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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. [ABSTRACT FROM AUTHOR]

Molecular ferroelectrics have gradually aroused great interest in both fundamental scientific research and technological applications because of their easy processing, light weight and mechanical flexibility. Hybrid organic–inorganic perovskite ferroelectrics (HOIPFs), as a class of molecule-based ferroelectrics, have diverse functionalities owing to their unique structure and have become a hot spot in molecular ferroelectrics research. Therefore, they are extremely attractive in the field of ferroelectrics. However, there seems to be a lack of systematic review of their design, performance and potential applications. Herein, we review the recent development of HOIPFs from lead-based, lead-free and metal-free perovskites, and outline the versatility of these ferroelectrics, including piezoelectricity for mechanical energy-harvesting and optoelectronic properties for photovoltaics and light detection. Furthermore, a perspective view of the challenges and future directions of HOIPFs is also highlighted. [ABSTRACT FROM AUTHOR]

With prosperity, decay, and another spring, molecular ferroelectrics have passed a hundred years since Valasek first discovered ferroelectricity in the molecular compound Rochelle salt. Recently, the proposal of ferroelectrochemistry has injected new vigor into this century-old research field. It should be highlighted that piezoresponse force microscopy (PFM) technique, as a non-destructive imaging and manipulation method for ferroelectric domains at the nanoscale, can significantly speed up the design rate of molecular ferroelectrics as well as enhance the ferroelectric and piezoelectric performances relying on domain engineering. Herein, we provide a brief review of the contribution of the PFM technique toward assisting the design and performance optimization of molecular ferroelectrics. Relying on the relationship between ferroelectric domains and crystallography, together with other physical characteristics such as domain switching and piezoelectricity, we believe that the PFM technique can be effectively applied to assist the design of high-performance molecular ferroelectrics equipped with multifunctionality, and thereby facilitate their practical utilization in optics, electronics, magnetics, thermotics, and mechanics among others. [ABSTRACT FROM AUTHOR]

Organic radical ferroics such as TEMPO have attracted widespread interest. 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 yet been found. Here, taking advantage of chemical design and supramolecular radical chemistry, we 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 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 is vital for the stabilization of the radical and extending the working temperature window. Both also have paramagnetism, non‐interacting spin moments, and excellent piezoelectric and electrostrictive behaviors comparable to that of LiNbO3. [ABSTRACT FROM AUTHOR]

Spreitzer I et al. i [96] provide a research update on the growth of ferroelectric oxide thin films on silicon, with a particular view toward their applications in piezoelectric micro electromechanical systems (MEMS), electro-optic devices for communications applications, and catalysis and a consideration of the complexities of the silicon-ferroelectric interface. The favored theory for oxide ferroelectrics is the soft-mode theory, and here, we have a perspective by Kamba[79] discussing the results of broadband dielectric, THz, and IR spectroscopic investigations of soft-mode phenomena in H-bonded ferroelectrics, BaTiO SB 3 sb , relaxors, and multiferroics. Domains are also of considerable interest in antiferroelectric materials, and An I et al. i [118] discuss the hierarchical nature of domains in PZT crystals with only 2 at. % Ti, close to the antiferroelectric PbZrO SB 3 sb composition, showing how this forms in the intermediate ferroelectric state and have a significant impact on the materials' physical properties. Subsequently, there has been shown to be a wide range of metal organic complex ferroelectrics, as reviewed by Hang I et al. i [123] In this collection, we have an overview by Yao I et al. i [124] of the potential for bandgap engineering in hybrid organic-inorganic perovskite (HOIP) ferroelectrics such as (MDABCO)(NH SB 4 sb )I SB 3 sb [MDABCO = I N i -methyl I N i '-diazabicyclo(2.2.2)octonium], with the potential for linking the excellent characteristics of the new perovskite materials for solar cells, such as methylammonium lead iodide (MAPbI SB 3 sb ),[125] with the photovoltaic effects seen in ferroelectrics. [Extracted from the article]

Switchable materials play an invaluable role in signal processing and encryption of smart devices. The development of multifunctional materials that exhibit switching characteristics in multiple physical channels has attracted widespread attention. Now, two chiral thermochromic ferroelastic crystals (S‐CTA)2CuCl4 and (R‐CTA)2CuCl4 (CTA=3‐chloro‐2‐hydroxypropyltrimethylammonium) have been prepared with switchable properties in dielectricity, conductivity, second harmonic generation (SHG), piezoelectricity, ferroelasticity, chiral, and thermochromic properties. Compared with traditional phase‐transition materials with switching features, thermochromism brings additional spectral encryption possibilities for future information processing. To the best of our knowledge, this is the first chiral thermochromic ferroelastic that exhibits switching properties in seven physical channels. This work is expected to promote further exploration of multifunctional molecular switchable materials. [ABSTRACT FROM AUTHOR]

Ferroelectrics are inseparable from symmetry breaking. Accompanying the paraelectric-to-ferroelectric phase transition, the paraelectric phase adopting one of the 32 crystallographic point groups is broken into subgroups belonging to one of the 10 ferroelectric point groups, i.e. C1, C2, C1h, C2v, C4, C4v, C3, C3v, C6 and C6v. The symmetry breaking is captured by the order parameter known as spontaneous polarization, whose switching under an external electric field results in a typical ferroelectric hysteresis loop. In addition, the responses of spontaneous polarization to other external excitations are related to a number of physical effects such as second-harmonic generation, piezoelectricity, pyroelectricity and dielectric properties. Based on these, this review summarizes recent developments in molecular ferroelectrics since 2011 and focuses on the relationship between symmetry breaking and ferroelectricity, offering ideas for exploring high-performance molecular ferroelectrics. [ABSTRACT FROM AUTHOR]

Molecular ferroelectric thin films are highly desirable for their easy and environmentally friendly processing, light weight, and mechanical flexibility. A thin film of imidazolium perchlorate processed from aqueous solution is an excellent molecular ferroelectric with high spontaneous polarization, high Curie temperature, low coercivity, and superior electromechanical coupling. These attributes make it a molecular alternative to perovskite ferroelectric films in sensing, actuation, data storage, electro-optics, and molecular/flexible electronics. [ABSTRACT FROM AUTHOR]

Transient implantable piezoelectric materials are desirable for biosensing, drug delivery, tissue regeneration, and antimicrobial and tumor therapy. For use in the human body, they must show flexibility, biocompatibility, and biodegradability. These requirements are challenging for conventional inorganic piezoelectric oxides and piezoelectric polymers. We discovered high piezoelectricity in a molecular crystal HOCH2(CF2)3CH2OH [2,2,3,3,4,4-hexafluoropentane-1,5-diol (HFPD)] with a large piezoelectric coefficient d33 of ~138 picocoulombs per newton and piezoelectric voltage constant g33 of ~2450 × 10−3 volt-meters per newton under no poling conditions, which also exhibits good biocompatibility toward biological cells and desirable biodegradation and biosafety in physiological environments. HFPD can be composite with polyvinyl alcohol to form flexible piezoelectric films with a d33 of 34.3 picocoulombs per newton. Our material demonstrates the ability for molecular crystals to have attractive piezoelectric properties and should be of interest for applications in transient implantable electromechanical devices. [ABSTRACT FROM AUTHOR]

Piezoelectric materials produce electricity when strained, making them ideal for different types of sensing applications. The most effective piezoelectric materials are ceramic solid solutions in which the piezoelectric effect is optimized at what are termed morphotropic phase boundaries (MPBs). Ceramics are not ideal for a variety of applications owing to some of their mechanical properties. We synthesized piezoelectric materials from a molecular perovskite (TMFM)x(TMCM)1–xCdCl3 solid solution (TMFM, trimethylfluoromethyl ammonium; TMCM, trimethylchloromethyl ammonium, 0 ≤ x ≤ 1), in which the MPB exists between monoclinic and hexagonal phases. We found a composition for which the piezoelectric coefficient d33 is ~1540 picocoulombs per newton, comparable to high-performance piezoelectric ceramics. The material has potential applications for wearable piezoelectric devices. [ABSTRACT FROM AUTHOR]

Molecular piezoelectrics are attracting tremendous interest because of their easy processing, light weight, low acoustical impedance, and mechanical flexibility. However, reports of molecular piezoelectrics with a piezoelectric coefficient d33 comparable to piezoceramics such as barium titanate (BTO, 90-190 pC/N) have been scarce. Here, we present a uniaxial molecular ferroelectric, trimethylchloromethylammonium tribromocadmium(II) (TMCM-CdBr3), in which the halogen bonding might be a possible critical point for the stabilization of one-dimensional (1D) {CdBr3}- chain and further reservation of its ferroelectricity in such organic- inorganic hybrid crystalline systems. It has a large d33 of 139 pC/N, 1 order of magnitude higher than those of most classically uniaxial ferroelectrics such as LiNbO3 (6-16 pC/N) and Rochelle salt (~7 pC/N), and comparable with those of multiaxial ferroelectrics such as BTO and trimethylbromomethylammonium tribromomanganese(II) (112 pC/N). Moreover, the simple single-crystal growth and easyto- find polar axis enable it to hold a great potential for applying in the single-crystal form. In light of the strong, specific, and directional halogen-bonding interactions, this work provides possibilities to explore new classes of molecular piezoelectrics and contribute to further developments. [ABSTRACT FROM AUTHOR]