Above-Room-Temperature Ferroelastic Phase Transitions in Two Tetrafluoroborate-Based Hexagonal Molecular Perovskites

This is the authors' abstract. We don't add key points for this paper.

ABX₃-type molecular perovskites provide an important platform to tune phase transitions, via judiciously choosing A-, B-, and X-site components, to approach advanced functional materials for applications. Although tetrafluoroborate can act as X-site component to assemble ten instances of ABX₃ molecular perovskites, only two of them possess hexagonal perovskite structures. Herein, we report two tetrafluoroborate-based hexagonal molecular perovskites, A[Na(BF₄)₃], by judiciously choosing two different A-site cations: 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium (Hmdabco²⁺) for 1 and 1-methylpiperazine-1,4-diium (H₂mpz²⁺) for 2. They have high-temperature phases in the same space group (P6₃/mmc) revealing highly disordered A-site cations. Upon cooling, 1 undergoes two-step P6₃/mmc ↔ P3̅c1 ↔ P2₁/n transitions at 344 and 338 K, respectively, including a ferroelastic one (3̅mF2/m) accompanied by a spontaneous strain of 0.013. In contrast, the smaller H₂mpz²⁺ cation with more adoptable conformations induces a one-step sharp P6₃/mmc ↔ P2₁/c ferroelastic transition (6/mmmF2/m(s)) at 418 K in 2, leading to more significant symmetry breaking and a considerable spontaneous strain of 0.129. This study provides important clues to modulate structural phase transitions by tuning diverse components for the multicomponent dense hybrid crystals.