0-D and 1-D Perovskite-like Hybrid Bismuth(III) Iodides.

Low-dimensional hybrid bismuth halide perovskites have recently emerged as a class of non-toxic alternative to lead perovskites with promising optoelectronic properties. Here, we report three hybrid bismuth(III)-iodides: 0-D (H2DAC)2Bi2I10 ⋅ 6H2O (H2DAC_Bi_I), 0-D (H2DAF)4Bi2I10 ⋅ 2I3 ⋅ 2I ⋅ 6H2O (H2DAF_Bi_I), and 1-D (H2DAP)BiI5 (H2DAP_Bi_I) (where H2DAC=trans-1,4-diammoniumcyclohexane; H2DAF=2,7-diammoniumfluorene and H2DAP=1,5-diammoniumpentane). Their synthesis, single-crystal X-ray structures, and photophysical properties are reported. The first two compounds comprise edge-sharing [Bi2I10]4- dimers, while the last compound has cis-corner-sharing 1-D chains of [BiI6]3- octahedra. Intercalation of triiodide (I3 -) and iodide (I-) ions enhance electronic coupling between the [Bi2I10]4- of H2DAF_Bi_I, leading to enhanced optical absorption, compared to H2DAC_Bi_I which lacks such intercalants. Furthermore, calorimetric and variable temperature X-ray diffraction measurements suggest a centrosymmetric to non-centrosymmetric phase transition (monoclinic P212121↔orthorhombic Pnma) of H2DAP_Bi_I at 448 K (in heating step) and at 443 K (in cooling step).