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

Chem Asian J. 2024 Mar 7:e202400048. doi: 10.1002/asia.202400048. Online ahead of print.ABSTRACTLow-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 when 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 443 K (in cooling step).PMID:38454534 | DOI:10.1002/asia.202400048
Source: Chemistry, an Asian Journal - Category: Chemistry Authors: Source Type: research