Supramolecular Rotor Assembly for the Design of a Hybrid Ferroelectric-Antiferromagnetic Multiferroic Semiconductor.

Ferroelectric (FE)-antiferromagnetic (AFM) multiferroic materials have sparked growing interest due to their huge possibilities in energy-saving, photoelectric devices, nonvolatile storage, and switches. However, realizing FE-AFM properties in a hybrid molecular material is difficult because ferroelectric and magnetic orders are commonly mutually exclusive. Here, we report an FE-AFM multiferroic semiconductor [NH(18-crown-6)][Mn(SCN)] (NCMS) by supramolecular assembly approach via molecular rotor synthon [NH(18-crown-6)] and inorganic magnetic module [Mn(SCN)].

Noncollinear ferroelectric and screw-type antiferroelectric phases in a metal-free hybrid molecular crystal.

Noncollinear dipole textures greatly extend the scientific merits and application perspective of ferroic materials. In fact, noncollinear spin textures have been well recognized as one of the core issues of condensed matter, e.g.

Effect of Substituents in Equatorial Hexaazamacrocyclic Schiff Base Ligands on the Construction and Magnetism of Pseudo Single-Ion Magnets.

Three mononuclear Dy compounds [DyL(PhSiO)][BPh]·MeCN·2HO (), [DyL(PhSiO)][BPh]·CHOH·HO (), and [DyL(PhSiO)(OAc)][BPh]·CHOH·3HO () and their corresponding Y diluted analogues [DyYL(PhSiO)][BPh]·MeCN·2HO (), [DyYL(PhSiO)][BPh]·CHOH·HO (), and [DyYL(PhSiO)(OAc)][BPh]·CHOH·3HO () were synthesized with hexaazamacrocyclic Schiff base ligands as an equatorial ligand. The substituents in the equatorial hexaazamacrocyclic Schiff base ligand show a significant effect on the replacement of the axial ligands. Compounds , , and are typical zero dc field single-molecule magnets with effective energy barriers () of 1092(6), 946.

Room-temperature Magnetocapacitance Spanning 97K Hysteresis in Molecular Material.

Magnetic capacitor, as a new type of device, has broad application prospects in fields such as magnetic field sensing, magnetic storage, magnetic field control, power electronics and so on. Traditional magnetic capacitors are mostly assembled by magnetic and capacitive materials. Magnetic capacitor made of a single material with intrinsic properties is very rare.

A Multiferroic Spin-Crossover Molecular Crystal.

Spin-crossover (SCO) ferroelectrics with dual-function switches have attracted great attention for significant magnetoelectric application prospects. However, the multiferroic crystals with SCO features have rarely been reported. Herein, a molecular multiferroic Fe(II) crystalline complex [Fe(C-F-pbh)] (1-F, C-F-pbh = (1Z,N'E)-3-F-4-(octyloxy)-N'-(pyridin-2-ylmethylene)-benzo-hydrazonate) showing the coexistence of ferroelectricity, ferroelasticity, and SCO behavior is presented for the first time.

Molecular Engineering Regulation Achieving Out-of-Plane Polarization in Rare-Earth Hybrid Double Perovskites for Ferroelectrics and Circularly Polarized Luminescence.

Out-of-plane polarization is a highly desired property of two-dimensional (2D) ferroelectrics for application in vertical sandwich-type photoferroelectric devices, especially in ultrathin ferroelectronic devices. Nevertheless, despite great advances that have been made in recent years, out-of-plane polarization remains unrealized in the 2D hybrid double perovskite ferroelectric family. Here, from our previous work 2D hybrid double perovskite HQERN ((S3HQ)EuRb(NO), S3HQ=S-3-hydroxylquinuclidinium), we designed a molecular strategy of F-substitution on organic component to successfully obtain FQERN ((S3FQ)EuRb(NO), S3FQ=S-3-fluoroquinuclidinium) showing circularly polarized luminescence (CPL) response.

Molecular ferroelectric with low-magnetic-field magnetoelectricity at room temperature.

Magnetoelectric materials, which encompass coupled magnetic and electric polarizabilities within a single phase, hold great promises for magnetic controlled electronic components or electric-field controlled spintronics. However, the realization of ideal magnetoelectric materials remains tough due to the inborn competion between ferroelectricity and magnetism in both levels of symmetry and electronic structure. Herein, we introduce a methodology for constructing single phase paramagnetic ferroelectric molecule [TMCM][FeCl], which shows low-magnetic-field magnetoelectricity at room temperature.

Synergetic Responses of Multiple Functions Induced by Phase Transition in Molecular Materials.

Materials that integrate magnetism, electricity and luminescence can not only improve the operational efficiency of devices, but also potentially generate new functions through their coupling. Therefore, multifunctional synergistic effects have broad application prospects in fields such as optoelectronic devices, information storage and processing, and quantum computing. However, in the research field of molecular materials, there are few reports on the synergistic multifunctional properties.

Three-Dimensional Bimetallic Ammonium K-Eu Nitrate with a Rare (6,6)-Connected Ion Topology Exhibiting Structural Phase Transition and Photoluminescence Properties.

A K-Eu bimetallic ammonium metal-nitrate three-dimensional (3D) framework incorporating R--methyl-3-hydroxyquinuclidine, (RM3HQ)KEu(NO) (RM3HQ = R--methyl-3-hydroxyquinuclidine, ), was characterized and reported. Distinguishing from the former hybrid rare-earth double perovskites, adopts a mixed corner- and face-sharing K/Eu-centered polyhedral connectivity to form a 3D inorganic framework, showing a rare (6, 6)-connected ion topology with a 6 framework. Notably, exhibits clear phase transition, and the switchable thermodynamic behavior is confirmed by variable-temperature dielectric measurements and second-harmonic generation response.

Gas-Liquid Interface Route to Hybrid Copper Bromine Perovskite Single-Crystal Membrane with Dielectric Transitions and Ferromagnetic Exchanges.

Single-crystal membranes (SCMs) show great promise in the fields of sensors, light-emitting diodes, and photodetection. However, the growth of a large-area single-crystal membranes is challenging. We report a new organic-inorganic SCMs [HCMA]CuBr (HCMA = cyclohexanemethylamine) crystallized at the gas-liquid interface.

Halogen-Regulated and X-ray Radiation Detection in 2D Hybrid Perovskite Ferroelastic Semiconductor.

Organic-inorganic hybrid perovskites (OIHPs) have received particular attention due to their characteristic structural tunability and flexibility. These features make OIHPs behave with excellent modifications on macroscopic properties, such as ferroicity or semiconductor performances, etc. Herein, we report two 2D hybrid stibium-based halide perovskite (CHN)SbX (X = Br, ; Cl, ) ferroelastic semiconductor possessing dual switching properties of dielectric and second harmonic generation (SHG).

Organic-Inorganic Hybrid Ferroelectric and Antiferroelectric with Afterglow Emission.

Luminescent ferroelectrics are holding exciting prospect for integrated photoelectronic devices due to potential light-polarization interactions at electron scale. Integrating ferroelectricity and long-lived afterglow emission in a single material would offer new possibilities for fundamental research and applications, however, related reports have been a blank to date. For the first time, we here achieved the combination of notable ferroelectricity and afterglow emission in an organic-inorganic hybrid material.

Ferroelectricity and Related Properties of Nitratecadmate(II) Hybrid with Metal-Vacancy.

All crystals are not ideal, and many of their properties are often determined not by the regular arrangement of atoms, but by the irregular arrangement of crystal defects. Many properties of materials can be controlled effectively by proper use of solid defects. By substitution of NH ion of a hexagonal perovskite structure (H dabco)(NH )(NO ) (dabco=1,4-diazabicyclo[2.

Large Enhancement of Polarization in a Layered Hybrid Perovskite Ferroelectric Semiconductor via Molecular Engineering.

Switchable spontaneous polarization is the vital property of ferroelectrics, which leads to other key physical properties such as piezoelectricity, pyroelectricity, and nonlinear optical effects, etc. Recently, organic-inorganic hybrid perovskites with 2D layered structure have become an emerging branch of ferroelectric materials. However, most of the 2D hybrid ferroelectrics own relatively low polarizations (<15 µC cm ).

Crystal Sponge Behavior in a Two-Dimensional Rare-Earth Hybrid Coordinate Polymer.

Stimuli-responsive multifunctional materials (SRMMs) have attracted tremendous attention due to their dynamic responses to external stimuli. However, it remains challenging to simultaneously achieve solvent-induced single-crystal to single-crystal (SCSC) transformation and structural phase transition after desolvation. Here, we report a two-dimensional (2D) rare-earth organic-inorganic hybrid coordinate polymer [(CH)NCHCl][Eu·HO][CH(SO)]·2HO () that exhibits a reversible SCSC transformation by changing to ([(CH)NCHCl][Eu·HO][CH(SO)]).

Zero-dimensional organic-inorganic hybrid manganese bromide with coexistence of dielectric-thermal double switches and efficient photoluminescence.

Zero-dimensional (0D) hybrid metal halides have attracted much attention due to their rich composition, excellent optical stability, large exciton binding energy, . Photoelectric switchable multifunctional materials can integrate multiple physical properties (, ferroelectricity, photoluminescence, magnetic, .) into one device and are widely used in many fields such as smart switches, sensors, .

Near-Room-Temperature Synergetic Response of Magnetism, Dielectricity and Luminescence Based on (C NH Cl) MnBr.

Multifunctional materials with working temperatures near room temperature are crucial for practical applications. Until now, it is still a great challenge to obtain such materials. In this paper, a complex of (C NH Cl) MnBr (1) with a structural phase transition near room temperature is reported.

Tuning the luminescent properties of a three-dimensional perovskite ferroelectric (Me-Hdabco)CsI Sn(II) doping.

As promising functional materials, organic-inorganic hybrid metal halide perovskites have attracted significant interest because of their excellent photovoltaic performance. However, although considerable efforts have been made, three-dimensional (3D) metal halide perovskites beyond lead halides have been rarely reported. Herein, a new 3D organic-inorganic hybrid ferroelectric material (Me-Hdabco)CsI (1, Me-Hdabco = -methyl-1,4-diazoniabicyclo[2.

Chiral Rashba Ferroelectrics for Circularly Polarized Light Detection.

Direct detection of circularly polarized light (CPL) is a challenging task due to limited materials and ambiguous structure-property relationships that lead to low distinguishability of the light helicities. Perovskite ferroelectric semiconductors incorporating chirality provide new opportunities in dealing with this issue. Herein, a pair of 2D chiral perovskite ferroelectrics is reported, which have enhanced CPL detection performance due to interplays among lattice, photon, charge, spin, and orbit.

Synthesis, dielectric, magnetic, and photoluminescence properties of two new hybrid rare-earth double perovskites.

Two new organic-inorganic hybrid double perovskites (R3HQ)CsSm(NO) () (R3HQ = ()-(-)-3-quinuclidinol) and (R3HQ)CsEu(NO) () were synthesized and characterized. Compounds and exhibit obvious phase transitions at 379 and 375 K, respectively, confirmed by differential scanning calorimetry (DSC) and variable temperature powder X-ray diffraction. The rapid switching between high- and low-dielectric states makes it a typical dielectric material with a switchable dielectric constant for thermal stimulus response.

Direct observation of geometric and sliding ferroelectricity in an amphidynamic crystal.

Sliding ferroelectricity is a recently observed polarity existing in two-dimensional materials. However, due to the weak polarization and poor electrical insulation in these materials, existing experimental evidences are indirect and mostly based on nanoscale transport properties or piezoresponse force microscopy. We report the direct observation of sliding ferroelectricity, using a high-quality amphidynamic single crystal (15-crown-5)CdCl, which possesses a large bandgap and so allows direct measurement of polarization-electric field hysteresis.

Achieving circularly polarized luminescence and large piezoelectric response in hybrid rare-earth double perovskite by a chirality induction strategy.

Chirality, an intrinsic property of nature, has received increased attention in chemistry, biology, and materials science because it can induce optical rotation, ferroelectricity, nonlinear optical response, and other unique properties. Here, by introducing chirality into hybrid rare-earth double perovskites (HREDPs), we successfully designed and synthesized a pair of enantiomeric three-dimensional (3D) HREDPs, [()--methyl-3-hydroxylquinuclidinium]RbEu(NO) (R1) and [()--methyl-3-hydroxylquinuclidinium]RbEu(NO) (S1), which possess ferroelasticity, multiaxial ferroelectricity, high quantum yields (84.71% and 83.

An Effective Strategy of Introducing Chirality to Achieve Multifunctionality in Rare-Earth Double Perovskite Ferroelectrics.

The hybrid rare-earth double perovskite (HREDP) system provides great convenience for the construction of multifunctional materials. However, suffering from the high symmetry of their intrinsic structure, HREDPs face the challenges in the realization and optimization of ferroelectric and piezoelectric properties. For the first time, after a systematic investigation of the chirality transformation principle, it is found that the introduction of chirality is an efficient strategy for the targeted construction of multifunctionality, which simultaneously increases the possibility of obtaining multiaxial ferroelectricity and ferroelasticity, and effectively realizes a large piezoelectric response.

Structural phase transition in a charge-transfer compound: tropylium hexafluoridoantimonate(V)-1,4-dimethylnaphthalene (1/1).

Molecular motion in crystals has attracted much attention for the development of stimuli-responsive materials. The most studied are molecules with few atoms or highly symmetrical molecules. To develop molecules with new motion characteristics, we synthesized a charge-transfer compound, namely, tropylium hexafluoridoantimonate(V)-1,4-dimethylnaphthalene (1/1), (CH)[SbF]·CH, and studied its structural phase transition.

Single-molecule magnet behaviour in a centrosymmetric dinuclear dysprosium(III) complex: sequential differentiation of triple relaxation pathways.

A dinuclear complex with the formula DyL(HL)Cl(EtOH) (Dy2) has been synthesized by reacting DyCl·HO with a ligand HL (HL = ,'-ethylenebis(salicylideneimine)) using ethanol as the solvent. Its crystal structure can be viewed as a dimer of two Dy(III) fragments, where each Dy(III) site shows a NOCl coordination sphere with a pentagonal bipyramid geometry (). Magnetic measurements reveal that Dy2 behaves as a single-ion magnet (SIM) under a zero field.