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 H2O 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. A solvent selective effect for the regulation of ferroelasticity and ferroelectricity of anilinium bromide is described, which is unprecedented in organic molecular ferroelectrics. Two forms of crystal structure were obtained from different crystallization solvents: ferroelastic AB‐1 and ferroelectric AB‐2. Atom key: Br (green), N (blue), H (light blue), C (gray).