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Since the discovery of TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) in 1973, organic radical ferroics attracted widespread interest among the scientific community. 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 been found to date. Here, taking advantage of chemical design theory and supramolecular radical chemistry, we successfully 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 the 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 plays a vital role in the stabilization of radical and extending working temperature window. Additionally, both of them can also present the paramagnetism and non-interacting spin moments, as well as excellent piezoelectric and electrostrictive behaviors comparable to that of LiNbO3. This work provides an efficient design strategy for enriching the family of high-temperature radical ferroics, and should inspire further exploration of multi-functional organic ferroics.

Chiral perovskites have emerged as a significant class of materials showing promising optoelectronic and spintronic applications. Reports of chiral perovskite ferroelectrics, however, have been scarce. In this work, we have successfully synthesized homochiral lead-iodide perovskite ferroelectrics [(R)-N-(1-phenylethyl)ethane-1,2-diaminium]PbI4 and [(S)-N-(1-phenylethyl)ethane-1,2-diaminium]PbI4 by the chemical design of introducing a methyl group into the organic cation of the parent (N-benzylethane-1,2-diaminium)PbI4. Vibrational circular dichroism spectra identify the chiral mirroring relationship. They both undergo 222F2 type paraelectric-ferroelectric behavior at around 378 K coupled with clear ferroelastic domains "ON/OFF" switching. Besides, they exhibit an evident thermochromism with color change from orange-yellow to orange-red. To our knowledge, the discovery of integrated ferroelectricity, ferroelasticity and reversible thermochromism in chiral perovskites is unprecedented. This finding offers a resultful path to design chiral perovskite ferroelectrics and is of great inspiration to the discovery of multifunctional perovskite materials.