Abstract

AbstractOrganic radical ferroics such as TEMPO have attracted widespread interest. However, the relatively low Curie temperature of 287 K and melting point of 311 K severely hinder its application potential. Despite extensive interest, high‐temperature radical ferroics have not yet been found. Here, taking advantage of chemical design and supramolecular radical chemistry, we designed two high‐temperature organic supramolecular radical ferroics [(NH3‐TEMPO)([18]crown‐6)](ReO4) (1) and [(NH3‐TEMPO)([18]crown‐6)](ClO4) (2), which can retain ferroelectricity up to 413 K and 450 K, respectively. To our knowledge, they are both the first supramolecular radical ferroics and unprecedented high‐temperature radical ferroics, where the supramolecular component is vital for the stabilization of the radical and extending the working temperature window. Both also have paramagnetism, non‐interacting spin moments, and excellent piezoelectric and electrostrictive behaviors comparable to that of LiNbO3.

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