Observation of Transition from Ferroelasticity to Ferroelectricity by Solvent Selective Effect in Anilinium Bromide.

Organic ferroelectrics are highly desirable for their light weight, mechanical flexibility and biocompatibility. However, the rational design of organic ferroelectrics has always faced great challenges. Anilinium bromide (AB) has two structures reported in the Cambridge Crystallographic Data Centre, which might be an mmmF2/m type ferroelastic (AB-1). When we studied its ferroelasticity, we were surprised to discover that there was another crystal (AB-2) in H2 O besides this one, and they were very difficult to separate. By changing the solvent, we found that AB-1 crystals could be formed in ethanol, where ferroelastic domains were visualized by polarized light microscopy, and AB-2 crystals could be obtained from various crystallization solvents of methanol, isopropanol, N-butanol, acetonitrile, dimethyl sulfoxide, and N,N-dimethylformamide, which undergo a ferroelectric phase transition with mm2Fm, showing clear ferroelectricity in two phases. To our knowledge, the regulation of ferroelasticity to ferroelectricity by solvent selective effect is unprecedented in the field of ferroelectrics. This work reveals the important role of solvent effect in organic ferroelectrics.

Dehydration-activated structural phase transition in a two-dimensional hybrid double perovskite.

As a feasible lead-free scheme, organic-inorganic hybrid double perovskites show many excellent properties, including ferroelectricity, ferroelasticity, self-powered circularly polarized light detection and so on. In this work, the solid-to-solid structural phase transition of a two-dimensional hybrid double perovskite (CHA)4CuBiI8 was successfully activated via the dehydration of (CHA)4CuBiI8·H2O, which was proven by differential scanning calorimetry (DSC) and temperature-dependent dielectric measurements. Using variable-temperature single-crystal X-ray diffractometry, the cause behind the phase transition of (CHA)4CuBiI8 was determined to be the overall coordination of distortion and movement of the inorganic skeleton and thermal deformation of the cationic structure. In addition, the substance after dehydration shows good stability in multiple reversible switching during dielectric tests. The interesting dehydration-activated results of the material contribute towards a further expansion of the properties and potential application of hybrid double perovskites.

Metal ion modulation triggers dielectric double switching and green fluorescence in A2MX4-type compounds.

Multifunctional switching materials show great potential for applications in sensors, smart switches, and other fields due to their ability to integrate different physical channels in one single device. However, multifunctional responsive materials with multiple switching and luminescence properties have rarely been reported. Here, we report three organic-inorganic hybrids: [TMAA]2[CoCl4] (compound 1), [TMAA]2[CdBr4] (compound 2) and [TMAA]2[MnCl4] (compound 3). Compound 1 and compound 2 undergo two reversible phase transitions at high temperature (328.95/359.25 K and 350.45/393.15 K, respectively). Since the inorganic skeleton has a strong influence on the luminescence properties of such structured substances, Cd and Co were replaced with Mn, after which compound 3 was obtained as expected. The above strategy triggered bright green luminescence with a quantum yield of 35.19%, and significantly increased the phase transition temperature of compound 3 to above 400 K. The above results show that the regulation of the inorganic skeleton provides a new strategy for researchers to develop dual phase change/luminous materials.