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Ferroelectric materials, traditionally comprising inorganic ceramics and polymers, are commonly used in medical implantable devices. However, their nondegradable nature often necessitates secondary surgeries for removal. In contrast, ferroelectric molecular crystals have the advantages of easy solution processing, lightweight, and good biocompatibility, which are promising candidates for transient (short-term) implantable devices. Despite these benefits, the discovered biodegradable ferroelectric materials remain limited due to the absence of efficient design strategies. Here, inspired by the polar structure of polyvinylidene fluoride (PVDF), a ferroelectric molecular crystal 1H,1H,9H,9H-perfluoro-1,9-nonanediol (PFND), which undergoes a cubic-to-monoclinic ferroelectric plastic phase transition at 339 K, is discovered. This transition is facilitated by a 2D hydrogen bond network formed through O-H···O interactions among the oriented PFND molecules, which is crucial for the manifestation of ferroelectric properties. In this sense, by reducing the number of -CF 2 - groups from ≈5 000 in PVDF to seven in PFND, it is demonstrated that this ferroelectric compound only needs simple solution processing while maintaining excellent biosafety, biocompatibility, and biodegradability. This work illuminates the path toward the development of new biodegradable ferroelectric molecular crystals, offering promising avenues for biomedical applications., (© 2024 Wiley‐VCH GmbH.)

As particles carry quantified energy, photon radiation enables orbital transitions of energy levels, leading to changes in the spin state of electrons. The resulting switchable structural bistability may bring a new paradigm for manipulating ferroelectric polarization. However, the studies on molecular orbital breaking in the ferroelectric field remain blank. Here, for the first time, a new mechanism of ferroelectrics-dual breaking of molecular orbitals and spatial symmetry, demonstrated in a photochromic organic crystal with light-induced polarization switching, is formally proposed. By alternating the ultraviolet/visible light irradiation, the states of electron spin and the radial distribution p atomic orbitals experience a change, showing a reversible switch from "shoulder-to-shoulder" form to a "head-to-head" form. This reflects a reversible conversion between π and σ bonds, which induces and couples with the variation of spatial symmetry. The intersection of spatial symmetry breaking and molecular orbital breaking in ferroelectrics present in this work will be more conducive to data encryption and anticounterfeiting., (© 2023 Wiley-VCH GmbH.)

Organosilicons have been used extensively in aerospace, electronics, food, medicine and other fields, due to their low viscosity, hydrophobicity, corrosion resistance, non-toxic, and physiologically inert features. Despite extensive interest, however, organosilicon ferroelectric crystals have never been found. Here, by using the chemical design strategy, we successfully obtained a molecular ferroelectric D-chiro-inositol-SiMe 3 with polar P4 3 symmetry, whose spontaneous polarization can be electrically switchable on thin film. The introduction of organosilicon groups endows the thin films with excellent softness, ductility and flexibility (extremely low hardness of 72.8 MPa and small elastic modulus of 5.04 GPa) that are desirable for biomedical and human-compatible applications. As the first case of organosilicon ferroelectric crystal to date, this work offers a new structural paradigm for molecular ferroelectrics, and highlights their potential for flexible bio-electronic applications., (© 2022 Wiley-VCH GmbH.)

Organic-inorganic hybrid perovskites (OIHPs) have gained tremendous interest for their rich functional properties. However, the coexistence of more than one of ferroelectricity, ferromagnetism and ferroelasticity has been rarely found in OIHPs. Herein, we report a two-dimensional Cr 2+ -based OIHP, [3,3-difluorocyclobutylammonium] 2 CrCl 4 ([DFCBA] 2 CrCl 4 ), which shows both ferroelectricity and ferromagnetism. It undergoes a 4/mmmFm type ferroelectric phase transition at a temperature as high as 387 K and shows multiaxial ferroelectricity with a saturate polarization of 2.1 μC cm -2 . It acts as a soft ferromagnet with a Curie temperature of 32.6 K. This work throws light on the exploration of OIHPs with the coexistence of ferroelectricity and ferromagnetism for applications in future multifunctional smart devices., (© 2022 Wiley-VCH GmbH.)

A high transition temperature (T c ) is essential for the practical application of ferroelectrics as electronic devices under extreme thermal conditions in the aerospace, automotive, and energy industries. In recent decades, the isotope effect and strain engineering are found to effectively modulate T c ; however, these strategies are limited to certain systems. Developing simple, universal, and practical methods to improve T c has become an imminent challenge for expanding the applications of ferroelectrics. Here, by adopting a molecular design strategy involving H/F substitution on an organic-inorganic hybrid perovskite (1-azabicyclo[2.2.1]heptane)CdCl 3 at a T c of 190 K, the successful synthesis of a multiaxial, ferroelectric hybrid perovskite (4-fluoro-1-azabicyclo[2.2.1]heptane)CdCl 3 is reported, which demonstrates a large spontaneous polarization of 11.2 µC cm -2 (greater than that of polyvinylidene difluoride) and a T c of 419 K (greater than that of BaTiO 3 ). This temperature enhancement (229 K) is the largest reported for molecular ferroelectrics, far exceeding the reported enhancements induced by the isotope effect and other techniques. This pioneering technique provides an effective and universal method for improving T c in ferroelectrics and represents an important step toward the development of high-performance ferroelectric technology., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Molecular ferroelectrics have attracted considerable interests because of their easy and environmentally friendly processing, low acoustical impedance and mechanical flexibility. Herein, a molecular thermochromic ferroelectric, N,N'-dimethyl-1,4-diazoniabicyclo[2.2.2]octonium tetrachlorocuprate(II) ([DMe-DABCO]CuCl 4 ) is reported, which shows both excellent ferroelectricity and intriguing thermochromism. [DMe-DABCO]CuCl 4 undergoes a ferroelectric phase transition from Pca2 1 to Pbcm at a significantly high Curie temperature of 413 K, accompanied by a color change from yellow to red that is due to the remarkable deformation of [CuCl 4 ] 2- tetrahedron, where the ferroelectric and paraelectric phases correspond to yellow and red, respectively. Combined with multiple bistable physical properties, [DMe-DABCO]CuCl 4 would be a promising candidate for next-generation smart devices, and should inspire further exploration of multifunctional molecular ferroelectrics., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Since the first perovskite CaTiO 3 was discovered in 1839, the development of perovskite has a history of 180 years. The emergence of solar cells (CH 3 NH 3 )PbI 3 has set off the trend of hybrid organic-inorganic perovskite (HOIP) materials. Since then, various HOIPs have sprung up and been widely used in various material devices. Among them, HOIP ferroelectrics have gained widespread attention. However, antiperovskite, as a twin brother of perovskite, has been neglected although it has similar structure with perovskite. Here, we successfully found that [C 3 H 7 FN] 3 [SnCl 6 ]Cl has a three-dimensional (3D) antiperovskite structure with the formula M 3 AB. Importantly, the compound exhibits obvious ferroelectric properties with an Aizu notation of 622F6 at 391 K. To the best of our knowledge, this is the first 3D hybrid organic-inorganic antiperovskite ferroelectric, which will greatly promote the development of antiperovskite families with more superior physical properties., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A ferroelectric with a high phase-transition temperature (T c ) is an indispensable condition for practical applications. Over the past decades, both strain engineering and the isotope effect have been found to effectively improve the T c within ferroelectric material systems. However, the former strategy seems to prefer working in inorganic ferroelectric thin films, while the latter is also limited to some certain systems, such as hydrogen-bonded ferroelectrics. It is noted that a mono-fluorinated molecule is geometrically very similar to its parent molecule and the substitution of H by an F atom can introduce a chiral center on the molecule to template or stabilize polar structures. Significantly, the barrier of rotation of the fluorinated organic molecules is raised, resulting in a remarkable increase in T c . Herein, by applying the molecular design strategy of H/F substitution to the organic-inorganic perovskite ferroelectric (pyrrolidinium)CdCl 3 with a low T c of 240 K, two high-T c chiral perovskite ferroelectrics, (R)- and (S)-3-F-(pyrrolidinium)CdCl 3 are successfully synthesized, for which the T c reaches 303 K. The significant enhancement of 63 K in T c extends the ferroelectric working temperature range to room temperature. This finding provides a new effective way to regulate the T c in ferroelectrics and to design high-T c molecular ferroelectrics., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

2D organic-inorganic lead iodide perovskites have recently received tremendous attention as promising light absorbers for solar cells, due to their excellent optoelectronic properties, structural tunability, and environmental stability. However, although great efforts have been made, no 2D lead iodide perovskites have been discovered as ferroelectrics, in which the ferroelectricity may improve the photovoltaic performance. Here, by incorporating homochiral cations, 2D lead iodide perovskite ferroelectrics [R-1-(4-chlorophenyl)ethylammonium] 2 PbI 4 and [S-1-(4-chlorophenyl)ethylammonium] 2 PbI 4 are successfully obtained. The vibrational circular dichroism spectra and crystal structural analysis reveal their homochirality. They both crystalize in a polar space group P1 at room temperature, and undergo a 422F1 type ferroelectric phase transition with transition temperature as high as 483 and 473.2 K, respectively, showing a multiaxial ferroelectric nature. They also possess semiconductor characteristics with a direct bandgap of 2.34 eV. Nevertheless, their racemic analogue adopts a centrosymmetric space group P2 1 /c at room temperature, exhibiting no high-temperature phase transition. The homochirality in 2D lead iodide perovskites facilitates crystallization in polar space groups. This finding indicates an effective way to design high-performance 2D lead iodide perovskite ferroelectrics with great application prospects., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The perovskite structure is rich in ferroelectricity. In contrast, ferroelectric antiperovskites have been scarcely confirmed experimentally since the discovery of M 3 AB-type antiperovskites in the 1930s. Ferroelectricity is now revealed in an organic-inorganic hybrid X 3 AB antiperovskite structure, which exhibits a clear ferroelectric phase transition 6/mmmF6mm with a high Curie point of 480 K. The physical properties across the phase transition are obviously changed along with the symmetry requirements, providing solid experimental evidence for the ferroelectric phase transition. More interestingly, the discovered antiperovskite shows intense photoluminescence and triboluminescence properties. The confirmation of the triboluminescent ferroelectric antiperovskite will open new avenues to explore excellent optoelectronic properties in the antiperovskite family., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Narrow band gaps and excellent ferroelectricity are intrinsically paradoxical in ferroelectrics as the leakage current caused by an increase in the number of thermally excited carriers will lead to a deterioration of ferroelectricity. A new molecular ferroelectric, hexane-1,6-diammonium pentaiodobismuth (HDA-BiI 5 ), was now developed through band gap engineering of organic-inorganic hybrid materials. It features an intrinsic band gap of 1.89 eV, and thus represents the first molecular ferroelectric with a band gap of less than 2.0 eV. Simultaneously, low-temperature solution processing was successfully applied to fabricate high-quality ferroelectric thin films based on HDA-BiI 5 , for which high-precision controllable domain flips were realized. Owing to its narrow band gap and excellent ferroelectricity, HDA-BiI 5 can be considered as a milestone in the exploitation of molecular ferroelectrics, with promising applications in high-density data storage and photovoltaic conversion., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A dual-function material in which ferroelectricity and spin crossover coexist in the same temperature range has been obtained. Our synthetic strategy allows the construction of acentric crystal structures in a predictable way and is based on the high directionality of hydrogen bonds. The well-known iron(II) spin crossover complex [Fe(bpp) 2 ] 2+ (bpp=2,6-bis(pyrazol-3-yl)pyridine), a four-fold noncentrosymmetric H-bond donor, was combined with a disymmetric H-bond acceptor such as the isonicotinate (isonic) anion to afford [Fe(bpp) 2 ](isonic) 2 ⋅2 H 2 O. This low-spin iron(II) compound crystallizes in the acentric nonpolar I4‾ space group and shows piezoelectricity and SHG properties. Upon dehydration, it undergoes a single-crystal to single-crystal structural rearrangement to a monoclinic polar Pc phase that is ferroelectric and exhibits spin crossover., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An outstanding advantage of inorganic ceramic ferroelectrics is their usability in the polycrystalline ceramic or thin film forms, which has dominated applications in the ferroelectric, dielectric, and piezoelectric fields. Although the history of ferroelectrics began with the molecular ferroelectric Rochelle salt in 1921, so far there have been very few molecular ferroelectrics, with lightweight, flexible, low-cost, and biocompatible superior properties compared to inorganic ceramic ferroelectrics, that can be applied in the polycrystalline form. Here, a multiaxial molecular ferroelectric, guanidinium perchlorate ([C(NH 2 ) 3 ]ClO 4 ), with a record-high phase transition temperature of 454 K is presented. It is the rectangular polarization-electric field (P-E) hysteresis loops recorded on the powder and thin film samples (with respective large P r of 5.1 and 8.1 µC cm -2 ) that confirm the ferroelectricity of [C(NH 2 ) 3 ]ClO 4 in the polycrystalline states. Intriguingly, after poling, the piezoelectric coefficient (d 33 ) of the powder sample shows a significant increase from 0 to 10 pC N -1 , comparable to that of LiNbO 3 single crystal (8 pC N -1 ). This is the first time that such a phenomenon has been observed in molecular ferroelectrics, indicating the great potential of molecular ferroelectrics being used in the polycrystalline form like inorganic ferroelectrics, as well as being viable alternatives or supplements to conventional ceramic ferroelectrics., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)