Hybrid perovskites are a technologically relevant family of materials, with potential applications in photovoltaics, solid-state lighting, and radiation detection. Interactions between the inorganic octahedral framework and the organic sublattice have been implicated in the structure and optoelectronic properties, but characterization of these interactions has been challenging, because of competition between organic-inorganic coupling and intraoctahedral interactions. Owing to their decreased octahedral connectivity, vacancy-ordered double perovskites present an ideal case study to examine organic-inorganic coupling in hybrid perovskites and their derivatives. Here, we describe the low-temperature, hysteretic phase transition of formamidinium tin(IV) iodide from the high-symmetry cubic phase to a lower-symmetry monoclinic phase. We propose that the hysteresis stems from organic-inorganic coupling mediated by local and spontaneous strain from the orientations of the formamidinium cations, which result in a ferroelastic phase transition.
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