CN102030785B - Method for preparing exoticmetal low-temperature magnetic material - Google Patents
Method for preparing exoticmetal low-temperature magnetic material Download PDFInfo
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- CN102030785B CN102030785B CN2010105934349A CN201010593434A CN102030785B CN 102030785 B CN102030785 B CN 102030785B CN 2010105934349 A CN2010105934349 A CN 2010105934349A CN 201010593434 A CN201010593434 A CN 201010593434A CN 102030785 B CN102030785 B CN 102030785B
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Abstract
The invention discloses a method for preparing an exoticmetal low-temperature magnetic material and relates to a method for preparing a magnetic material. In the method, 1-hydrogen-benzimidazole-5,6-dicarboxylicaid is taken as a ligand; gadolinium oxide and nickel sulfate are used for providing metal central atoms; a single crystal material of an exoticmetal coordination polymer having a three-dimensional structure with a binuclear center containing Gd (III) is synthesized under a hydrothermal condition; and a test result shows that a compound plays a role in ferromagnetic coupling among binuclear Gd(III) ions at the temperature of over 28K, or plays a role in antiferromagnetic coupling among binuclear Gd(III) ions at the temperature of between 2 and 28k. The magnetism of the compound changes at the temperature of 28k, and is the novel coordination polymer which is dependent on the temperature and can be taken as the potential magnetic material. The structure of the magnetic material is satisfactory, and the novel single crystal structure adds new data into a crystal database.
Description
Technical field
The present invention relates to a kind of preparation method of magneticsubstance, particularly relate to a kind of preparation method of different metal low-temperature magnetic material.
Background technology
Common crystal type is divided into two kinds, and a kind of is powder crystal, and a kind of is monocrystalline.Powder crystal is difficult to test out molecular structure accurately.And another kind is a crystal, can react the variety of the complex structure and the weak mode of action really through X-single crystal diffractometer (being Bruker Smart 1000 CCD type single crystal diffractometers).Simultaneously can also be through various software to bond distance, bond angle, torsional angle between atom in its molecular structure, the mode of action variety between them characterizes.In the preparation for monocrystalline, conventional method has solvent evaporation method, diffusion process, top and bottom process, test tube method and water (solvent) heat or the like.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of different metal low-temperature magnetic material; Alternating temperature susceptibility test result according to title complex; Its magnetic behavior has dependency to temperature; The transformation of coupling is arranged when 28 K, the invention provides a preparation method as the new single-crystal title complex of magneticsubstance.
The objective of the invention is to realize through following technical scheme:
A kind of preparation method of different metal low-temperature magnetic material comprises following process: with 1-hydrogen-benzoglyoxaline-5, and 6-dicarboxylicacid (H
3Bidc), single nickel salt and gadolinium sesquioxide are according to the 2:1:1 stoichiometric ratio, through 160 ℃ hydrothermal methods acquisition target title complex; That is, get gadolinium sesquioxide 0.2 mmol, seven water single nickel salts, 0.2 mmol, 1-hydrogen-benzoglyoxaline-5,6-dicarboxylicacid (H
3Bidc) 0.4 mmol and zero(ppm) water 10 mL stirred 10 minutes, were sealed in then in the 25 mL tetrafluoroethylene reaction kettles; 160 ℃ of down reactions 3 days, cool to room temperature gradually in three days then obtains the crystal of light green long strip type; Clean with zero(ppm) water, in air, dry.
The preparation method of described a kind of different metal low-temperature magnetic material; Described title complex The Nomenclature Composition and Structure of Complexes is clear and definite, the alternating temperature susceptibility test result of title complex, and its magnetic behavior has dependency to temperature; The transformation of coupling is arranged when 28 K, be the new single-crystal title complex of magneticsubstance.
Advantage of the present invention and effect are:
In the synthetic novel complexes of the present invention, 1-hydrogen-benzoglyoxaline-5,6-dicarboxylicacid are multiple tooth multi-functional parts, and wherein the nitrogen-atoms on the benzoglyoxaline ring tends to transition-metal coordination, and the carboxylic acid Sauerstoffatom on the phenyl ring helps and the group of the lanthanides Atomic coordinate.Thereby the experiment through repeatedly; Through changing the stoichiometric ratio of experiment condition such as part and metal, the type of metal-salt and temperature of reaction etc., successful this title complex that synthesized; Its structure is satisfactory, and its novel single crystal structure has increased new data for the crystal data storehouse.
Description of drawings
Fig. 1 is the coordination structure figure of title complex;
Fig. 2 is the alternating temperature susceptibility figure of title complex;
Fig. 3 is χ
M -1Law fitted figure to temperature T curve K300;
Fig. 4 is χ
M -1Law fitted figure to temperature T curve K30.
Embodiment
Be elaborated in the face of the present invention down.
From Fig. 1, can find out, there are former subcenter of this Gd (III) and the former subcenter of Ni (II) in this structure simultaneously.Each Gd (III) central atom all is the center that is in the anti-four prisms cylinder of single cap of a distortion, with its coordinate Sauerstoffatom mainly be from 4 different ligands on carboxylic acid Sauerstoffatom and two coordinated water molecules.Wherein two Gd of carboxylic acid Sauerstoffatom O3B and O3A bridging (III) ion has formed a double-core center, and the distance between the Gd (III) is 4.038, two sulfate radicals at Gd1-O3B-Gd1A-O3A is that the both sides, prismatic plane on summit are with μ
1The form of-O further connects Gd (III) double-core center.The former subcenter of Ni (II) is to be in a more regular octahedra center, summit wherein be by from the nitrogen-atoms on the part imidazole ring (N1, N1D) occupied, and equatorial plane is to be occupied by the Sauerstoffatom in 4 coordinated water.Through the research to the three-dimensional structure of this title complex, the three-dimensional structure that can find this title complex is by Ni (H
2O)
4 2+The unit connects adjacent Gd (III)-part-sulfate radical two-dimensional layer and forms.Have the double-core gadolinium center with the bridging of carboxylic acid Sauerstoffatom in the structure, oxo bridge provides the path of magnetic superexchange, so this title complex has the potential magneticsubstance.
Fig. 2 is the alternating temperature susceptibility of this title complex, and wherein zero is molar susceptibility and the product χ that spends temperature extremely
MT is to the curve of absolute temperature T.Its test condition is: outside 1000 Oe, under the field intensity, use Quantum Design MPMS-7 SQUID type quantity of magnetism instrumentation fixed in 2-300 K TRs, all data are all carried out anti-magnetic through the Pascal's constant and are proofreaied and correct.By χ
MT can find out the T curve, in temperature during greater than 28 K, and χ
MThe T value descends and rises along with temperature, has embodied a ferromegnetism coupling.χ between 2-28 K
MThe T value descends and descends fast along with temperature, demonstrates the antiferromagnetism coupling.
χ reciprocal through molar susceptibility
M -1To the Curie-Weiss law match of the curve of temperature T, see Fig. 3 and Fig. 4.Temperature draws Weiss constant θ=1.60 K greater than 28K, Curie constant C=15.11 cm
3K mol
-1Explanation during greater than 28 K, exists ferromagnetic coupling effect between double-core Gd (III) ion in temperature.When temperature when 2 K are between 28 K, best fit parameters Weiss constant θ=-2.65 K, Curie constant C=42.265 cm
3K mol
-1Explanation exists the antiferromagnetic coupling effect between this temperature range Gd (III) ion.
Complex polymerisation thing [Gd
2Ni (Hbidc)
2(SO
4)
2(H
2O)
8]
nMethod for preparing single crystal and condition, and through its structure of single crystal diffraction test.Owing to comprised double-core Gd (III) center in the compound, the magnetic exchange center be provided.
Get gadolinium sesquioxide (0.2 mmol), seven water single nickel salts (0.2 mmol), 1-hydrogen-benzoglyoxaline-5,6-dicarboxylicacid (H
3Bidc) (0.4 mmol) and zero(ppm) water (10 mL) stirred 10 minutes, were sealed in then in the 25 mL tetrafluoroethylene reaction kettles; 160 ℃ of down reactions 3 days, cool to room temperature gradually in three days then obtains the crystal of light green long strip type; Clean with zero(ppm) water, in air, dry.Record its single crystal structure with the X-single crystal diffractometer, its novel structure has been enriched the monocrystalline DB.Seeing that REE shows the character of outstanding magneticsubstance, the new monocrystalline title complex [Gd that is synthesized
2Ni (Hbidc)
2(SO
4)
2(H
2O)
8]
nAlso has the potential magneticsubstance.
Present method is with 1-hydrogen-benzoglyoxaline-5, and the 6-dicarboxylicacid provides metal center as part with gadolinium sesquioxide and single nickel salt; Zero(ppm) water places 25mL tetrafluoroethylene reaction kettle as solvent, stirs 10 minutes in the air; Be sealed in then in the stainless steel casing, 160 ℃ of down reactions 3 days, cool to room temperature gradually in three days then; Obtain the crystal of light green long strip type, clean, in air, dry with zero(ppm) water.This crystal records its structure through X-single crystal diffractometer.
Claims (2)
1. the preparation method of a different metal low-temperature magnetic material is characterized in that, comprises following process: with 1-hydrogen-benzoglyoxaline-5, and 6-dicarboxylicacid (H
3Bidc), seven water single nickel salts and gadolinium sesquioxide are according to the 2:1:1 stoichiometric ratio, through 160 ℃ hydrothermal methods acquisition target title complex; That is, get gadolinium sesquioxide 0.2 mmol, seven water single nickel salts, 0.2 mmol, 1-hydrogen-benzoglyoxaline-5,6-dicarboxylicacid (H
3Bidc) 0.4 mmol and zero(ppm) water 10 mL stirred 10 minutes, were sealed in then in the 25 mL tetrafluoroethylene reaction kettles; 160 ℃ of down reactions 3 days, cool to room temperature gradually in three days then obtains the crystal of light green long strip type; Clean with zero(ppm) water, in air, dry.
2. the preparation method of a kind of different metal low-temperature magnetic material according to claim 1; It is characterized in that; Described title complex The Nomenclature Composition and Structure of Complexes is clear and definite, the alternating temperature susceptibility test result of title complex, and its magnetic behavior has dependency to temperature; The transformation of coupling is arranged when 28 K, be the monocrystalline title complex of magneticsubstance.
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| CN102516316A (en) * | 2011-11-04 | 2012-06-27 | 南开大学 | Preparation method of oxamide macrocyclic octanuclear complex [Cu6Ln2] (Ln=Gd, tb, dy, ho) |
| CN106633097A (en) * | 2017-01-10 | 2017-05-10 | 黄秋颖 | Tetranuclear nickel complex with antiferromagnetic coupling function and synthesis method thereof |
| CN107474076B (en) * | 2017-08-25 | 2019-10-25 | 广州科技贸易职业学院 | A kind of mixed metal cluster and its preparation method and application |
| CN108191921B (en) * | 2017-12-29 | 2020-07-24 | 李辉 | Multi-core metal cluster compound based on iminodiacetic acid ligand and preparation method thereof |
| CN109467714A (en) * | 2018-11-14 | 2019-03-15 | 江苏师范大学 | A kind of magnetic coupling metal-organic framework materials and its application |
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| CN1911946A (en) * | 2006-07-11 | 2007-02-14 | 南开大学 | Fe (II)-Nd (III) hexascrew nanometer pipe polymer and preparation method |
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Non-Patent Citations (1)
| Title |
|---|
| 陈秋云等.Gd(III)-Ni(II)大环配合物合成和磁性.《黄山学院学报》.2004,第6卷(第3期),48-50. * |
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