Three‐dimensional organic–inorganic hybrid sodium halide perovskite: C 4 4 H 12 12 N 2 2 ·NaI 3 3 and a hydrogen‐bonded supramolecular three‐dimensional network in 3C 4 4 H 12 12 N 2 2 ·NaI 4 4 ·3I·H 2 2 O

摘要

The rational selection of ligands is vitally important in the construction of new organic–inorganic hybrid three‐dimensional perovskite complexes. As part of an exploration of perovskite‐type materials, two new Na–I compounds based on the piperazine ligand, namely poly[piperazinediium [tri‐μ‐iodido‐sodium]], {(C 4 H 12 N 2 )[NaI 3 ]} n , 1 , and catena ‐poly[tris(piperazinediium) [[triiodidosodium]‐μ‐iodido] triiodide monohydrate], {(C 4 H 12 N 2 ) 3 [NaI 4 ]I 3 ·H 2 O} n , 2 , have been synthesized by adjusting the stoichiometric ratio of sodium iodide and piperazine, and were characterized by single‐crystal X‐ray diffraction. In the crystal structures of 1 and 2 , each Na I cation is linked to six I atoms, but the compounds show completely different configurations. In 1 , the structure includes a perovskite‐like array of vertex‐sharing NaI 6 octahedra stretching along the direction of the three axes, and each piperazinediium dication is enclosed in the NaI 3 perovskite cage. However, in 2 , each Na I atom bridges a single I atom to form a one‐dimensional linear chain, and complex intermolecular hydrogen bonds connect these one‐dimensional chains into a three‐dimensional supramolecular network.