A dysprosium-based magnetoelectric compound with magnetoelectric behavior, its preparation method, and its applications.

Abstract

This application relates to the field of functional materials preparation technology, specifically to a dysprosium-based magnetoelectric compound with magneto-controlled electrical behavior constructed using chiral proline as a ligand, its preparation method, and its application. This dysprosium-based magnetoelectric compound allows for the modulation of its electrical properties using a magnetic field. This dysprosium-based magnetoelectric compound addresses the limitations of molecular-based magnetoelectric coupling materials and their demanding preparation conditions. It is an eight-coordinate dysprosium-based molecular magnetoelectric material that simultaneously exhibits slow magnetic relaxation behavior and magnetic field-controlled electrical properties. The resulting magnetoelectric properties can significantly improve the information storage density of non-volatile memories and contribute to improving the performance of molecular spintronic devices. Its unique performance advantages not only help overcome the performance bottlenecks of traditional silicon-based electronic devices but also provide a new breakthrough for the fundamental research and application development of magnetoelectric materials.

Description

Technical Field

[0001] This application relates to the field of functional materials preparation technology, specifically to a dysprosium-based magnetoelectric compound with magnetoelectric behavior, its preparation method, and its application. Background Technology

[0002] Molecular-based materials are crystalline materials composed of ordered arrangements and assemblies of metal ions and organic ligands. They possess high designability, rich structures, tunable spin states, and unique macroscopic physical properties. Compared to inorganic materials, molecular-based materials have a greater advantage in flexible lattices, overcoming the limitations of the rigid structures of inorganic materials. Therefore, molecular-based materials require lower magnetic field strengths to achieve magnetoelectric coupling, making them more promising for practical device applications.

[0003] Molecular-based materials with magnetoelectric coupling effects can exhibit unique magnetic, electrical, and magnetoelectric coupling effects. The materials involved in this application have been experimentally verified to exhibit slow magnetic relaxation behavior, and their dielectric properties can be effectively controlled by an external magnetic field, demonstrating a clear "magnetically controlled electricity" behavior. Devices fabricated from these functional materials can exhibit four-fold reconfiguration characteristics, which will greatly improve the non-volatile information storage density and contribute to the enhancement and improvement of the performance of non-silicon-based electronic devices. However, current research on magnetoelectric coupling materials faces two major challenges: firstly, naturally occurring magnetoelectric materials are scarce; and secondly, the preparation conditions for oxide-type compounds are usually quite demanding, while molecular-based materials show significant advantages.

[0004] With the development and progress of chemical synthesis technology and molecular crystallography engineering, obtaining molecular-based magnetoelectric coupling materials through chemical synthesis is a better approach. This study successfully prepared dysprosium-based magnetoelectric compounds exhibiting magnetoelectric behavior using a simple synthesis method and mild experimental conditions. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this application is to provide a dysprosium-based magnetoelectric compound with magnetoelectric behavior, its preparation method, and its application. The following technical solutions address the problems mentioned in the background art.

[0006] The primary objective of this application is to provide a dysprosium-based magnetoelectric compound with the chemical formula [Dy(C5H9NO2)2(H2O)6]Cl3, belonging to the monoclinic crystal system, with space group P21 chiral space group, and cell parameters a=8.27480(10)Å, b=11.0261(2)Å, c=11.8147(2)Å, α=γ=90°, β≠90°.

[0007] The second objective of this application is to provide a method for preparing the above-mentioned dysprosium-based magnetoelectric compound, comprising the following steps: S1, mixing L-proline and DyCl3·6H2O at a molar ratio of 2:1 to obtain a mixture for later use; S2, mixing acetonitrile and methanol at a volume ratio of 3~3.5:1 to obtain a mixed solvent for later use; S3, mixing the mixture and the mixed solvent at a ratio of 7.7mg:1mL, stirring at room temperature and allowing to stand to obtain colorless cuboid crystals as the dysprosium-based magnetoelectric compound. Further, the preparation method may also include a purification step: S4, washing the obtained dysprosium-based magnetoelectric compound with icy ethanol to obtain purified dysprosium-based magnetoelectric compound.

[0008] The third objective of this application is to provide an application of the aforementioned dysprosium-based magnetoelectric compound, which simultaneously possesses slow magnetic relaxation behavior and magnetic field-controlled electrical properties. This compound can be used as a core material for magnetoelectric sensors to develop high-density non-volatile memories, high-performance molecular spintronic devices, and high-sensitivity magnetoelectric sensors. In memories and spintronic devices, its magnetoelectric coupling characteristics help improve information storage density and device performance. In magnetoelectric sensors, high-sensitivity magnetoelectric signal detection is achieved by measuring the nonlinear change in the compound's dielectric constant with respect to an applied magnetic field.

[0009] Compared with existing technologies, this application has the following beneficial effects: This application relates to a dysprosium-based magnetoelectric compound with magnetoelectric behavior. This dysprosium-based magnetoelectric compound is an eight-coordinate dysprosium-based molecular magnetoelectric material that addresses the problems of the scarcity of molecular-based magnetoelectric coupling materials and the harsh preparation conditions. It can simultaneously exhibit slow magnetic relaxation behavior and magnetic field-controlled electrical properties. The exhibited magnetoelectric properties can significantly improve the information storage density of non-volatile memory and help improve the performance of molecular spintronic devices. Its unique performance advantages not only help to break through the performance bottleneck of traditional silicon-based electronic devices, but also provide a new breakthrough for the basic research and application development of magnetoelectric materials. The preparation method of this novel chiral dysprosium-based molecular magnetoelectric material adopts a simple and mild solution chemical synthesis method. The prepared dysprosium-based magnetoelectric compound not only exhibits typical slow magnetic relaxation behavior, but also shows significant magnetic field-controlled electrical properties. Attached Figure Description

[0010] Other features, objects, and advantages of this application will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings.

[0011] Figure 1 The structure diagram of [Dy(C5H9NO2)2(H2O)6]Cl3 obtained by single-crystal diffraction analysis;

[0012] Figure 2Experimental diagram of DC magnetic susceptibility of [Dy(C5H9NO2)2(H2O)6]Cl3;

[0013] Figure 3 Experimental diagram of the variable field magnetic susceptibility of [Dy(C5H9NO2)2(H2O)6]Cl3;

[0014] Figure 4 The experimental plot of temperature-dependent alternating current magnetic susceptibility of [Dy(C5H9NO2)2(H2O)6]Cl3;

[0015] Figure 5 The diagram shows the Cole-Cole experiment for [Dy(C5H9NO2)2(H2O)6]Cl3;

[0016] Figure 6 The diagram shows the magnetic control experiment of [Dy(C5H9NO2)2(H2O)6]Cl3. Detailed Implementation

[0017] The present application will be further described below with reference to specific embodiments. These embodiments are only used to more clearly illustrate the technical solutions of the present application and should not be construed as limiting the scope of protection of the present application. Anything not described in detail in this patent application is considered common knowledge in the art.

[0018] The term "and / or" as used in this application includes any and all combinations of one or more of the associated listed items. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized by conventional methods and are ready for use without further processing, as are the instruments used in the examples. All technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in this application and in its specification is for the purpose of describing particular embodiments only and is not intended to be limiting of this application.

[0019] like Figure 1 As shown, the octetral dysprosium magnetoelectric compound exhibiting magnetoelectric behavior in this application has the chemical formula [Dy(C5H9NO2)2(H2O)6]Cl3, belongs to the monoclinic crystal system, and has the space group P21 chiral space group. In the formula, C5H9NO2 represents chiral L-proline, and the chiral central dysprosium ion Dy... 3+ In an eight-coordinated environment, the eight coordinating atoms are derived from the oxygen atoms in the six H₂O ligands and the carboxyl oxygen atoms in the two L-proline ligands. Three monovalent Cl ions exist in the crystal lattice as free counterions to balance the cation of the compound [Dy(C₅H₉NO₂)₂(H₂O)₆]. 3+The charge is used to maintain electrical neutrality.

[0020] In some embodiments, the preparation method of the dysprosium-based magnetoelectric compound includes the following steps: S1, mixing the ligand L-proline with the metal salt dysprosium chloride hexahydrate (DyCl3·6H2O) at a molar ratio of 2:1 to obtain a mixture for later use; S2, mixing acetonitrile and methanol at a volume ratio of 3~3.5:1 to obtain a mixed solvent for later use; S3, mixing the mixture obtained in step S1 with the mixed solvent obtained in step S2 at a ratio of 7.7mg:1mL, stirring at room temperature for 3h~4h, and separating by standing at room temperature for 3 to 7 days to obtain colorless cuboid crystals as the dysprosium-based magnetoelectric compound.

[0021] In some other embodiments, step S4 is also included, in which the dysprosium-based magnetoelectric compound is washed with ice-cold ethanol for purification to obtain a dysprosium-based magnetoelectric compound with higher purity.

[0022] In some embodiments, the dysprosium-based magnetoelectric compound obtained by the above preparation method is used as a core material for magnetoelectric sensors. This dysprosium-based magnetoelectric compound simultaneously exhibits slow magnetic relaxation behavior and magnetic field-controlled electrical properties. It can be used to develop high-density non-volatile memories, high-performance molecular spintronic devices, and high-sensitivity magnetoelectric sensors. In memories and spintronic devices, its magnetoelectric coupling characteristics help improve information storage density and device performance. In magnetoelectric sensors, high-sensitivity magnetoelectric signal detection is achieved by measuring the nonlinear change in the compound's dielectric constant with respect to an applied magnetic field.

[0023] Example 1

[0024] This embodiment provides a dysprosium-based magnetoelectric compound [Dy(C5H9NO2)2(H2O)6]Cl3 and its preparation method. The preparation method is as follows: 120.4 mg of L-proline solution and 188.5 mg of DyCl3·6H2O are dissolved and added to a beaker, followed by 30 mL of acetonitrile and 10 mL of methanol. The mixture is stirred at room temperature for 4 h and allowed to stand at room temperature for 3 days to obtain colorless cuboid crystals. The crystals are washed with ice-cold ethanol to purify the product.

[0025] Example 2

[0026] This embodiment provides a dysprosium-based magnetoelectric compound [Dy(C5H9NO2)2(H2O)6]Cl3 and its preparation method. The preparation method is as follows: 120.4 mg of L-proline solution and 188.5 mg of DyCl3·6H2O are dissolved and added to a beaker, followed by 25 mL of acetonitrile and 15 mL of ethanol. The mixture is stirred at room temperature for 4 hours and then allowed to stand at room temperature for 3 days to obtain colorless cuboid crystals. The crystals are washed with ice-cold ethanol to purify the product.

[0027] To further verify the technical solution of this application and its beneficial effects, the performance of the dysprosium-based magnetoelectric compound prepared in Example 1 was tested.

[0028] Experimental Example 1: Determination of Crystal Structure

[0029] 1. Crystal structure determination was performed using an X-ray single-crystal diffractometer with Mo-K monochromated graphite. α The incident radiation source was X-ray (λ=0.71073Å). Diffraction points were collected using ω-φ scanning. The unit cell parameters were obtained after correction by the least squares method. The crystal structure was obtained by direct solution using the SHELXL-97 method from the difference Fourier electron density map and corrected by Lorentz and polarization effects. All H atoms were synthesized by difference Fourier and determined by calculation of ideal positions. The crystallographic data are shown in Table 1.

[0030] Table 1. Crystallographic data of dysprosium-based magnetoelectric compounds

[0031] formula <![CDATA[C 10 H 26 Cl3DyN2O9]]> fw 587.18 temp(K) 80.0(3) cryst system Monoclinic space group <![CDATA[P21]]> a (Å) 8.27480(10) b (Å) 11.0261(2) c (Å) 11.8147(2) α (deg) 90 β (deg) 106.872(2) γ (deg) 90 <![CDATA[V (Å 3 )]]> 1031.56(3) Z 2 <![CDATA[Dc (g·cm -3 )]]> 1.890 Limiting indices -9 ≤ h ≤ 10, -13 ≤ k ≤ 13, -14 ≤ l ≤ 14 <![CDATA[μ (mm -1 )]]> 23.347 <![CDATA[R int ]]> 0.0579 GOOF 1.134 R1 0.0587 wR2 0.1635 <![CDATA[△ρmax (e Å -3 )]]> 2.55 △ρmin (eÅ-3) -1.65 Flack -0.029(9)

[0032] 2. The structural diagram of [Dy(C5H9NO2)2(H2O)6]Cl3 prepared in Example 1 is shown below. Figure 1 As shown in the figure, the eight-coordinated dysprosium ion of the dysprosium-based magnetoelectric compound is located at the center of a tetragonal antiprism and is coordinated with eight oxygen atoms: two oxygen atoms come from the carboxyl oxygen of two L-proline molecules, and the other six oxygen atoms come from the oxygen in six water molecules.

[0033] Experimental Example 2: Characterization of Magnetic Properties

[0034] Magnetic measurements were performed using a Quantum Design MPMS SQUID superconducting quantum interference device, and the results are as follows: Figure 2 As shown, at a temperature of 300 K, the product of DC magnetic susceptibility (χ) and temperature (T) is 14.37 cm³ K mol. -1 , and spin-only Dy³ + Ions (ground state is) 6 H 15 / 2 The theoretical value (S=5 / 2, L=5, g=4 / 3) is 14.17 cm³ K mol. -1 Consistent.

[0035] The variable field magnetic susceptibility curve of this dysprosium-based magnetoelectric compound at low temperatures (2K-10K) is shown below. Figure 3 As shown, at a temperature of 2K, when the magnetic field reaches 7T, the magnetization of this compound is 5.43 Nβ, which does not reach the theoretical saturation value of 10 Nβ. The non-overlapping magnetic susceptibility curves at different temperatures indicate that this compound exhibits significant magnetic anisotropy or low-energy state excitation.

[0036] To further investigate its magnetic properties, AC magnetic susceptibility measurements were performed, demonstrating that the compound exhibits significant temperature and frequency dependence under a 1200 Oe applied DC field. Figure 4 As shown.

[0037] The Cole-Cole data obtained from frequency-based experimental data also confirm its magnetic relaxation behavior, such as... Figure 5 As shown.

[0038] Experimental Example 3: Magnetic Field Controlling Electrical Properties

[0039] Magnetoelectric coupling measurements were performed using a Quantum Design PPMS integrated physical property testing system with a superconducting quantum interference device. Under an applied magnetic field, the relative permittivity of the single-ion magnet at temperatures ranging from 2K to 200K varies with the magnetic field from -7T to 7T, as shown in the curve. Figure 6 As shown, the relative permittivity of this material exhibits a nonlinear change with the applied magnetic field, indicating that the compound possesses magnetoelectric behavior with magnetic field-controlled electrical properties.

[0040] Experimental Example 4: Yield Determination

[0041] The yield of Example 1 was calculated to be 52% based on dysprosium.

[0042] Based on the preferred embodiments of this application, and through the above description, those skilled in the art can make various changes and modifications without departing from the technical concept of this application. The technical scope of this application is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A dysprosium-based magnetoelectric compound having magnetically controlled electrical behavior, wherein, The crystal of the dysprosium-based magnetoelectric compound with magnetron electric behavior, with the chemical formula of [Dy(C5H9NO2)2(H2O)6]Cl3, belongs to a monoclinic crystal system, a P21 chiral space group, and a cell parameter of a=8.27480(10) Å, b=11.0261(2) Å, c=11.8147(2) Å, α=γ=90°, and β≠90°.

2. A method of producing the dysprosium-based magnetoelectric compound of claim 1, wherein, The method comprises the following steps: L-proline is mixed with DyCl3·6H2O at a molar ratio of 2:1 to obtain a mixture, which is used for later mixing; Acetonitrile and methanol are mixed at a volume ratio of 3-3.5:1 to obtain a mixed solvent, which is used for later mixing; The mixture and the mixed solvent are mixed at a ratio of 7.7 mg:1 mL, stirred at room temperature, and left to stand to obtain colorless cuboid crystals of the dysprosium-based magnetoelectric compound.

3. The production method according to claim 2, wherein, The method further comprises a purification step of washing the obtained dysprosium-based magnetoelectric compound with ice ethanol to obtain a purified dysprosium-based magnetoelectric compound.

4. Use of a dysprosium-based magneto-electric compound as claimed in claim 1, wherein, The dysprosium-based magnetoelectric compound is used as a core material of a magnetoelectric sensing device, and simultaneously has slow magnetic relaxation behavior and magnetic field-regulated electrical properties.

5. Use according to claim 4, wherein, The dysprosium-based magnetoelectric compound is applied to a magnetoelectric sensing device, and the dielectric constant of the device changes nonlinearly with an applied magnetic field.

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