High-performance Pyroelectric Property Accompanied by Spin Crossover in a Single Crystal of Fe(II) Complex.

Pyroelectric materials hold significant potential for energy harvesting, sensing, and imaging applications. However, achieving high-performance pyroelectricity across a wide temperature range near room temperature remains a significant challenge. Herein, we demonstrate a single crystal of Fe(II) spin-crossover compound shows remarkable pyroelectric properties accompanied by a thermally controlled spin transition. In this material, the uniaxial alignment of polar molecules results in a polarization of the lattice. As the molecular geometry is modulated during a gradual spin transition, the polar axis experiences a colossal thermal expansion with a coefficient of 796×10-6 K-1. Consequently, the material's polarization undergoes significant modulation as a secondary pyroelectric effect. The considerable shift in polarization (pyroelectric coefficient, p=3.7-22 nC K-1cm-2), coupled with a low dielectric constant (ϵ'=4.4-5.4) over a remarkably wide temperature range of 298 to 400 K, suggests this material is a high-performance pyroelectric. The demonstration of pyroelectricity combined with magnetic switching in this study will inspire further investigations in the field of molecular electronics and magnetism.

Electrically Detectable Photoinduced Polarization Switching in a Molecular Prussian Blue Analogue.

Light, a nondestructive and remotely controllable external stimulus, effectively triggers a variety of electron-transfer phenomena in metal complexes. One prime example includes using light in molecular cyanide-bridged [FeCo] bimetallic Prussian blue analogues, where it switches the system between the electron-transferred metastable state and the system's ground state. If this process is coupled to a ferroelectric-type phase transition, the generation and disappearance of macroscopic polarization, entirely under light control, become possible. In this research, we successfully executed a nonpolar-to-polar phase transition in a trinuclear cyanide-bridged [Fe2Co] complex crystal via directional electron transfer. Intriguingly, by exposing the crystal to the wavelength of light─785 nm─without any electric field─we can drive this ferroelectric phase transition to completely depolarize the crystal, during which a measurable electric current response can be detected. These discoveries signify an important step toward the realization of fully light-controlled ferroelectric memory devices.

High-Temperature Metal-Free Molecular Ferroelectrics with Large Spontaneous Polarization.

In the past two decades, numerous molecular ferroelectrics have been reported. However, metal-free molecular ferroelectrics with high working temperatures and large spontaneous polarizations are still uncommon. Herein, we present two metal-free molecular ferroelectrics prepared from monoprotonated hexamethylenetetramine (HMTA), namely (HMTAH)Cl and (HMTAH)Br, which crystallize in a polar point group of 3m. In these crystals, the polar HMTAH+ organic cations can be reoriented 180° along the polar axis because of the quasispherical molecular geometry. As a result of the large shift of the positively charged protonated N atoms, these compounds demonstrate large spontaneous polarizations with values of 8.3 and 8.1 µC cm-2 and high working temperatures of 390 and 435 K, respectively. The ferroelectric property of these compounds is characterized with second-harmonic generation, ferroelectric hysteresis loop, and pyroelectric current measurements.

Photoinduced Persistent Polarization Change in a Spin Transition Crystal.

Using light as a local heat source to induce a temporary pyroelectric current is widely recognized as an effective way to control the polarization of crystalline materials. In contrast, harnessing light directly to modulate the polarization of a crystal via excitation of the electronic bands remains less explored. In this study, we report an FeII spin crossover crystal that exhibits photoinduced macroscopic polarization change upon excitation by green light. When the excited crystal relaxes to the ground state, the corresponding pyroelectric current can be detected. An analysis of the structures, magnetic properties and the Mössbauer and infrared spectra of the complex, supported by calculations, revealed that the polarization change is dictated by the directional relative movement of ions during the spin transition process. The spin transition and polarization change occur simultaneously in response to light stimulus, which demonstrates the enormous potential of polar spin crossover systems in the field of optoelectronic materials.

A series of dynamic single crystals of [MII(en)3]SO4 (M = Ni, Mn, and Cd) shows tunable dielectric properties and anisotropic thermal expansion.

A series of dynamic single crystals with a chemical formula of [MII(en)3]SO4 (en = ethylene and MII = NiII, MnII, and CdII) was synthesized. As the temperature decreases, these materials exhibit dielectric switching in the vicinity of the phase transition point accompanied by anisotropic thermal expansion in the cell parameters as a consequence of the order-disorder structural change of SO2-4 in a cavity surrounded by five [MII(en)3]2+ complex cations. Because the variation of metal centers with different ionic radii changes the shape of the complex cation, which affects the distribution of hydrogen-bond interactions around the SO2-4, the dynamic motion of SO2-4 is substantially tuned. Correspondingly, the dielectric properties and anisotropic thermal expansion of materials were largely shifted, especially in the single crystals of [MnII(en)3]SO4, whose structural change is distinctly different from the crystals of Ni(II) and Cd(II). The detailed structural mechanism accounting for the different physical properties of these materials was discussed.

High-Temperature Molecular Ferroelectric Tris(2-hydroxyethyl) Ammonium Bromide with Dielectric Relaxation.

We obtained one new molecular ferroelectric material tris(2-hydroxyethyl) ammonium bromide (TAB) that crystallizes in aqueous solution at room temperature with a space group of R3m which belongs to ten polar space groups. There is a paraelectric-to-ferroelectric phase transition at 424 K (from hexagonal R3̅m to hexagonal R3m phase). Such a high transition temperature is close to that of diisopropylamine bromide (426 K) and higher than that of many other molecular ferroelectrics, such as triethylmethylammonium tetrabromoferrate(III) (360 K); some of the organic-inorganic perovskite ferroelectrics, such as (cyclohexylammonium)2PbBr4 (363 K); and some inorganic ferroelectrics, including BaTiO3 (393 K). The saturated polarization and the coercive field of TAB measured from the ferroelectric hysteresis loop are about 0.54 µC·cm-2 and 0.62 kV/cm, respectively. Given its superior performance, including high phase transition temperature, room-temperature ferroelectricity, small coercive electric field, and adjustable ladder-shaped dielectric constant, TAB will have many potential applications.