Jahn-Teller Distortion-Enabled Interfacial Chemical Recognition for Chiral Hybrid Halides: ( R/S -3AP)BiCl5

Abstract Noncentrosymmetric (NCS) materials with intrinsic chirality are highly desirable for diverse symmetry-dependent functional applications, yet their rational construction remains challenging because asymmetric building units frequently undergo centrosymmetric packing during crystallization. Herein, we develop a Jahn–Teller distortion-enabled interfacial chemical recognition strategy to realize the chiral hybrid halides (R/S-3AP)BiCl5 crystallizing in the chiral NCS space group P212121. The stereochemically active 6s2 lone pair of Bi3+ induces anisotropic distortion of the [BiCl6] octahedra, creating chemically differentiated chloride acceptor sites. Meanwhile, the chiral 3-aminopyrrolidine cations (3AP2+) exhibit two chemically distinct nitrogen centers with differentiated protonation behaviors, producing pyrrolidinium and ammonium N–H donors with distinct hydrogen-bonding capabilities. The stronger donor ability of exocyclic ammonium (NH3+) sites enables preferential N–H···Cl interactions with chloride sites possessing enhanced acceptor characteristics, establishing a chemically complementary organic–inorganic interface. This directional donor–acceptor recognition regulates chiral cation orientations and promotes chirality transfer from molecular units to the extended crystalline framework. This work demonstrates that coupling Jahn–Teller distortion-mediated acceptor regulation with protonation-dependent donor differentiation provides an effective strategy for programming directional interfacial chemical recognition and translating local structural asymmetry into macroscopic chiral ordering in NCS crystals.