Two metal-free perovskite molecules with different 3D frameworks show reversible phase transition, dielectric anomaly and SHG effect.

Three-dimensional (3D) hybrid organic-inorganic perovskites (HOIPs) have attracted tremendous research interest due to their unique structure and promising applications. However, research on the design, synthesis and properties of this kind of metal-free crystalline material is still in the exploratory stage. Herein, two 3D perovskite molecules [1,4-3.2.2-dabcn]NH 4 Br 3 (1) and [1,4-3.2.2-dabcn]NH 4 I 3 ·0.5H 2 O (2) were obtained by reacting 1,4-diazabicyclo[3.2.2]nonane (1,4-3.2.2-dabcn) with NH 4 X (X = Br and I) in the corresponding concentrated halogen acids. The single X-ray diffraction results demonstrated that the inorganic framework structures in compounds 1 and 2 constructed with NH 4 Br and NH 4 I are completely different, caused by the radius of the bromide ion being smaller than that of the iodide ion. The 3D framework of compound 1 is constructed with a coplanar dimer [(NH 4 ) 2 Br 6 ] 2- as the basic building unit, leading to the expanded 3D perovskite framework structure with a larger cavity to accommodate the 1,4-3.2.2-dabcn molecule. Nevertheless, compound 2 adopts a familiar 3D crystal framework structure with corner-sharing [(NH 4 )I 6 ] octahedra, where the [1,4-3.2.2-dabcn] cations and water solvent molecule are confined in the cavities enclosed by the octahedra. Notably, both compounds exhibit reversible phase transition, dielectric anomaly and the second harmonic generation (SHG) effect. From the perspective of molecular design, this work is of great significance to guide the construction of new 3D metal-free perovskite molecular materials with reversible properties.