CN110790699A - Cobalt-based single-ion magnet material, preparation method and application thereof - Google Patents

Cobalt-based single-ion magnet material, preparation method and application thereof Download PDF

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CN110790699A
CN110790699A CN201911145565.8A CN201911145565A CN110790699A CN 110790699 A CN110790699 A CN 110790699A CN 201911145565 A CN201911145565 A CN 201911145565A CN 110790699 A CN110790699 A CN 110790699A
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cobalt
based single
magnet material
tpa
bpa
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陈磊
蔡星伟
易刚吉
赵文
张春洋
袁爱华
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Jingfeng Technology Zhoushan Co ltd
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Jiangsu University of Science and Technology
Marine Equipment and Technology Institute Jiangsu University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/42Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13Crystalline forms, e.g. polymorphs

Abstract

The invention relates to a cobalt-based single-ion magnet magnetic material, a preparation method and application thereof, wherein the chemical formula of the cobalt-based single-ion magnet material is [ Co (BPA-TPA)]·(BF4)2Wherein BPA-TPA is an organic ligand 2, 6-bis (di (2-pyridylmethyl) amine) picoline, and the chemical structure is as follows:
Figure DDA0002282089050000011
co (II) coordinates with seven nitrogen atoms of an organic ligand BPA-TPA to form a coordination configuration of a single-crown triangular prism; the mononuclear cobalt complex belongs to a triclinic system, P-1 space group and has unit cell parameters of α=71.015(2), β -67.784 (2) and gamma-70.936 (2) have the advantages that the invention develops a high-coordination (coordination number is 7-8) transition metal single ion magnet, the provided preparation method is simple and has good controllability, and the prepared complex can be used for preparing magnetic materials.

Description

Cobalt-based single-ion magnet material, preparation method and application thereof
Technical Field
The invention belongs to a novel high-density magnetic storage material, and particularly relates to a cobalt-based single-ion magnet material, a preparation method and application thereof.
Background
The magnetic material has wide application, and the application market of the magnetic material exceeds that of a semiconductor material. Among them, information storage has been one of the largest applications of magnetic materials. With the development of information technology, the number of integrated electronic devices is required to exponentially increase and the device size is continuously reduced. The continuous development of integration and miniaturization is limited by the processing technology and cost, which causes the difficulty of overcoming the obstacles of modern electronic device integration technology. Therefore, the development of molecular-based magnetic materials has become a focus of attention of scientists. Single Molecule Magnets (SMMs) are an important area of molecular-based magnetic material research. The magnetic material can represent the macroscopic magnetism of a classic magnet and the quantum tunneling effect of microscopic particles, becomes a bridge connecting the classic magnetism theory and the quantum theory, and has huge application potential in high-density information storage, quantum computers and molecular spinning.
The switching energy barrier U of the SMM is determined by the ground state spin value (S) of the system and the negative zero field splitting energy parameter (D), and the relationship is that U is S2| D | or (S)2-1/4) | D |. Initially, researchers selected appropriate bridging ligands to modulate the magnetic interaction between the respective spin carriers to a ferromagnetic interaction, increasing the ground state spin value (S), and thus obtaining unimolecular magnets. Such SMMs are mainly focused on clusters containing transition metals such as manganese, cobalt, iron and nickel. However, researchersIt was found that an increase in S decreases the value of D, and that the value of the inversion energy barrier U cannot be effectively increased by increasing S alone. Therefore, researchers have constructed mononuclear complexes using lanthanide ions and transition metal ions having relatively strong magnetic anisotropy, and have obtained monomolecular magnets by increasing the D value. This type of single-molecule magnet is also called a single-ion magnet (SIM) because the molecular structure has only one magnetic center.
The first example of transition metal single ion magnet K [ (tpa) was reported in 2010 by Long et alMes)FeII][1]Single ion magnets based on 3d transition metals have attracted the attention of researchers and have been rapidly developed. Currently, single ion magnets based on magnetic centers such as Mn (III), Fe (I/II/III), Co (II), Ni (I), Cr (II), and Re (IV) have been reported. However, most of transition metal-based single-ion magnets are low-coordination (coordination number is 2-6) compounds, and transition metal-based single-ion magnets with high coordination (coordination number is 7-8) are rarely reported.
Disclosure of Invention
The invention aims to provide a cobalt-based single-ion magnet magnetic material with a single-crown triangular prism configuration, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows: the cobalt-based single-ion magnet material has the innovation points that: the chemical formula of the cobalt-based single-ion magnet material is [ Co (BPA-TPA)]·(BF4)2Wherein BPA-TPA is an organic ligand 2, 6-bis (di (2-pyridylmethyl) amine) picoline, and the chemical structure is as follows:
Figure BDA0002282089030000021
co (II) coordinates with seven nitrogen atoms of an organic ligand BPA-TPA to form a coordination configuration of a single-crown triangular prism;
the mononuclear cobalt complex belongs to a triclinic system, P-1 space group and has unit cell parameters of
Figure BDA0002282089030000031
Figure BDA0002282089030000032
α=71.015(2)°,β=67.784(2)°,γ=70.936(2)°。
The preparation method of the cobalt-based single-ion magnet material has the innovation points that: the preparation method comprises the following steps:
step 1: in the closed state, anhydrous cobalt halide CoX2Reacting with silver tetrafluoroborate AgBF in acetonitrile solution4Stirring, mixing and reacting to generate AgX precipitate, wherein X is Cl or Br;
step 2: filtering to remove AgX precipitate generated in the step 1, adding organic ligand BPA-TPA into the filtrate, and stirring for 30-35 min;
and step 3: and (3) after stirring, transferring the mixed solution formed in the step (2) into a test tube, and slowly adding diethyl ether for two-phase diffusion to obtain the cobalt-based single-ion magnet material.
Further, AgBF in the step 14And CoX2In a molar ratio of 2:1, the amount of acetonitrile used being per 0.5mmoL of CoX2Corresponding to 4-7mL of acetonitrile.
Further, the organic ligand BPA-TPA in the step 2 and the CoX in the step 12The molar ratio of (A) to (B) is 1-1.3: 1.
Further, the amount of the diethyl ether in the step 3 is 2-4 times of that of the acetonitrile in the step 1.
The application of the cobalt-based single-ion magnet material is characterized in that: the cobalt-based single ion magnet material is used as a molecular-based magnetic material.
The invention has the advantages that: the cobalt-based single-ion magnet magnetic material, the preparation method and the application thereof provided by the invention develop a high-coordination (coordination number is 7-8) transition metal single-ion magnet, the provided preparation method is simple and has good controllability, and the prepared complex can be used for preparing a magnetic material.
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The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows a cobalt-based single ion magnet [ Co (BPA-TPA) ] of example 3]·(BF4)2Middle complex cation [ Co (BPA-TPA)]2+Crystal structure of (2).
FIG. 2 shows a cobalt-based single ion magnet [ Co (BPA-TPA) ] of example 3]·(BF4)2Powder X-ray diffraction pattern of (1).
FIG. 3 shows a cobalt-based single ion magnet [ Co (BPA-TPA) of example 3]·(BF4)2The direct current magnetic susceptibility test chart.
FIG. 4 shows a cobalt-based single ion magnet [ Co (BPA-TPA) of example 3]·(BF4)2Field-dependent magnetization diagram.
FIG. 5 shows a cobalt-based single ion magnet [ Co (BPA-TPA) of example 3]·(BF4)2Plot of imaginary alternating magnetic susceptibility versus temperature dependence.
FIG. 6 shows a cobalt-based single ion magnet [ Co (BPA-TPA) of example 3]·(BF4)2Cole-Cole plot of (1).
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
The cobalt-based single ion magnet material has a chemical formula of [ Co (BPA-TPA)]·(BF4)2Wherein BPA-TPA is an organic ligand 2, 6-bis (di (2-pyridylmethyl) amine) picoline, and the chemical structure is as follows:
co (II) coordinates with seven nitrogen atoms of an organic ligand BPA-TPA to form a coordination configuration of a single-crown triangular prism;
the mononuclear cobalt complex belongs to a triclinic system, P-1 space group and has unit cell parameters of
Figure BDA0002282089030000053
α=71.015(2)°,β=67.784(2)°,γ=70.936(2)°。
The preparation method of the cobalt-based single-ion magnet material comprises the following steps:
step 1: in the closed state, anhydrous cobalt halide CoX2Reacting with silver tetrafluoroborate AgBF in acetonitrile solution4Stirring, mixing and reacting to generate AgX precipitate, wherein X is Cl or Br;
step 2: filtering to remove AgX precipitate generated in the step 1, adding organic ligand BPA-TPA into the filtrate, and stirring for 30-35 min;
and step 3: and (3) after stirring, transferring the mixed solution formed in the step (2) into a test tube, and slowly adding diethyl ether for two-phase diffusion to obtain the cobalt-based single-ion magnet material.
As an example, the specific implementation is AgBF in step 14And CoX2In a molar ratio of 2:1, the amount of acetonitrile used being per 0.5mmoL of CoX2Corresponding to 4-7mL of acetonitrile, organic ligand BPA-TPA in step 2 and CoX in step 12The molar ratio of (A) to (B) is 1-1.3: 1, and the amount of diethyl ether in the step (3) is 2-4 times of that of acetonitrile in the step (1).
The cobalt-based single ion magnet material is used as a molecular-based magnetic material.
The cobalt-based single ion magnet material of the present invention is described in detail below by way of specific examples, specifically as follows:
example 1:
adding CoCl2(0.5mmol) and AgBF4(1mmol) is stirred and mixed in 5mL acetonitrile solution, white flocculent AgCl precipitate is generated immediately, the precipitate is removed by filtration, organic ligand BPA-TPA (0.5mmol) is added into the filtrate, the mixture is stirred for 30min, the mixture is transferred into a test tube, 10mL diethyl ether is slowly dripped to form two-phase layering, and after 2 days, the diethyl ether is completely diffused into the lower acetonitrile solution, thus obtaining the crystal of the cobalt-based single ion magnet material.
The yield of the single ion magnet prepared in this example was 43.8%.
Example 2:
adding CoCl2(0.5mmol) and AgBF4(1mmol) was stirred in 7mL acetonitrile and mixed to give a white flocculent AgCl precipitate immediately, which was filtered off to remove the precipitateAdding organic ligand BPA-TPA (0.7mmol) into the filtrate, stirring for 30min, transferring into a test tube, slowly dropping 20mL of diethyl ether to form two-phase layering, and completely diffusing diethyl ether into the lower acetonitrile solution after 3 days to obtain the crystal of the cobalt-based single ion magnet material.
The yield of the single ion magnet prepared in this example was 42.4%.
Example 3:
adding CoBr2(0.5mmol) and AgBF4(1mmol) is stirred and mixed in 5mL acetonitrile solution, white flocculent AgCl precipitate is generated immediately, the precipitate is removed by filtration, organic ligand BPA-TPA (0.5mmol) is added into the filtrate, the mixture is stirred for 30min, the mixture is transferred into a test tube, 10mL diethyl ether is slowly dripped to form two-phase layering, and after 2 days, the diethyl ether is completely diffused into the lower acetonitrile solution, thus obtaining the crystal of the cobalt-based single ion magnet material.
The yield of the single ion magnet prepared in this example was 41.9%.
The cobalt-based single ion magnet prepared in this example was characterized as follows:
(1) determination of Crystal Structure
Selecting a single crystal with proper size under a microscope, and monochromating a molybdenum target by using graphite on a Bruker SMART Apex II CCD single crystal instrument at room temperature
Figure BDA0002282089030000071
Test structure[15]. Data were collected and unit cells determined using the APEXII program. Structural data was normalized and absorption corrected using SAINT and SADABS programs[16]. Structure analysis by using SHELXTL-97 program[17]. All non-hydrogen atom coordinates are obtained by a difference Fourier synthesis method, the atom coordinates and the anisotropic temperature factors are corrected by using a full matrix least square method, and all hydrogen atoms are hydrogenated by using a theory. The block diagram is shown in FIG. 1. The crystallographic data are shown in table 1.
TABLE 1 crystallographic data for the complexes
Figure BDA0002282089030000072
The block diagram of fig. 1 shows: co (II) coordinates with seven nitrogen atoms of the organic ligand BPA-TPA, forming a coordination configuration of a distorted single-crown triangular prism.
(2) Determination of phase purity by powder X-ray diffraction
The phase purity of the red bulk crystalline product obtained in this example was characterized using a Bruker D8 Advance powder X-ray diffractometer. As shown in fig. 2, the simulation curve was obtained by simulation of the single crystal structure data using Mercury software. The result shows that the cobalt-based single ion magnet has reliable phase purity, and provides guarantee for the application of the cobalt-based single ion magnet in molecular-based magnetic materials.
(3) And (3) magnetic property characterization:
the magnetic measurement adopts a superconducting Quantum interferometer Quantum Design MPMS SQUID VSM magnetic measurement system. The testing temperature of the direct current magnetic susceptibility is 1.8-300K, and the magnetic field is 0.1T. The testing temperature of the magnetization is 1.8K, 3K and 5K, and the magnetic field is 0-7T. The frequency range of the imaginary part alternating current magnetic susceptibility and the real part alternating current magnetic susceptibility is 1-999 Hz, the temperature range is 1.8-3.8K, and the external direct current magnetic field is 0.1T.
As shown in FIG. 3, the product of the DC magnetic susceptibility (χ) and the temperature (T) is 2.32cm at 300K3mol-1K, much greater than the theoretical value of co (ii) (g 2) with S3/2 spin only, 1.875cm3mol-1K. Therefore, the complex has not only a spin magnetic moment but also a significant orbital contribution. In the range 300-50K the product remains essentially constant, whereas at temperatures below 50K the value starts to drop sharply, due to the important magnetic anisotropy present in the system. The magnetization curve (fig. 4) shows that none of the complexes reached saturation in magnetization when the magnetic field reached 7T, confirming that the complexes have strong magnetic anisotropy. Under the condition that the applied direct current field is 0.1T, the imaginary part alternating current magnetic susceptibility x' of the complex presents obvious temperature dependence and frequency dependence phenomena (figure 5), and slow magnetic relaxation behavior is generated. The corresponding Cole-Cole curve shows good halfA circular distribution and can be fitted with the debye function of a single relaxation process (fig. 6). By combining the phenomena, the rare earth complex prepared by the invention can show a typical slow relaxation behavior under the condition that the external magnetic field is 0.1T, has the characteristics of a monomolecular magnet, and can be used as a molecular-based magnetic material in novel high-density information storage equipment (such as an optical disk, a hard disk and the like).
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. A cobalt-based single ion magnet material, characterized in that: the chemical formula of the cobalt-based single-ion magnet material is [ Co (BPA-TPA)]·(BF4)2Wherein BPA-TPA is an organic ligand 2, 6-bis (di (2-pyridylmethyl) amine) picoline, and the chemical structure is as follows:
Figure FDA0002282089020000011
co (II) coordinates with seven nitrogen atoms of an organic ligand BPA-TPA to form a coordination configuration of a single-crown triangular prism;
the mononuclear cobalt complex belongs to a triclinic system, P-1 space group and has unit cell parameters of
Figure FDA0002282089020000012
Figure FDA0002282089020000013
α=71.015(2)°,β=67.784(2)°,γ=70.936(2)°。
2. A method for producing a cobalt-based single ion magnet material according to claim 1, characterized in that: the preparation method comprises the following steps:
step 1: in the closed state, anhydrous cobalt halide CoX2Reacting with silver tetrafluoroborate AgBF in acetonitrile solution4Stirring, mixing and reacting to generate AgX precipitate, wherein X is Cl or Br;
step 2: filtering to remove AgX precipitate generated in the step 1, adding organic ligand BPA-TPA into the filtrate, and stirring for 30-35 min;
and step 3: and (3) after stirring, transferring the mixed solution formed in the step (2) into a test tube, and slowly adding diethyl ether for two-phase diffusion to obtain the cobalt-based single-ion magnet material.
3. The method for producing a cobalt-based single ion magnet material according to claim 2, characterized in that: AgBF in the step 14And CoX2In a molar ratio of 2:1, the amount of acetonitrile used being per 0.5mmoL of CoX2Corresponding to 4-7mL of acetonitrile.
4. The method for producing a cobalt-based single ion magnet material according to claim 2, characterized in that: the organic ligand BPA-TPA in the step 2 and the CoX in the step 12The molar ratio of (A) to (B) is 1-1.3: 1.
5. The method for producing a cobalt-based single ion magnet material according to claim 2, characterized in that: the dosage of the diethyl ether in the step 3 is 2-4 times of that of the acetonitrile in the step 1.
6. Use of a cobalt-based single ion magnet material according to claim 1, wherein: the cobalt-based single ion magnet material is used as a molecular-based magnetic material.
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CN113683645A (en) * 2021-09-02 2021-11-23 湖北科技学院 Dinuclear Pt (II) complex with anti-tumor activity and preparation method and application thereof
WO2023165155A1 (en) * 2022-03-04 2023-09-07 江苏科技大学 High-energy-barrier dysprosium-based single-ion magnet, preparation method, and use thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113105512A (en) * 2021-04-15 2021-07-13 温州大学 Novel cobalt (III) -sulfur cluster-based coordination polymer with monomolecular magnet property
CN113683645A (en) * 2021-09-02 2021-11-23 湖北科技学院 Dinuclear Pt (II) complex with anti-tumor activity and preparation method and application thereof
CN113683645B (en) * 2021-09-02 2023-11-07 湖北科技学院 Binuclear Pt (II) complex with anti-tumor activity and preparation method and application thereof
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