CN108191921B - Multi-core metal cluster compound based on iminodiacetic acid ligand and preparation method thereof - Google Patents
Multi-core metal cluster compound based on iminodiacetic acid ligand and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000005389 magnetism Effects 0.000 abstract description 9
- 230000003993 interaction Effects 0.000 abstract description 5
- -1 rare earth ions Chemical class 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000011160 research Methods 0.000 description 6
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- 238000002474 experimental method Methods 0.000 description 3
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- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 230000005343 Curie-Weiss law Effects 0.000 description 1
- 102000008857 Ferritin Human genes 0.000 description 1
- 238000008416 Ferritin Methods 0.000 description 1
- 108050000784 Ferritin Proteins 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005303 antiferromagnetism Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 229920001795 coordination polymer Polymers 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000005388 metamagnetism Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- 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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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
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Abstract
The invention relates to a polynuclear metal cluster compound based on iminodiacetic acid ligand and a preparation method thereof. The chemical formula of the polynuclear metal cluster is: tb26Ni28(ida)28(OH)70](NO3)8·35H2And O. The invention also provides a preparation method of the multi-core metal cluster compound, which comprises the following steps: tb (NO)3)3·6H2O、Ni(NO3)2·6H2Dissolving O and iminodiacetic acid in water, and adjusting the pH value to 3.5-4.5 to obtain a mixture; and (3) reacting the mixture at the temperature of 160-200 ℃ for 65-72 hours to obtain the catalyst. The multi-core metal cluster is a metal cluster containing rare earth ions, and a hydroxyl-oxygen bridge is arranged in a molecular structure, so that the distance between metal ions is shortened, the interaction between metals is enhanced, and novel magnetism is shown, such as special magnetism of monomolecular magnetism, spin conversion and the like.
Description
Technical Field
The invention relates to a cluster compound and a preparation method thereof, in particular to a polynuclear metal cluster compound based on iminodiacetic acid ligand and a preparation method thereof.
Background
In recent years, synthesis of zero-dimensional multi-core or high-core transition metal and lanthanide metal clusters is an emerging research hotspot. This is not only because of the novelty and perfection of the structure of these coordination polymers, but also the potential application value of these compounds in the magnetoelectric, biochemical and optical fields. For example, synthetic Mn, a group of subjects taught by Armstrong, university of Boston, USA4The cluster compound has the photosynthesis-like effect and is used for simulating the process of converting water into oxygen in photosynthesis. As another example, ferritin, which is well known to scientists, is a metal cluster that has been found to possess superparamagnetic as well as molecular nanomagnet properties due to its high spin ground state. Still other metal clusters exhibit spinning properties and catalytic activity (M.J. science,1995,268: 77; J.Nature,1996,383: 145).
As mentioned above, the research on molecular magnetism has been carried out from conventional ferromagnetism and antiferromagnetism to a deeper level, wherein the behaviors of monomolecular magnets, single chain magnetics, spin transfer, metamagnetism and the like are gradually focused on the research, in the field of molecular magnetism research, transition metals or rare earths are generally selected to synthesize three-dimensional or one-dimensional structures, but the research on zero-dimensional clusters of linearly arranged transition metals and rare earth ions is less [6-10], while the research on Ni + L n clusters is less.
Disclosure of Invention
The invention aims to provide a polynuclear metal cluster based on iminodiacetic acid ligand; the multi-core metal cluster has a novel four-layer nested structure and has excellent molecular magnetism.
The chemical formula of the polynuclear metal cluster is: tb26Ni28(ida)28(OH)70](NO3)8·35H2O；
Wherein ida denotes iminodiacetic acid.
The metal cluster is a triclinic system and the space group is
The multinuclear metal cluster contains 26 independent Tb (III) ions, 28 independent Ni (II) ions, 28 independent ida ligand ions and 70 hydroxyl ions.
The complete structure of the multi-core metal cluster is a four-layer nested structure, as shown in fig. 2 and 3A to D, the structure of the multi-core metal cluster is from inside to outside, specifically:
the first layer comprises 8 Ni (II) ions, mu 3-OH is used as a bridge to closely link eight ions together to form a core of a nested structure, and each Ni (II) ion is hexa-coordinated and deformed octahedral configuration;
the second layer comprises 20 Tb (III) ions, 8 of which form the apex of the cube, the remaining Tb (III) ions being located at the midpoint of each side of the cube, μ 3-OH acting as a bridge connecting the 20 Tb (III) ions to form 12 sides of the cube, μ 3-OH acting simultaneously as a bridge connecting the Tb (III) ions in the second layer to the first layer Ni (II) ions;
the third layer contains 32 Tb (III) ions, with 3 μ 3-OH groups on the Tb (III) ions on each side of the cube, one bridging adjacent Tb (III) ions in the second layer, and another pair bridging the Ni (II) ions of the fourth layer;
the fourth layer contains 48 ni (ii) ions, the layer structure resembles a cube without vertices, each vertex is positioned with three ni (ii) ions arranged in a triangle, the geometry of the whole molecule resembles a cube, the ni (ii) ions at the vertices of the cube are complexed by N and O atoms in ida ligands (two carboxyl groups from ida), at the same time, the O atoms are complexed with two independent Tb (iii) ions of the third layer. The other two O atoms of the ida carboxyl groups coordinate to adjacent ni (ii) ions.
Wherein, all Ni (II) ions are in a hexa-coordination environment and in a deformed octahedral configuration;
the Tb (III) ions have two coordination modes, the Tb (III) ions on the second layer are all seven coordination modes and are in a crowned triangular prism geometric configuration, and the Tb (III) ions on the third layer are all nine coordination modes to form a three-cap triangular prism configuration.
Spacing of adjacent metal ions
The spacings are all within the normal range.
A second object of the present invention is to provide a method for preparing the above metal cluster.
Preferably, the preparation method provided by the invention at least comprises the following steps:
tb (NO)3)3·6H2O、Ni(NO3)2·6H2Dissolving O and iminodiacetic acid in water, and adjusting the pH value to 3.5-4.5 to obtain a mixture; and (3) heating the mixture to 175-185 ℃ at a constant speed within 10-20 h, maintaining the temperature for 35-70 h, and cooling to room temperature at a constant speed after 6-24 h to obtain the catalyst.
The above reaction is preferably carried out in a muffle furnace.
The pH value can be adjusted by a conventional method, preferably by a sodium hydroxide solution, wherein the concentration of the sodium hydroxide is 0.8-1.2 mol/L.
In the process of the present invention, Tb (NO)3)3·6H2O can be obtained commercially or prepared by conventional methods in the field, and is preferably prepared by the following preparation method:
the Tb (NO)3)3·6H2The O is prepared by the following method: tb is to be4O7Reacting with 65-70% nitric acid at 90-110 ℃ for 25-35 min, and adjusting the pH value to 3.4-4.
In the preparation method of the invention, preferably, Tb (NO) is used3)3·6H2O and the Ni (NO)3)2·6H2The molar ratio of O is: 1.4-1.9: 1, preferably 1.65-1.72: 1;
the Ni (NO)3)2·6H2The molar ratio of O to the iminodiacetic acid is 1:1.6 ℃2.4, preferably 1: 1.9-2.1.
Preferably, 0.2-0.25 mol of Tb (NO) is dissolved in 1m L of water3)3·6H2O。
The conditions of the preparation method are further preferably that the mixture is heated to 155-165 ℃ at a constant speed within 14-16 h, then is continuously heated to 175-185 ℃ at a constant speed within 4.5-5.5 h, is maintained at the temperature for 36-38 h, and is cooled to room temperature at a constant speed within 14-16 h, so as to obtain the catalyst.
Most preferably, the mixture is heated to 160 ℃ at a constant speed within 15h, then is heated to 180 ℃ at a constant speed within 5h, and is cooled to room temperature at a constant speed within 15h after the temperature is maintained for 37h, so as to obtain the compound.
The invention provides a preferable scheme, and the preparation method of the polynuclear metal cluster compound specifically comprises the step of adding Tb (NO)3)3·6H2O、Ni(NO3)2·6H2Dissolving O and iminodiacetic acid in water, and adjusting the pH value to 3.5-4.5 to obtain a mixture; heating the mixture to 175-185 ℃ at a constant speed within 8-12 h, maintaining the temperature for 45-55 h, cooling to room temperature at a constant speed within 6-12 h, filtering, and drying to obtain the compound;
wherein, the Tb (NO)3)3·6H2O and the Ni (NO)3)2·6H2The molar ratio of O is 1.65-1.72: 1; the Ni (NO)3)2·6H2The mol ratio of O to the iminodiacetic acid is 1: 1.9-2.1.
The present invention also provides the application of the above-mentioned multi-core metal cluster compound in the fields of molecular magnetic materials, multi-metal multi-iron materials and molecular memory materials.
The multi-core metal cluster is a metal cluster containing rare earth ions, and a hydroxyl-oxygen bridge is arranged in a molecular structure, so that the distance between metal ions is shortened, the interaction between metals is enhanced, and novel magnetism is shown, such as special magnetism of monomolecular magnetism, spin conversion and the like.
Preferably, the multi-core metal cluster compound is applied to the fields of low-temperature nano temperature control magnetic switches and nano magnetic controllers.
Drawings
FIG. 1A is a graph of the temperature swing susceptibility of a multi-core metal cluster made in example 1;
FIG. 1B is a plot of the variable field magnetization of the multi-core metal cluster prepared in example 1;
FIG. 2 is a schematic structural view of a multinuclear metal cluster prepared in example 1;
FIG. 3A is a schematic diagram of the structure of a first layer of the multinuclear metal cluster prepared in example 1;
FIG. 3B is a schematic diagram of the second layer structure of the multinuclear metal cluster prepared in example 1;
FIG. 3C is a schematic diagram of the third layer structure of the multinuclear metal cluster prepared in example 1;
FIG. 3D is a schematic diagram of the fourth layer structure of the multinuclear metal cluster prepared in example 1;
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Tb (NO) in the following examples3)3·6H2The O is prepared by the following method: tb is to be4O7Reacting with 65-70% nitric acid at 100 ℃ for 30min, neutralizing redundant unreacted raw materials by using alkali, and adjusting the pH value to 3.5-4.5 to obtain the final product.
Example 1
1.69mmol Tb (NO)3)3·6H2O、1mmol Ni(NO3)2·6H2Adding O and 2mmol ida into 8m L water, adjusting the pH value to 3.5-4.5 by using 1 mol/L NaOH, uniformly stirring to obtain a mixture, heating the mixture to 160 ℃ within 15h at a constant speed, continuously heating to 180 ℃ within 5h at a constant speed, maintaining the temperature for 37h, and then cooling to room temperature within 15h at a constant speed to obtain the compound.
The multi-core metal cluster prepared in this example is a green bulk crystal with a yield of 62%.
Elemental analysis result C112H150N36Ni28Tb26O251 (%): c11.48, H1.26, N4.29. IR (KBr, cm-1): 3259(s),2969(vs),2934(vs),1641(m),1585(m),1397(m),1221(m),798 (m).
Characterization experiments were performed on the polynuclear metal cluster prepared in example 1. Selecting crystals with the size of about 0.1mm, and performing single crystal diffraction experiments by adopting a Rigaku R-axis Rapid IP surface detector at normal temperature or low temperature. By using
Collecting diffraction data of the cluster compound by using rays in an omega-2 theta scanning mode, and detecting the results, wherein the crystallographic parameters of the cluster compound are shown in the following table:
TABLE 1 crystallographic parameters of Cluster Compound
a R1＝Σ||Fo|-|Fc||/|Fo|,wR2＝[Σw(Fo2-Fc2)2/Σw(Fo2)2]1/2.
The multi-core metal cluster prepared in example 1 was subjected to a temperature-changing magnetic susceptibility test using an external magnetic field of 1000Oe at a temperature range of 2-300K.
The value of χ mT is 451.5cm at room temperature of 300K3K mol–1Slightly lower than 56 independent uncoupled ground states of Ni2+And 52 independent uncoupled ground states Tb3+Addition (468.76 cm)3Kmol–1). As the temperature decreases, the value of χ mT also slowly decreases, beginning to rapidly decrease at 50K and reaching a minimum value of 400.0cm at 2K3K mol–1The trend of the curves shows that before 2K, Ni2+、Tb3+The interaction between ions is antiferromagnetic coupling, as shown in FIG. 1A.
The above experimental data were fitted using Curie-Weiss law at temperatures ranging from 2K to 300K to obtain a Curie constant C of 458.7cm3K mol–1The Weiss constant θ is-1.29K, and a negative Weiss constant further indicates a weak antiferromagnetic interaction between ions in the cluster. The isothermal susceptibility curve at 2K also demonstrates weak antiferromagnetic interactions between the ions, with a rapid increase in M with increasing field strength, a slow increase after 2T, and up to 482N μ at 7TBApproximate theoretical saturation value 476N muBAs shown in fig. 1B.
Example 2
1.69mmol Tb (NO)3)3·6H2O、1mmol Ni(NO3)2·6H2Adding O and 2mmol ida into 8m L of water, adjusting the pH value to 3.5-4.5 by adopting 1 mol/L of NaOH, uniformly stirring to obtain a mixture, uniformly heating the mixture to 180 ℃ within 10h, maintaining the temperature for 70h, uniformly cooling to room temperature within 12-24 h, filtering, and naturally drying to obtain the multi-core metal cluster.
The multi-core metal cluster prepared in this example is a green bulk crystal with a yield of 82%.
Elemental analysis result C112H150N36Ni28Tb26O251 (%): c11.48, H1.26, N4.29. IR (KBr, cm-1): 3268(s),2998(vs),3010(vs),1680(m),1545(m),1354(m),1288(m),787 (m);
from the analysis results, it was found that although the yield of the metal cluster was high, there were fewer crystals satisfying the crystallographic parameters of table 1.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (11)
1. A preparation method of a polynuclear metal cluster compound based on an iminodiacetic acid ligand is characterized in that the chemical formula of the polynuclear metal cluster compound is as follows: tb26Ni28(ida)28(OH)70](NO3)8·35H2O; wherein ida refers to iminodiacetic acid; the multi-core metal cluster is a triclinic system and the space group is
Cell parameters
α＝69.38(3)°，β＝69.42(3)°，γ＝69.49(3)°；
The preparation method specifically comprises the following steps:
tb (NO)3)3·6H2O、Ni(NO3)2·6H2Dissolving O and iminodiacetic acid in water, and adjusting the pH value to 3.5-4.5 to obtain a mixture; heating the mixture to 175-185 ℃ at a constant speed within 10-20 h, maintaining the temperature for 35-70 h, and cooling to room temperature at a constant speed within 6-24 h to obtain the product;
the Ni (NO)3)2·6H2The molar ratio of O to the iminodiacetic acid is 1: 1.6-2.4.
2. Preparation process according to claim 1, characterized in that the Tb (NO) is3)3·6H2O and the Ni (NO)3)2·6H2The molar ratio of O is: 1.4-1.9: 1.
3. Preparation process according to claim 2, characterized in that the Tb (NO) is3)3·6H2O and the Ni (NO)3)2·6H2The molar ratio of O is 1.65-1.72: 1.
4. The production method according to any one of claims 1 to 3, wherein the Ni (NO) is3)2·6H2The molar ratio of O to the iminodiacetic acid is 1: 1.9-2.1.
5. The production method according to any one of claims 1 to 3, characterized in that0.2 to 0.25mol of Tb (NO) per 1m of L dissolved in water3)3·6H2O。
6. The method according to claim 4, wherein 0.2 to 0.25mol of the Tb (NO) is dissolved in 1m L of the water3)3·6H2O。
7. The preparation method according to any one of claims 1 to 3 and 6, wherein the mixture is heated to 155-165 ℃ at a constant speed within 14-16 h, then is heated to 175-185 ℃ at a constant speed within 4.5-5.5 h, is maintained at the temperature for 36-38 h, and is cooled to room temperature at a constant speed within 14-16 h to obtain the catalyst.
8. The preparation method according to claim 4, wherein the mixture is heated to 155-165 ℃ at a constant speed within 14-16 h, then is heated to 175-185 ℃ at a constant speed within 4.5-5.5 h, is maintained at the temperature for 36-38 h, and is cooled to room temperature at a constant speed within 14-16 h, so as to obtain the catalyst.
9. The preparation method according to claim 5, wherein the mixture is heated to 155-165 ℃ at a constant speed within 14-16 h, then is heated to 175-185 ℃ at a constant speed within 4.5-5.5 h, is maintained at the temperature for 36-38 h, and is cooled to room temperature at a constant speed within 14-16 h, so as to obtain the catalyst.
10. The preparation method according to claim 7, wherein the mixture is heated to 160 ℃ at a constant speed within 15h, then is heated to 180 ℃ at a constant speed within 5h, and is cooled to room temperature at a constant speed within 15h after the temperature is maintained for 37 h.
11. The preparation method according to claim 8 or 9, characterized in that the mixture is heated to 160 ℃ at a constant speed within 15h, then is heated to 180 ℃ at a constant speed within 5h, and is cooled to room temperature at a constant speed within 15h after the temperature is maintained for 37 h.
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