CN110790699B - Cobalt-based single-ion magnet material, preparation method and application thereof - Google Patents
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- 239000010941 cobalt Substances 0.000 title claims abstract description 43
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- 239000000696 magnetic material Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 claims abstract description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004700 cobalt complex Chemical class 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- -1 cobalt halide Chemical class 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 7
- 150000003624 transition metals Chemical class 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 2
- 230000005291 magnetic effect Effects 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 22
- 239000013078 crystal Substances 0.000 description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- GPAAEXYTRXIWHR-UHFFFAOYSA-N (1-methylpiperidin-1-ium-1-yl)methanesulfonate Chemical compound [O-]S(=O)(=O)C[N+]1(C)CCCCC1 GPAAEXYTRXIWHR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- 229910019131 CoBr2 Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002547 FeII Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
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- 238000010595 magnetization diagram Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic 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
- C07D213/02—Heterocyclic 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
- C07D213/04—Heterocyclic 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
- C07D213/24—Heterocyclic 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
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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:
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 is 71.015(2) °, β is 67.784(2) °, and γ is 70.936(2) °. The invention has the advantages that: the invention researches and 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
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, researchers have found that increasing S decreases the value of D, and that increasing S alone does not effectively increase the value of the inversion energy barrier U. Therefore, researchers have constructed mononuclear complexes by using lanthanide ions and transition metal ions having relatively strong magnetic anisotropy, and have increased the D valueAnd a monomolecular magnet is obtained. 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 high-coordination (coordination number is 7-8) transition metal-based single-ion magnets 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:
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)°，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;
and 2, step: 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.
Drawings
The invention is described in further detail below with reference to the drawings and the detailed description.
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:
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)°，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 CoX2In acetonitrileNeutralizing silver tetrafluoroborate AgBF in liquid4Stirring, 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) is stirred and mixed in 7mL acetonitrile solution to generate white flocculent AgCl precipitate immediately, the precipitate is removed by filtration, organic ligand BPA-TPA (0.7mmol) is added into the filtrate, the mixture is stirred for 30min and is transferred into a test tube, 20mL diethyl ether is slowly dripped to form two-phase layering, after 3 days, the diethyl ether is completely diffused into the lower layer acetonitrile solution to obtain the cobalt-based single ion magnet materialCrystals of the 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
Test structure[15]. Data were collected and unit cells were determined using the APEXII program. Structural data was normalized and absorption corrected using SAINT and SADABS programs[16]. Structure analysis 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 structure is shown in figure 1. The crystallographic data are shown in table 1.
TABLE 1 crystallographic data for the complexes
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 300K3 mol-1K, much greater than the theoretical value of co (ii) (g 2) with S3/2 spin only, 1.875cm3 mol-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 curves represent a good semicircular 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 applies a magnetic fieldThe material can show typical slow relaxation behavior at 0.1T, has the characteristics of a single-molecule magnet, and can be used as a molecule-based magnetic material in novel high-density information storage devices (such as optical disks, hard disks 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:
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)°，γ＝70.936(2)°。
2. A method for preparing 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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