The extraordinary thermal stability of [NH₂CHNH₂]₃Bi₂I₉ (FA₃Bi₂I₉) crystals, up to around 600 K, has been enhanced by using the evaporating method. DSC measurements have revealed reversible structural phase transitions: at 203 K (Phase I → Phase II), 173 K (II → III), 134.7 K (III → IV), 131.4 K (IV → V), and 120 K (V → VI). The crystal structures of FA₃Bi₂I₉ adopt the polar space groups P6₃mc at 220 K (Phase I) and Cmc2₁ at 190 K (Phase II). The pyroelectric current (I_pyr) measured in the temperature range covering all the phases of FA₃Bi₂I₉ confirmed their polar nature. The reversibility of the spontaneous polarization in each phase has been confirmed by the observed hysteresis loops. All the phase transitions are dielectrically active. The dielectric response (ε*(ω,T) close to 134.7 and 131.4 K) is characteristic of ferroelectrics with a critical slowing-down process. Optical bandgaps estimated from the UV-vis measurements and calculated using the DFT method are equal to 1.85 and 1.89 eV, respectively. On the basis of the structural, dielectric, and spectroscopic results, the molecular mechanisms of the phase transitions have been proposed.

Ferroelectric properties of haloantimonates(III) and halobismuthates(III) have been detected for as much as 40 structures belonging to 7 different types of anionic networks, with RMX₄, R₂MX₅, R₃M₂X₉, and R₅M₂X₁₁ stoichiometries being the most frequently reported to host these properties. We report on the first ferroelectric of the halobismuthate(III) family with a R₃MX₆ stoichiometry, that is, tris(acetamidinium)hexabromobismuthate(III), ₃C(NH₂)₂)₃[BiBr₆] (ABB), characterized by a one-component organic network. While the stoichiometry and crystal packing of ABB might seem uncomplicated, the temperature-resolved structural and spectroscopic studies paint a different picture in which rich polymorphism in the solid state occurs between tetragonal (paraelastic) and triclinic (ferroelastic) crystal phases: I (P4₂/n) → II (P1̅) at 272/277 K (cooling/heating), II (P1̅) → III (P1̅) at 207 K, and III (P1̅) → IV (P1) at 98/127 K. The ferroelectric properties of phase IV have been confirmed by the pyroelectric current and hysteresis loop measurements; additionally, the acentric symmetry has been further supported by second harmonic generation measurements. Crystallographic analysis of phase III reveals the antiparallel alignment of acetamidinium dipoles, pointing to the antiferrroelectric nature of this phase. The ferroelectric transition (III → IV) also reveals a mixed nature: an anionic substructure subject to “displacive” and a cationic substructure to “order–disorder” changes. In turn, the character of the ferroelectric transition (III → IV) should be considered as “displacive” for both cationic and anionic substructures.) In this report, we also explore the two-photon absorption property of ABB at 800 nm, a property that is unexplored for any halobismuthate(III) thus far. We also present periodic ab initio calculations for ABB crystals. The Berry-phase approach at the Hartree–Fock and density functional theory (DFT-D3) method levels is employed for spontaneous polarization calculations. The origin of ferroelectric polarization is studied using DFT-D3 and RHF electronic structure calculations, emphasizing the relationship between P_s and the relative orientation of organic/inorganic components.

We report the physicochemical characteristics of a novel Sb-based formamidinium ferroelectric material, (NH₂CHNH₂)₃Sb₂I₉ (FAIA). FAIA crystallizes at room temperature in the hexagonal P6₃mc space group. The crystal structure of FAIA is isomorphic to that of its bismuth analog, [NH₂CHNH₂]₃Bi₂I₉ (FAIB), which is characterized by a zero dimensional (0D) anionic network (discrete bioctahedral units). From the DSC results three phase transitions (PT) have been found for FAIA: at 187.4/189 K (phase I ↔ phase II), 177.6/177.9 K (II ↔ III) and 148.2/152.3 K (III ↔ IV). The compound exhibits ferroelectricity in the room temperature phase I and in the successive temperature phases (II and III). The spontaneous polarization (P_S = 0.5 × 10⁻² μC cm⁻²) reversibility has been confirmed by the presence of the ferroelectric hysteresis loops and pyroelectric measurements. The origin of ferroelectricity is discussed in terms of the cationic dynamics. This material may be considered as a semiconductor (σ ∼ 10⁻⁶ S m⁻¹, 300 K).

Novel lead-free ferroelastic materials, (C ₃ N ₂ H ₅ ) ₃ Sb ₂ I ₉ and (C ₃ N ₂ H ₅ ) ₃ Bi ₂ I ₉ , exhibit rich sequences of phase transitions and reveal semiconducting properties.

In halogenoantimonate(III) and halogenobismuthate(III) organic–inorganic hybrids, chains of trans-connected octahedra, trans-[MX₅]_∞, are considered attractive anionic structures for inducing ferroelectricity. The latter is realized by displacing the bridging halogen atoms along the chain direction – the process that changes the polarity of the whole unit. Advances in the identification of such materials have been hindered, however, by substantial difficulty in obtaining such structures. Here we investigate structural and dielectric properties of three families of compounds based on 2-mercaptopyrimidinium, 2-aminopyrimidinium, and 2-amino-4-methylpyrimidinium cations in which 8 out of 12 compounds show trans-[MX₅]_∞ chains in their crystal structures. Two of the compounds adopt a polar P2₁ space group and are potentially ferroelectric. We perform a detailed structural analysis of all compounds with trans-[MX₅]_∞ chains discovered by far to understand the factors that lead to the chains' formation. We reveal that the size of a cation predominantly defines the accessibility of structures with this anionic form and we provide rules for designing hybrids with trans-[MX₅]_∞ chains to help guide future efforts to engineer materials with interesting non-linear electrical properties.