Organic radical ferroelectric crystals with martensitic phase transition

Organic martensitic compounds are an emerging type of smart material with intriguing physical properties including thermosalient effect, ferroelasticity, and shape memory effect. However, due to the high structural symmetry and limited design theories for these materials, the combination of ferroelectricity and martensitic transformation has rarely been found in organic systems. Here, based on the chemical design strategies for molecular ferroelectrics, we show a series of asymmetric 1,4,5,8-naphthalenediimide derivatives with the homochiral amine and 2,2,6,6-tetramethylpiperidine-N-oxyl components, which adopt the low-symmetric polar structure and so allow ferroelectricity. Upon H/F substitution, the fluorinated compounds exhibit reversible ferroelectric and martensitic transitions at 399 K accompanied by a large thermal hysteresis of 132 K. This large thermal hysteresis with two competing (meta)-stable phases is further confirmed by density functional theory calculations. The rare combination of martensitic phase transition and ferroelectricity realizes the bistability with two different ferroelectric phases at room temperature. Our finding provides insight into the exploration of martensitic ferroelectric compounds with potential applications in switchable memory devices, soft robotics, and smart actuators.