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.

Large Phase-Transition Temperature Enhancement Achieved in a Layered Lead Iodide Hybrid Crystal by H/F Substitution.

Organic-inorganic hybrid metal halides with structural flexibility and solution processability have been widely investigated for different application scenarios. However, the effective construction of phase-transition materials with a high phase-transition temperature (Ttr) for potential practical applications remains a great challenge, and reports on the regulation of Ttr with significant enhancement have been rare. In this manuscript, we have realized a large Ttr increase of 148 K in a layered hybrid lead iodide crystal (4-FTMBA)4Pb3I10 (4-FTMBA = 4-fluoro-N,N,N-trimethylbenzenaminium) by the H/F substitution strategy. Compared to the parent (TMBA)4Pb3I10 (TMBA = N,N,N-trimethylbenzenaminium), H/F substitution preserves the structural framework and crystal symmetry in (4-FTMBA)4Pb3I10. The introduction of heavier fluorine will significantly increase the motion barrier for the order-disorder transition, resulting in the remarkably improved Ttr. Temperature-dependent crystal structures, Raman spectra, and dielectric analyses well support the phase-transition behavior. In addition, evident thermochromism with a tunable direct band gap in (4-FTMBA)4Pb3I10 has been observed using UV-vis spectra. To the best of our knowledge, the achieved Ttr enhancement of 148 K by H/F substitution is the highest among the organic-inorganic hybrid lead halide phase-transition materials. This finding would greatly inspire the rational design of functional materials with high performance.

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.

Tuning Dielectric Transitions in Two-Dimensional Organic-Inorganic Hybrid Lead Halide Perovskites.

Organic-inorganic hybrid metal halide perovskites possessing unique two-dimensional (2D)-layered structures have been demonstrated with excellent molecular tunability and stability, especially the promising semiconductor properties for solar cell applications. In this work, three 2D lead halide organic-inorganic hybrid perovskites (IAA)2PbX4 (IAA = isoamylammonium cation and X = Cl, Br, and I) were synthesized by employing a solution processing method and demonstrate distinct tuning solid-state phase transitions coupled with dielectric responses, as well as light absorption properties. Among the title perovskites, the phase transition temperature decreases gradually, and their band gap also indicates a narrowing trend. The results are mainly derived from slight changes in the crystal structure by halogen regulation. These findings might provide an effective crystal engineering strategy for exploring high-performance functional perovskite materials.

Discovery of molecular ferroelectric catalytic annulation for quinolines.

Ferroelectrics as emerging and attractive catalysts have shown tremendous potential for applications including wastewater treatment, hydrogen production, nitrogen fixation, and organic synthesis, etc. In this study, we demonstrate that molecular ferroelectric crystal TMCM-CdCl3 (TMCM = trimethylchloromethylammonium) with multiaxial ferroelectricity and superior piezoelectricity has an effective catalytic activity on the direct construction of the pharmacologically important substituted quinoline derivatives via one-pot [3 + 2 + 1] annulation of anilines and terminal alkynes by using N,N-dimethylformamide (DMF) as the carbon source. The recrystallized TMCM-CdCl3 crystals from DMF remain well ferroelectricity and piezoelectricity. Upon ultrasonic condition, periodic changes in polarization contribute to the release of free charges from the surface of the ferroelectric domains in nano size, which then quickly interacts with the substrates in the solution to trigger the pivotal redox process. Our work advances the molecular ferroelectric crystal as a catalytic route to organic synthesis, not only providing valuable direction for molecular ferroelectrics but also further enriching the executable range of ferroelectric catalysis.

Photochromic Single-Component Organic Fulgide Ferroelectric with Photo-Triggered Polarization Response.

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 Z)-3-(1-(4-(tert-butyl)phenyl)ethylidene)-4-(propan-2-ylidene)dihydrofuran-2,5-dione (1E 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.

Highest-T c single-component homochiral organic ferroelectrics.

Organic single-component ferroelectrics with low molecular mass have drawn great attention for application in organic electronics. However, the discovery of high-T c single-component organic ferroelectrics has been very scarce. Herein, we report a pair of homochiral single-component organic ferroelectrics (R)-10-camphorsulfonylimine and (S)-10-camphorsulfonylimine under the guidance of ferroelectric chiral chemistry. They crystallize in the chiral-polar space group P21, and their mirror image relations have been identified using vibrational circular dichroism spectra. They both exhibit 422F2 multiaxial ferroelectricity with T c as high as 429 K. Besides, they possess superior acoustic impedance characteristics with a value of 2.45 × 106 kg s-1 m-2, lower than that of PVDF. To our knowledge, enantiomeric (R and S)-10-camphorsulfonylimine show the highest T c among the known organic single-component ferroelectrics and low acoustic impedance well matching with that of bodily tissues. This work promotes the development of high-performance organic single-component ferroelectrics and is of great inspiration to explore their application in next-generation flexible smart devices.

A Photoluminescent Lead Bromide Hybrid Perovskite Molecular Ferroelastic Semiconductor with Sequential High-Tc Phase Transitions.

Organic-inorganic hybrid lead halide perovskites have attracted great interest for their use in promising optoelectronic applications. However, reports of photoluminescent perovskite molecular ferroelastic semiconductors with sequential high-Tc phase transitions have been scarce. In this work, a one-dimensional lead bromide hybrid perovskite [N,N-dimethylethanolammonium]PbBr3 has been synthesized, undergoing high-Tc sequential phase transitions at around 351 and 444 K, higher than those of most previously discovered hybrid perovskite phase transition materials. The specific intermolecular hydrogen bond between cationic molecules provides the greatest contribution to its high Tc by increasing the barrier of molecular motion under the temperature stimuli. The prominent ferroelastic domain evolution is visually observed under orthogonally polarized light. In addition, [N,N-dimethylethanolammonium]PbBr3 exhibits semiconducting and orange light emission characteristics. This finding opens up an avenue for designing high-performance ferroelastic materials and provides great motivation for discovering new multifunctional materials for the next generation of smart devices.