Organic radical ferroics such as TEMPO have attracted widespread interest. However,the relatively low Curie temperature of 287 Ka nd melting point of 311 Ks everely 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,w ed esigned two high-temperature organic supramolecular radical ferroics [(NH 3 -TEMPO)([18]crown-6)](ReO 4 )( 1)and [(NH 3 -TEMPO)([18]crown-6)](ClO 4 )(2), which can retain ferroelectricity up to 413 Ka nd 450 K, respectively.T oo ur knowledge,t hey are both the first supramolecular radical ferroics and unprecedented hightemperature radical ferroics,w here 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,a nd excellent piezoelectric and electrostrictive behaviors comparable to that of LiNbO 3 .

The well-developed design strategy of molecular modification for assembling molecular ferroelectrics mainly focus on the cations. Herein, by homochiral anionic modification of the non-ferroelectric (quinuclidinium)(HSO4), we designed high-temperature multiaxial organic...

Organic photochromic compounds have been widely investigated for optical memory storage and switches. Very recently, we pioneeringly discovered optical control of ferroelectric polarization switching in organic photochromic salicylaldehyde Schiff base and diarylethene derivatives, differently from the traditional ferroelectrics. However, the study of such intriguing photo-triggered ferroelectrics is still in its infancy and relatively scarce. In this manuscript, we synthesized a pair of new organic single-component fulgide isomers, (E and and 1Z). They undergo prominent photochromism from yellow to red. Interestingly, only polar 1E has been proven to be ferroelectric, while the centrosymmetric 1Z does not meet the basic requirement for ferroelectricity. Besides, experimental evidence shows that the Z-form can be converted to the E-form by light irradiation. More importantly, the ferroelectric domains of 1E can be manipulated by light in the absence of an electric field, benefiting from the remarkable photoisomerization. 1E also adopts good fatigue resistance to the photocyclization reaction. As far as we know, this is the first example of organic fulgide ferroelectric reported with photo-triggered ferroelectric polarization response. This work has developed a new system for studying photo-triggered ferroelectrics and would also provide an expected perspective on developing ferroelectrics for optical applications in trap future.

Organic radical ferroics such as TEMPO have attracted widespread interest. However,the relatively low Curie temperature of 287 Ka nd melting point of 311 Ks everely 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,w ed esigned two high-temperature organic supramolecular radical ferroics [(NH 3 -TEMPO)([18]crown-6)](ReO 4 )( 1)and [(NH 3 -TEMPO)([18]crown-6)](ClO 4 )(2), which can retain ferroelectricity up to 413 Ka nd 450 K, respectively.T oo ur knowledge,t hey are both the first supramolecular radical ferroics and unprecedented hightemperature radical ferroics,w here 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,a nd excellent piezoelectric and electrostrictive behaviors comparable to that of LiNbO 3 .