectively, compared to the monomer. While the gel of 3 remained stable for months, the gel of 2 transformed to microcrystals over days driven by π‐π interactions. The findings illuminate a macrocyclic strategy to control luminophore arrangement by tuning molecular rigidity and flexibility with macrocycle size, offering a route for creating CPL‐active materials with amplified chirality and gels with controlled stability.