Jahn-Teller Distortion-Enabled Interfacial Chemical Recognition for Chiral Hybrid Halides: (R/S-3AP)BiCl5.
Wu Yuxuan Y, Pei Can C, Zhang Yujie Y, Liu Haonan H et al.
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.