Local Symmetry Breaking in 3D Hybrid Perovskites with 3-Hydroxyazetidinium

Two-dimensional (2D) hybrid perovskite semiconductors with nonprimary ammonium cations (NPACs) have recently attracted interest for spin-optoelectronics owing to the symmetry-breaking distortions in their crystal structures. However, implementing this design strategy in three-dimensional (3D) analogs remains largely unexplored, primarily due to stricter restrictions on cation size. Here, we introduce a family of 3D hybrid perovskites (3DHPs), ASnX₃, where A = 3-hydroxyazetidinium (AzOH; ⁺NH₂(CH₂)₂CHOH) and X = Cl, Br, and I. The choice of a bulky NPAC, coupled with the incorporation of a polar group (-OH), targets broken symmetry within the 3D frameworks. While single-crystal X-ray diffraction analysis reveals spatially averaged centrosymmetric cubic (i.e., <i>Pm</i>-3<i>m</i> space group) unit cells, with the largest lattice parameters among existing ASnX₃ analogs, first-principles molecular dynamics and electronic structure calculations indicate that the relatively fixed dipoles of AzOH within the SnX₆-derived framework introduce local inversion asymmetry and spin polarization. By incorporating a polar cation with limited mobility into the 3D perovskite framework, (AzOH)SnX₃ unlocks potential for spin-optoelectronics, photovoltaics, ferroelectrics, and nonlinear optics.