High-temperature ferroelastic phase transition in a perovskite-like complex: [Et4N]2[PbBr3]2

A new lead-bromide hybrid organic-inorganic complex [Et4N](2)[PbBr3](2) (Et = ethyl) was synthesized, and its crystal structures could be described as a distorted perovskite-like one (at room temperature phase and at high temperature phase) and a step-like dielectric anomaly was obtained at around 375 K upon heating and 367 K upon cooling. It underwent a reversible structural phase transition with the Aizu notation of 6/mmmF2/m belonging to one of the 94 species of ferroelastic phase transitions, displayed switchable dielectric behaviors triggered by the motion or reorientation of the tetraethylammonium cations and the displacement of Pb2+ and Br- ions in a solid-state crystal. Ferroelastic domain walls were also observed in atomic-force microscopy. Differential scanning calorimetry, dielectric measurements and variable-temperature X-ray structure determinations indicated this complex exhibited a dielectric anomaly associated with the structural phase transition. All of these demonstrate its potential application as a temperature switchable molecular dielectric material in the ferroic-related field.