Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.
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.
Simultaneous control of the magnetic and electric properties of materials is crucial for their application in next-generation memory and sensor devices. Herein, we report a single-crystal Co(II) complex that exhibits unprecedented two-step magnetic switching accompanied by paraelectric-ferroelectric-paraelectric phase transition. The ferroelectricity of the material is governed by changes in the directionality of the sulfate dianions therein that trigger nonpolarpolar-nonpolar variation of the crystal symmetry and induce slight structural changes in the Co(II) complex. The unquenched orbital angular momentum of the Co(II) ion, which has trigonal antiprismatic coordination geometry, is susceptible to the coordination environment. Accordingly, two-step magnetic switching accompanied by ferroelectric phase transitions is demonstrated, and the detailed mechanism of the paraelectric-ferroelectric-paraelectric phase transitions and the consequent magnetic switching are investigated. Thus, this study presents a unique multifunctional material as well as a viable strategy for the development of superior molecular magnetoelectric materials.
A proton–electron coupling system, exhibiting unique bistability or multistability of the protonated state, is an attractive target for developing new switchable materials based on proton dynamics. Herein, we present an iron(II) hydrazone crystalline compound, which displays the stepwise transition and bistability of proton transfer at the crystal level. These phenomena are realized through the coupling with spin transition. Although the multi‐step transition with hysteresis has been observed in various systems, the corresponding behavior of proton transfer has not been reported in crystalline systems; thus, the described iron(II) complex is the first example. Furthermore, because proton transfer occurs only in one of the two ligands and π electrons redistribute in it, the dipole moment of the iron(II) complexes changes with the proton transfer, wherein the total dipole moment in the crystal was canceled out owing to the antiferroelectric‐like arrangement.
Some cyanide‐bridged complexes are known for exhibiting slow magnetic relaxation behavior in a light‐induced metastable state. Herein, an unexpected reverse effect is observed for the first time in the S=1/2 {FeIILS‐CoIIILS‐FeIIILS} (HS=high spin, LS=low spin) ground state of a novel V‐shaped trinuclear cyanide‐bridged {Fe2Co} complex. In this complex, light‐switchable iron‐cobalt charge transfer with repeatable off/on switching of slow magnetic relaxation is discovered upon alternating laser irradiation at 785 and 560 nm. An important characteristic of the present compound is that the S=1/2 ground state exhibits slow magnetic relaxation before irradiation, whereas this is accelerated after irradiation. This is different from the typical behavior, where the light‐induced metastable state exhibits slow magnetic relaxation.
The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)3]8[Fe(H2O)(DMSO)]6 (abbreviated as [Fe14], Tp−, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe14] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10−8 s). Partial reduction of N-terminal high spin FeIII sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe14] complex.
Atypically anisotropic and large changes in magnetic susceptibility, along with a change in crystalline shape, were observed in a Co II complex at near room temperature. This was achieved by combining oxalate molecules, acting as rotor, and a Co II ion with unquenched orbital angular momentum. A thermally controlled 908 rotation of the oxalate counter anion triggered a symmetry-breaking ferroelastic phase transition, accompanied by contraction-expansion behavior (ca. 4.5 %) along the long axis of a rod-like single crystal. The molecular rotation induced a minute variation in the coordination geometry around the Co II ion, resulting in an abrupt decrease and a remarkable increase in magnetic susceptibility along the direction perpendicular and parallel to the long axis of the crystal, respectively. Theoretical calculations suggested that such an unusual anisotropic change in magnetic susceptibility was due to a substantial reorientation of magnetic anisotropy induced by slight disruption in the ideal D 3 coordination environment of the complex cation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.