Modulating the ferroelectric phases in cholesteryl-based organic compounds with perfluoroalkyl tail engineering.

Here, we synthesized a series of cholesteryl-based compounds, whose phases and their transformation can be modulated by temperature and the chain length of the fluoroalkyl moieties. To our knowledge, this is the first time that the phase transition could be modulated with perfluoroalkyl tail engineering in organic single-component ferroelectric crystals.

A Homochiral Fulgide Organic Ferroelectric Crystal with Photoinduced Molecular Orbital Breaking.

Thermally triggered spatial symmetry breaking in traditional ferroelectrics has been extensively studied for manipulation of the ferroelectricity. However, photoinduced molecular orbital breaking, which is promising for optical control of ferroelectric polarization, has been rarely explored. Herein, for the first time, we synthesized a homochiral fulgide organic ferroelectric crystal (E)-(R)-3-methyl-3-cyclohexylidene-4-(diphenylmethylene)dihydro-2,5-furandione (1), which exhibits both ferroelectricity and photoisomerization. Significantly, 1 shows a photoinduced reversible change in its molecular orbitals from the 3 π molecular orbitals in the open-ring isomer to 2 π and 1 σ molecular orbitals in the closed-ring isomer, which enables reversible ferroelectric domain switching by optical manipulation. To our knowledge, this is the first report revealing the manipulation of ferroelectric polarization in homochiral ferroelectric crystal by photoinduced breaking of molecular orbitals. This finding sheds light on the exploration of molecular orbital breaking in ferroelectrics for optical manipulation of ferroelectricity.

Discovery of Ferroelectricity in the Fullerene Adduct C60S8.

Fullerenes offer versatile functionalities and are promising materials for a widespread range of applications from biomedicine and energy to electronics. Great efforts have been made to manipulate the symmetries of fullerene and its derivatives for studying material properties and novel effects, such as ferroelectricity with polar symmetry; however, no documentary report has been obtained to realize their ferroelectricity. Here, for the first time, we demonstrated clear ferroelectricity in a fullerene adduct formed by C60 and S8. More is different: the combination of the most symmetric molecule C60 with the highest Ih symmetry and molecule S8 with high D4d symmetry resulted in the polar C60S8 adduct with a low crystallographic symmetry of the C2v (mm2) point group at room temperature. The presented C60S8 undergoes polar-to-polar ferroelectric phase transition with the mm2Fm notation, whose ferroelectricity was confirmed by a ferroelectric hysteresis loop and ferroelectric domain switching. This finding opens up a new functionality for fullerenes and sheds light on the exploration of more ferroelectric fullerenes.

A chiral two-dimensional perovskite-like lead-free bismuth(III) iodide hybrid with high phase transition temperature.

Bismuth(III) iodide perovskites have attracted great attention as lead-free hybrid semiconductors, but they mainly show zero- and one-dimensional structures. Herein, we report the first two-dimensional chiral perovskite-like bismuth(III) iodide hybrid [(S)-3-aminopyrrolidinium I]2Bi2/3I4 (1) with a high phase transition temperature of 408.8 K, higher than most of the reported chiral lead-free hybrid semiconductors.

Dual Breaking of Molecular Orbitals and Spatial Symmetry in an Optically Controlled Ferroelectric.

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.

The First Enantiomeric Stereogenic Sulfur-Chiral Organic Ferroelectric Crystals.

Chiral ferroelectric crystals with intriguing features have attracted great interest and many with point or axial chirality based on the stereocarbon have been successively developed in recent years. However, ferroelectric crystals with stereogenic heteroatomic chirality have never been documented so far. Here, we discover and report a pair of enantiomeric stereogenic sulfur-chiral single-component organic ferroelectric crystals, Rs -tert-butanesulfinamide (Rs -tBuSA) and Ss -tert-butanesulfinamide (Ss -tBuSA) through the deep understanding of the chemical design of molecular ferroelectric crystals. Both enantiomers adopt chiral-polar point group 2 (C2 ) and exhibit mirror-image relationships. They undergo high-temperature 432F2-type plastic ferroelectric phase transition around 348 K. The ferroelectricity has been well confirmed by ferroelectric hysteresis loops and domains. Polarized light microscopy records the evolution of the ferroelastic domains, according with the fact that the 432F2-type phase transition is both ferroelectric and ferroelastic. The very soft characteristics with low elastic modulus and hardness reveals their excellent mechanical flexibility. This finding indicates the first stereosulfur chiral molecular ferroelectric crystals, opening up new fertile ground for exploring molecular ferroelectric crystals with great application prospects.

The First Ring Enlargement Induced Large Piezoelectric Response in a Polycrystalline Molecular Ferroelectric.

Inorganic ferroelectrics have long dominated research and applications, taking advantage of high piezoelectric performance in bulk polycrystalline ceramic forms. Molecular ferroelectrics have attracted growing interest because of their environmental friendliness, easy processing, lightweight, and good biocompatibility, while realizing the considerable piezoelectricity in their bulk polycrystalline forms remains a great challenge. Herein, for the first time, through ring enlargement, a molecular ferroelectric 1-azabicyclo[3.2.1]octonium perrhenate ([3.2.1-abco]ReO4 ) with a large piezoelectric coefficient d33 up to 118 pC/N in the polycrystalline pellet form is designed, which is higher than that of the parent 1-azabicyclo[2.2.1]heptanium perrhenate ([2.2.1-abch]ReO4 , 90 pC/N) and those of most molecular ferroelectrics in polycrystalline or even single crystal forms. The ring enlargement reduces the molecular strain for easier molecular deformation, which contributes to the higher piezoelectric response in [3.2.1-abco]ReO4 . This work opens up a new avenue for exploring high piezoelectric polycrystalline molecular ferroelectrics with great potential in piezoelectric applications.

Solid-Liquid Crystal Biphasic Ferroelectrics with Tunable Biferroelectricity.

Ferroelectricity has been separately found in numerous solid and liquid crystal materials since its first discovery in 1920. However, a single material with biferroelectricity existing in both solid and liquid crystal phases is very rare, and the regulation of biferroelectricity has never been studied. Here, solid-liquid crystal biphasic ferroelectrics, cholestanyl 4-X-benzoate (4X-CB, X = Cl, Br, and I), which exhibits biferroelectricity in both the solid and liquid crystal phases, is presented. It is noted that the ferroelectric liquid crystal phase of 4X-CB is a cholesteric one, distinct from the ordinary chiral smectic ferroelectric liquid crystal phase. Moreover, 4X-CB shows solid-solid and solid-liquid crystal phase transitions, of which the transition temperatures gradually increase from Cl to Br to I substitution. The spontaneous polarization (Ps ) of 4X-CB in both solid and liquid crystal phases can also be regulated by different halogen substitutions, where the 4Br-CB has the optimal Ps because of the larger molecular dipole moment. To the authors' knowledge, 4X-CB is the first ferroelectric with tunable biferroelectricity, which offers a feasible case for the performance optimization of solid-liquid crystal biphasic ferroelectrics.

Fluorination Enables Dual Ferroelectricity in Both Solid- and Liquid-Crystal Phases.

Ferroelectric materials are a special type of polar substances, including solids or liquid crystals. However, obtaining a material to be ferroelectric in both its solid crystal (SC) and liquid crystal (LC) phases is a great challenge. Moreover, although cholesteric LCs inherently possess the advantage of high fluidity, their ferroelectricity remains unknown. Here, through the reasonable H/F substitution on the fourth position of the phenyl group of the parent nonferroelectric dihydrocholesteryl benzoate, we designed ferroelectric dihydrocholesteryl 4-fluorobenzoate (4-F-BDC), which shows ferroelectricity in both SC and cholesteric LC phases. The fluorination induces a lower symmetric polar P1 space group and a new solid-to-solid phase transition in 4-F-BDC. Beneficial from fluorination, the SC and cholesteric LC phases of 4-F-BDC show clear ferroelectricity, as confirmed by well-shaped polarization-voltage hysteresis loops. The dual ferroelectricity in both SC and cholesteric LC phases of a single material was rarely found. This work offers a viable case for the exploration of the interplay between ferroelectric SC and LC phases and provides an efficient approach for designing ferroelectrics with dual ferroelectricity and cholesteric ferroelectric liquid crystals.

Large Piezoelectric Response in a Metal-Free Three-Dimensional Perovskite Ferroelectric.

Metal-free perovskites with light weight and eco-friendly processability have received great interest in recent years due to their superior physical features in ferroelectrics, X-ray detection, and optoelectronics. The famous metal-free perovskite ferroelectric MDABCO-NH4-I3 (MDABCO = N-methyl-N'-diazabicyclo[2.2.2]octonium) has been demonstrated to exhibit excellent ferroelectricity comparable to that of inorganic ceramic ferroelectric BaTiO3, such as large spontaneous polarization and high Curie temperature (Ye et al. Science 2018, 361, 151). However, piezoelectricity as a vitally important index is far from enough in the metal-free perovskite family. Here, we report the discovery of large piezoelectric response in a new metal-free three-dimensional perovskite ferroelectric NDABCO-NH4-Br3 (NDABCO = N-amino-N'-diazabicyclo[2.2.2]octonium) by replacing the methyl group of MDABCO with the amino group. Besides the evident ferroelectricity, strikingly, NDABCO-NH4-Br3 shows a large d33 of 63 pC/N more than 4 times that of MDABCO-NH4-I3 (14 pC/N). The d33 value is also strongly supported by the computational study. To the best of our knowledge, such a large d33 value ranks the highest among the documented organic ferroelectric crystals to date and represents a major breakthrough in metal-free perovskite ferroelectrics. Combined with decent mechanical properties, NDABCO-NH4-Br3 is expected to be a competitive candidate for medical, biomechanical, wearable, and body-compatible ferroelectric devices.

A photoluminescent chiral lead-free hybrid ferroelastic semiconductor with switchable second-harmonic generation.

Chiral organic-inorganic hybrid semiconductors (COIHSs) dominated by lead halides have recently gained tremendous interest. Here, we report a lead-free photoluminescent COIHS [R-3-hydroxylpiperidinium]2SbCl5 with a bandgap of 3.14 eV. It shows a ferroelastic phase transition at 341 K accompanied by a switchable second-harmonic generation response and presents clear ferroelastic domains, which are rarely found in lead-free COIHSs.

Remarkable Enhancement of Piezoelectric Performance by Heavy Halogen Substitution in Hybrid Perovskite Ferroelectrics.

Piezoelectric materials that enable electromechanical conversion have great application value in actuators, transducers, sensors, and energy harvesters. Large piezoelectric (d33) and piezoelectric voltage (g33) coefficients are highly desired and critical to their practical applications. However, obtaining a material with simultaneously large d33 and g33 has long been a huge challenge. Here, we reported a hybrid perovskite ferroelectric [Me3NCH2Cl]CdBrCl2 to mitigate and roughly address this issue by heavy halogen substitution. The introduction of a large-size halide element softens the metal-halide bonds and reduces the polarization switching barrier, resulting in excellent piezoelectric response with a large d33 (∼440 pC/N), which realizes a significant optimization compared with that of previously reported [Me3NCH2Cl]CdCl3 (You et al. Science2017, 357, 306-309). More strikingly, [Me3NCH2Cl]CdBrCl2 simultaneously shows a giant g33 of 6215 × 10-3 V m/N, far exceeding those of polymers and conventional piezoelectric ceramics. Combined with simple solution preparation, easy processing of thin films, and a high Curie temperature of 373 K, these attributes make [Me3NCH2Cl]CdBrCl2 promising for high-performance piezoelectric sensors in flexible, wearable, and biomechanical devices.

Inch-Size Molecular Ferroelectric Crystal with a Large Electromechanical Coupling Factor on Par with Barium Titanate.

Molecular ferroelectrics with large piezoelectric responses have long been sought for their advantages of light weight, mechanical flexibility, and easy preparation, in contrast to the widely used inorganic counterparts. Representatively, a molecular ferroelectric crystal [Me3NCH2Cl]CdCl3 (TMCM-CdCl3) has been found to show a large piezoelectric coefficient d33 of 220 pC/N exceeding that of BaTiO3 (You et al. Science2017, 357, 306-309). However, although the d33 of molecular ferroelectrics has achieved great progress, their electromechanical coupling factor k33, which is essential for various piezoelectric applications, including ultrasonic transducers and actuators, was rarely explored and is far below the level of inorganic ferroelectrics. The major reason for this situation is the great challenge of growing large-size crystals which is a key limiting factor for measuring k33. Here, we grew inch-size crystals of organic-inorganic perovskite ferroelectric TMCM-CdCl3 with a high d33 (383 pC/N) for investigating its piezoelectric responses including the k33 (0.483) by the resonance method. Such high k33 (0.483) is much larger than those of other molecular ferroelectrics and competitive with that of BaTiO3 (0.5). In addition, TMCM-CdCl3 has a low elastic modulus of 13.03 GPa, an order of magnitude lower than that of BaTiO3. This finding sheds light on the exploration of large electromechanical coupling factors in molecular ferroelectrics for potential applications in flexible and portable piezoelectric devices.

Biferroelectricity of a homochiral organic molecule in both solid crystal and liquid crystal phases.

Ferroelectricity, existing in either solid crystals or liquid crystals, gained widespread attention from science and industry for over a century. However, ferroelectricity has never been observed in both solid and liquid crystal phases of a material simultaneously. Inorganic ferroelectrics that dominate the market do not have liquid crystal phases because of their completely rigid structure caused by intrinsic chemical bonds. We report a ferroelectric homochiral cholesterol derivative, ß-sitosteryl 4-iodocinnamate, where both solid and liquid crystal phases can exhibit the behavior of polarization switching as determined by polarization-voltage hysteresis loops and piezoresponse force microscopy measurements. The unique long molecular chain, sterol structure, and homochirality of ß-sitosteryl 4-iodocinnamate molecules enable the formation of polar crystal structures with point group 2 in solid crystal phases, and promote the layered and helical structure in the liquid crystal phase with vertical polarization. Our findings demonstrate a compound that can show the biferroelectricity in both solid and liquid crystal phases, which would inspire further exploration of the interplay between solid and liquid crystal ferroelectric phases.

An unprecedented azobenzene-based organic single-component ferroelectric.

Organic single-component ferroelectrics, as an important class of metal-free ferroelectrics, are highly desirable because of their easy processing, mechanical flexibility, and biocompatibility. However, although nearly 50 years have passed since the discovery of photochromism in azobenzene-doped cholesteric liquid crystals, ferroelectricity has never been found in azobenzene-based crystals. Here, we use an amino group to substitute a fluorine atom of 2,2',4,4',6,6'-hexafluoroazobenzene, which successfully introduces ferroelectricity into 2-amino-2',4,4',6,6'-pentafluoroazobenzene (APFA). APFA shows an extremely high Curie temperature (T c) of 443 K, which is outstanding among single-component ferroelectrics. It also exhibits an indirect optical band gap of 2.27 eV as well as photoisomerization behavior between the trans-form and the cis-form triggered by pedal motion. To our knowledge, APFA is the first azobenzene-based ferroelectric crystal. This work opens an avenue to design excellent single-component ferroelectrics and will inspire the exploration of azobenzene-based ferroelectrics for promising applications in biofriendly ferroelectric devices.

Unprecedented Ferroelectricity and Ferromagnetism in a Cr2+ -Based Two-Dimensional Hybrid Perovskite.

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 Cr2+ -based OIHP, [3,3-difluorocyclobutylammonium]2 CrCl4 ([DFCBA]2 CrCl4 ), 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.

Domain memory effect in the organic ferroics.

Shape memory alloys have been used extensively in actuators, couplings, medical guide wires, and smart devices, because of their unique shape memory effect and superelasticity triggered by the reversible martensitic phase transformations. For ferroic materials, however, almost no memory effects have been found for their ferroic domains after reversible phase transformations. Here, we present a pair of single-component organic enantiomorphic ferroelectric/ferroelastic crystals, (R)- and (S)-N-3,5-di-tert-butylsalicylidene-1-(1-naphthyl)ethylamine SA-NPh-(R) and SA-NPh-(S). It is notable that not only can their ferroic domain patterns disappear and reappear during reversible thermodynamic phase transformations, but they can also disappear and reappear during reversible light-driven phase transformations induced by enol-keto photoisomerization, both of which are from P1 to P21 polar space groups. Most importantly, the domain patterns are exactly the same in the initial and final states, demonstrating the existence of a memory effect for the ferroic domains in SA-NPh-(R) and SA-NPh-(S). As far as we are aware, the domain memory effect triggered by both thermodynamic and light-driven ferroelectric/ferroelastic phase transformations remains unexplored in ferroic materials. Thermal and optical control of domain memory effect would open up a fresh research field for smart ferroic materials.

Giant electromechanical effects in polymers.

A four-ingredient polymer chain has record-breaking piezoelectric capability.

Multichannel Control of Multiferroicity in Single-Component Homochiral Organic Crystals.

A ferroelectric/ferroelastic is a material whose spontaneous polarization/strain can be switched by applying an external electric field/mechanical stress. However, the optical control of spontaneous polarization/strain remains relatively unexplored in crystalline materials, although photoirradiation stands out as a nondestructive, noncontact, and remote-controlled stimulus beyond stress or electric field. Here, we present two new organic single-component homochiral photochromic multiferroics, (R)- and (S)-N-3,5-di-tert-butylsalicylidene-1-4-bromophenylethylamine (SA-Ph-Br(R) and SA-Ph-Br(S)), which show a full ferroelectric/ferroelastic phase transition of 222F2 type at 336 K. Under photoirradiation, their spontaneous polarization/strain can be switched quickly within seconds and reversibly between two ferroelectric/ferroelastic phases with the respective enol and trans-keto forms triggered by structural photoisomerizations. In addition, they possess a superior acoustic impedance characteristic with a value of ∼2.42 × 106 kg·s-1·m-2, lower than that of polyvinylidene fluoride (PVDF, (3.69-4.25) × 106 kg·s-1·m-2), which can better match human tissues. This work realizes for the first time that multiple ferroic orders in single-component organic crystals with ultralow acoustic impedance can be simultaneously controlled and coupled by three physical channels (electric, stress, light fields), suggesting their great potential in multichannel data storage, optoelectronics, and related applications compatible with all-organic electronics and human tissues.

Optically Induced Ferroelectric Polarization Switching in a Molecular Ferroelectric with Reversible Photoisomerization.

Ferroelectrics usually exhibit temperature-triggered structural changes, which play crucial roles in controlling their physical properties. However, although light is very striking as a non-contact, non-destructive, and remotely controlled external stimuli, ferroelectric crystals with light-triggered structural changes are very rare, which holds promise for optical control of ferroelectric properties. Here, an organic molecular ferroelectric, N-salicylidene-2,3,4,5,6-pentafluoroaniline (SA-PFA), which shows light-triggered structural change of reversible photoisomerization between cis-enol and trans-keto configuration is reported. SA-PFA presents clear ferroelectricity with the saturate polarization of 0.84 µC cm-2 , larger than those of some typical organic ferroelectrics with thermodynamically structural changes. Benefit from the reversible photoisomerization, the dielectric real part of SA-PFA can be reversibly switched by light. More strikingly, the photoisomerization enables SA-PFA to show reversible optically induced ferroelectric polarization switching. Such intriguing behaviors make SPFA a potential candidate for application in next-generation photo-controlled ferroelectric devices. This work sheds light on further exploration of more excellent molecular ferroelectrics with light-triggered structural changes for optical control of ferroelectric properties.