Meltable Hybrid Antimony and Bismuth Iodide One-Dimensional Perovskites

Hybrid lead-halide perovskites have been studied extensively for their promising optoelectronic properties and prospective applications, including photovoltaics, solid-state lighting, and radiation detection. Research into these materials has also been aided by the simple and low-temperature synthetic conditions involved in solution-state deposition/crystallization or melt-processing techniques. However, concern over lead toxicity has plagued the field since its infancy. One of the most promising routes to mitigating toxicity in hybrid perovskite materials is substituting isoelectronic Bi(III) for Pb(II). Various methods have been developed to allow pnictide-based systems to capture properties of the Pb(II) analogues, but the ability to melt extended hybrid pnictide-halide materials has not been investigated. In this work, we prepare a series of one-dimensional antimony- and bismuth-iodide hybrid materials employing tetramethylpiperazinium (TMPZ)-related cations. We observe, for the first time, the ability to melt extended hybrid pnictide-halide materials for both the Sb(III) and Bi(III) systems. Additionally, we find that Sb(III) analogues melt at lower temperatures and attribute this observation to structural changes induced by the increased stereochemical activity of the Sb(III) lone pair coupled with the reduction in effective dimensionality due to steric interactions with the organic cations. Finally, we demonstrate the ability to melt process phase pure thin films of (S-MeTMPZ)SbI₅.