Rare-earth-based magnet material, preparation method and application

Abstract

The invention belongs to the technical field of magnetic functional materials. The invention discloses a rare-earth-based magnet material, a preparation method and application. The chemical formula of the rare earth based magnet material disclosed by the invention is [Dy5 (L) 12 (mu3-OH) 2 (H2O) 2] Cl. 4EtOH. 2CH3CN. 5H2O, and L is 2-hydroxy-1-naphthaldehyde. The rare-earth-based magnet material is applied to manufacturing of high-density information storage devices.

Description

Technical Field

[0001] The present application belongs to the technical field of magnetic functional materials, and in particular relates to a rare earth-based magnetic material, a preparation method and an application thereof. Background Art

[0002] Single-molecule magnets (SMMs) are a type of nanomaterials whose magnetism originates from the molecular level. They have the characteristics of magnetic bistability, slow magnetic relaxation behavior, magnetic anisotropy and size uniformity. Due to their unique magnetic and quantum properties, they have shown excellent application potential in many cutting-edge fields such as high-density information storage, magnetic resonance imaging, quantum computing and molecular motors. Summary of the invention

[0003] Purpose of the invention: This application provides a rare earth-based magnetic material, preparation method and application. The rare earth-based magnetic material of this application is a metal complex with single-molecule magnetic behavior, and has broad application prospects in high-density information storage devices.

[0004] Technical solution: The embodiment of the present application provides a rare earth-based magnet material, the chemical formula of the rare earth-based magnet material is: [Dy5(L) 12 ( m 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O, wherein the L ligand is 2-hydroxy-1-naphthaldehyde.

[0005] In some embodiments, the rare earth-based magnet material is composed of five Dy ions, twelve deprotonated ligands L, two m 3-OH ion, two coordinated water molecules, five free water molecules, two acetonitrile molecules, four ethanol molecules and one chloride ion; five Dy ions pass through m The 3-OH groups are connected to form a double triangular five-nuclear structure with common vertices, and each Dy ion has an octahedral coordination configuration.

[0006] In some specific embodiments, [Dy5(L) 12 ( m The structure of 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O consists of five Dy ions, twelve deprotonated ligands L - ,two m 3-OH ion, two coordinated water molecules, five free water molecules, two acetonitrile molecules, four ethanol molecules and one chloride ion. The five Dy ions are Dy1, Dy2, Dy3, Dy1A and Dy3A. Among them, Dy1 is composed of four L - The seven oxygen atoms and one m The oxygen atom of 3-OH is coordinated, and Dy2 is composed of four L- The six oxygen atoms and two m The oxygen atom of 3-OH is coordinated to form Dy3, which is composed of four L - The six oxygen atoms of the ligand, a coordinating water molecule and a m The oxygen atom of 3-OH is coordinated. The Dy(III)-O bond length formed by Dy(III) and oxygen (O) is between 2.241(10)-2.516(10)Å, and the bond angle of O-Dy(III)-O is between 67.8(4)°-152.9(4)°. m 3-OH is connected to form a double triangular five-nuclear structure with common vertices. Each Dy(III) ion is octahedrally coordinated, forming an eight-coordinate configuration close to a tetragonal antiprism.

[0007] In some embodiments, the chemical formula of the rare earth-based magnet material of the present application is C 144 H 130 N2ClDy5O 37 , molecular weight is 3328.49.

[0008] In some embodiments, the coordination polymer formed by the rare earth-based magnet material belongs to the tetragonal system. Space group, the unit cell parameters of the rare earth-based magnet material are: a =18.6608(3)Å, b =18.6608(3)Å, c =51.5002(8)Å, α = 90.00º, β= 90.00º, c= 90.00º.

[0009] In some embodiments, the rare earth-based magnet material is prepared by the following method: Dy(ClO4)3·6H2O, 2-hydroxy-1-naphthaldehyde and 2-amino-2-methyl-1,3-propanediol are dissolved in an organic solvent to obtain a mixed solution, and the obtained mixed solution is placed at room temperature to obtain [Dy5(L) 12 ( m 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O.

[0010] In some embodiments, the room temperature conditions described in the present application are at a temperature of 20°C to 25°C.

[0011] The present application successfully synthesized a dysprosium single-molecule magnet under room temperature conditions. The synthesis method of the present application has the advantages of low energy consumption and low pollution, and provides a new approach for synthesizing metal complexes.

[0012] In some embodiments, the organic solvent comprises anhydrous ethanol and acetonitrile in a volume ratio of 1:(2-3).

[0013] In some embodiments, the standing time at room temperature is 5 h to 24 h.

[0014] In some embodiments, the molar ratio of Dy(ClO4)3·6H2O, 2-hydroxy-1-naphthaldehyde and 2-amino-2-methyl-1,3-propanediol is 0.1:0.4:0.2.

[0015] In some embodiments, the above rare earth-based magnetic material or the rare earth-based magnetic material prepared by the above method for preparing the rare earth-based magnetic material is used in preparing a high-density information storage device.

[0016] Beneficial effects: The present application provides a rare earth-based magnet material, a preparation method and an application. The chemical formula of the rare earth-based magnet material of the present application is: [Dy5(L) 12 ( m 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O, wherein L is 2-hydroxy-1-naphthaldehyde. The rare earth-based magnetic material of the present application is used for manufacturing high-density information storage devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a molecular structure diagram of the rare earth-based magnet material prepared in Example 1 of the present invention; Figure 2 is a molecular skeleton diagram of the rare earth-based magnet material prepared in Example 1 of the present invention; Figure 3 is a skeleton structure diagram of the rare earth-based magnet material prepared in Example 1 of the present invention; Figure 4 is a polyhedron diagram of the rare earth-based magnet material prepared in Example 1 of the present invention with Dy1 as the center; Figure 5 is a polyhedron diagram of the rare earth-based magnet material prepared in Example 1 of the present invention with Dy2 as the center; Figure 6 is a polyhedron diagram of the rare earth-based magnet material prepared in Example 1 of the present invention with Dy3 as the center; Figure 7 The rare earth-based magnet material prepared in Example 1 of the present invention xM、xMT Temperature T Change curve chart; Figure 8 The rare earth-based magnet material prepared in Example 1 of the present invention x′ ' -v Graphs; Figure 9The rare earth-based magnet material prepared in Example 1 of the present invention x ''- T picture; Figure 10 The rare earth-based magnet material prepared in Example 1 of the present invention x′′-x′ Isotherm curve; Figure 11 The rare earth-based magnet material prepared in Example 1 of the present invention right The change curve of Figure 12 This is an infrared spectrum of the rare earth-based magnet material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0018] Example 1: Rare earth-based magnet material [Dy5(L) 12 ( m Preparation of 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O Dy(ClO4)3·6H2O (0.1mmol, 0.0568g), 2-hydroxy-1-naphthaldehyde (0.4mmol, 0.0688g), and 2-amino-2-methyl-1,3-propanediol (0.1mmol, 0.0210g) were accurately weighed in a lead-free glass bottle in turn, and 1.5mL of acetonitrile and 0.5mL of anhydrous ethanol were added. The mixture was fully shaken to ensure uniform mixing to form a yellow solution. The solution was exposed to air at room temperature and left statically for 10h to obtain light yellow crystals, which were rare earth-based magnet materials [Dy5(L) 12 ( m 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O.

[0019] Example 2: Performance measurement of rare earth-based magnet materials (1) Structural characterization: The single crystal rare earth-based magnet material with good texture and regular crack-free structure prepared in Example 1 was selected and characterized by using a SuperNova X-ray single crystal diffractometer on a graphite monochromator. Mo- Under Kα radiation (λ=0.7107Å), 293(2)K conditions, at a specific i Range f-o The diffraction points were collected by scanning mode for single crystal structure analysis and correction. All compounds were solved by direct method and refined by full matrix least squares method using ShelXL-2014 and SHELXL program packages. All non-hydrogen atoms were refined by direct method. The crystal determination data of the rare earth-based magnet material prepared in Example 1 of the present application are shown in Table 1, and the specific bond lengths and bond angles are shown in Table 2. The molecular structure is shown in Figure 1~Figure 6 shown.

[0020] Table 1 Crystal measurement data of rare earth-based magnet material prepared in Example 1

[0021] Data in Table 1 represents the number of independent diffraction points involved in the correction, Restrains represents the number of restrictions used in the correction process, and parameters represents the number of variables involved in the correction.

[0022] Table 2 Bond lengths and angles of rare earth-based magnet materials prepared in Example 1

[0023] (2) Determination of magnetic properties The rare earth-based magnet material prepared in Example 1 was subjected to variable temperature DC magnetic susceptibility measurement in a 1000 Oe external DC magnetic field and a temperature range of 2 K to 300 K. Figure 7 As shown, the rare earth-based magnet material prepared in Example 1 is x M T The value is 69.63cm 3 Kmol -1 , and the theory of five independent Dy(III) ions x M T The value is very close to this value. When the temperature is 113.15K~300K, x M T First, it remains stable, and when the temperature is lower than 113.15K, the rare earth-based magnet material prepared in Example 1 x M T The value begins to drop sharply and reaches the minimum value of 48.69cm at a temperature of 2K. 3 Kmol -1 In the entire test environment, the molar magnetic susceptibility of the rare earth-based magnet material prepared in Example 1 is x M It shows a negative correlation with temperature. At the same time, the variable frequency AC magnetic susceptibility of the rare earth-based magnet material prepared in Example 1 was measured under the conditions of an external oscillating AC magnetic field of 2Oe and a temperature of 2K. The rare earth-based magnet material prepared in Example 1 showed a very obvious frequency dependence in a low temperature environment and a very obvious temperature dependence at a high frequency. It can be seen from the above results that the complex prepared in Example 1 is a metal complex with single-molecule magnet behavior.

[0024] like Figure 8As shown, when the rare earth-based magnet material prepared in Example 1 is at a temperature of 2K and an oscillating AC magnetic field of 2Oe, it exhibits obvious frequency dependence, and exhibits obvious temperature dependence in the high-frequency region, which indicates that the rare earth-based magnet material prepared in Example 1 exhibits single-molecule magnet behavior.

[0025] like Figure 9 As shown, when the rare earth-based magnet material is at a temperature of 2K, an oscillating AC magnetic field of 2Oe and an external DC field of 2000Oe, it exhibits obvious temperature dependence and obvious frequency dependence in the low temperature region, which indicates that the rare earth-based magnet material prepared in Example 1 exhibits single-molecule magnet behavior.

[0026] like Figure 10 As shown, in order to explore the relaxation mechanism of the rare earth-based magnet material prepared in Example 1, the AC magnetic susceptibility of the rare earth-based magnet material was plotted. x ''- x ′ is the Cole-Cole curve. Figure 11 As shown, according to x ''- x ′ Curve fitting derivative data plotting right According to formula (1): Formula (1); Over the entire measuring temperature range right The curve is linearly fitted, ignoring the QTM process . It turns out that: .

[0027] (3) Infrared spectroscopy analysis like Figure 12 As shown, the absorption peak of the rare earth-based magnet material prepared in Example 1 is at 3424 cm -1 It is relatively wide and long near 1619cm. It is believed that this segment belongs to the signal peak generated by the stretching vibration of rare earth-based magnet materials or water molecules in the environment. -1 There is a sharp peak at 1188cm, which is the signal peak generated by the stretching vibration of the C=C conjugated double bond in the benzene ring. -1 There is a weaker peak, which belongs to the signal peak generated by the CO stretching vibration of phenolic hydroxyl group.

[0028] It can be seen from the above results that the rare earth-based magnetic material prepared in the examples of the present application is a metal complex with single-molecule magnetic behavior, and has broad application prospects in high-density information storage devices.

[0029] The above is a detailed introduction to a rare earth-based magnet material, preparation method, application and application provided in the embodiments of the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for technical personnel in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A rare earth-based magnet material, characterized in that: The chemical formula of the rare earth-based magnet material is: [Dy5(L) 12 ( μ 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O, wherein L is 2-hydroxy-1-naphthaldehyde.

2. The rare earth-based magnet material according to claim 1, characterized in that: The rare earth-based magnet material comprises five Dy ions, twelve deprotonated ligands L, and two μ 3-OH ion, two coordinated water molecules, five free water molecules, two acetonitrile molecules, four ethanol molecules and one chloride ion; five Dy ions are connected by two μ The 3-OH groups are connected to form a double-triangular five-nuclear structure with common vertices, and each Dy ion is an octahedral coordination configuration.

3. The rare earth-based magnet material according to claim 1, characterized in that: The coordination polymer formed by the rare earth-based magnet material belongs to the tetragonal system. Space group, the unit cell parameters of the rare earth-based magnet material are: a =18.6608(3)Å, b =18.6608(3)Å, c =51.5002(8)Å, α= 90.00º, β= 90.00º, γ= 90.00º.

4. The rare earth-based magnet material according to claim 1, characterized in that: The rare earth-based magnet material is prepared by the following method: Dy(ClO4)3·6H2O, 2-hydroxy-1-naphthaldehyde and 2-amino-2-methyl-1,3-propanediol are dissolved in an organic solvent to obtain a mixed solution, and the obtained mixed solution is allowed to stand at room temperature to obtain [Dy5(L) 12 ( μ 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O.

5. A method for preparing a rare earth-based magnet material as claimed in claim 1, characterized in that: The following steps are involved: Weigh Dy(ClO4)3·6H2O, 2-hydroxy-1-naphthaldehyde and 2-amino-2-methyl-1,3-propanediol and dissolve them in an organic solvent to obtain a mixed solution. The obtained mixed solution is placed at room temperature to obtain [Dy5(L) 12 ( μ 3-OH)2(H2O)2]Cl·4EtOH·2CH3CN·5H2O.

6. The method for preparing a rare earth-based magnet material according to claim 5, characterized in that: The organic solvent includes anhydrous ethanol and acetonitrile in a volume ratio of 1:(2-3).

7. The method for preparing a rare earth-based magnet material according to claim 5, characterized in that: The standing time under the room temperature condition is 5h~24h.

8. The method for preparing a rare earth-based magnet material according to claim 5, characterized in that: The molar ratio of Dy(ClO4)3·6H2O, 2-hydroxy-1-naphthaldehyde and 2-amino-2-methyl-1,3-propanediol is 0.1:0.4:0.

2.

9. Use of a rare earth-based magnetic material as claimed in any one of claims 1 to 4 or a rare earth-based magnetic material prepared by the method for preparing a rare earth-based magnetic material as claimed in any one of claims 5 to 8 in preparing a high-density information storage device.

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