Two-dimensional layered germanium vanadium oxygen cluster compound and synthesis method and application thereof
1. A two-dimensional layered germanium vanadium oxygen cluster compound is characterized in that: it has the chemical formula as follows: [ Zn (en)) (H2O)]4[Zn(en)2]2[Ge6V15O48]·4.5H2O, wherein en is ethylenediamine.
2. The two-dimensional layered germanium vanadium oxy cluster compound of claim 1, wherein: it belongs to the orthorhombic system, the space group is Pbcn, the unit cell parameterα＝90.00°，β＝90.00°，γ＝90.00°。
3. A method for preparing the two-dimensional layered germanium vanadium oxy cluster compound according to claim 1, wherein: it comprises the following steps:
(1) reacting NH4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid and1,2, 4-triazole is charged into the polytetrafluoroethylene lining, followed by ethylenediamine and H2O, stirring for 20-35 min to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) in an oven at 140-180 ℃ for reaction for 3-6 days, and cooling to room temperature;
(3) washing the product obtained in the step (2) with distilled water, and filtering to obtain brown flaky crystals, namely the two-dimensional layered germanium vanadium oxygen cluster compound.
4. The method for preparing two-dimensional layered germanium vanadium oxygen cluster compound according to claim 3, wherein: NH in step (1)4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid, 1,2, 4-triazole, ethylenediamine and H2The molar ratio of O is 1.4-2.0: 1.7-2.2: 3.7-4.3: 1: 1.5-2.1: 25.1-66.9: 931.3-2172.6.
5. The method for preparing two-dimensional layered germanium vanadium oxygen cluster compound according to claim 4, wherein: NH in step (1)4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid, 1,2, 4-triazole, ethylenediamine and H2The molar ratio of O is 1.68:2.01:4.06:1:1.66:41.78: 1551.96.
6. Use of the two-dimensional layered germanium vanadium oxy cluster compound according to any one of claims 1 to 5 in the preparation of a magnetic material.
Background
Polyoxometalates, also called Polyoxometalates (POMs), are formed by Mo, W, V, Nb and Ta as early transition elements, in the form of MOX(X is usually 5 or6) Is a polyoxo cluster compound with special properties and structure formed by unit polycondensation. Among numerous polyoxometalate compounds, vanadium has the advantages of various coordination modes, variable valence states, various connection modes and the like compared with other metal elements, so that vanadium oxometalate compounds (POVs) have the characteristics of structural diversity and excellent physicochemical properties, and can form vanadium oxometalate with complex structures such as one-dimensional chain, two-dimensional layer and three-dimensional net due to the variable coordination geometrical configuration, so that the vanadium oxometalate compounds are favored by researchers.
Compared with ferromagnetic materials, antiferromagnetic materials have attracted much attention from many researchers because of their advantages of being diamagnetic, fast in spin dynamics, and free of stray magnetic fields in the application of information storage devices. Due to the variability of the valence state of vanadium in the germanium-vanadium oxygen cluster compound, the germanium-vanadium oxygen cluster compound has important application prospects in the fields of photoelectric materials, magnetic materials, catalysis, biological medicines and the like. However, the synthesis conditions of germanium-vanadium-oxygen clusters are harsh due to the low solubility of germanium oxide, and thus, the research on germanium-vanadium-oxygen cluster compounds has been relatively few.
Disclosure of Invention
The invention aims to provide a two-dimensional layered germanium vanadium oxygen cluster compound with an antiferromagnetic effect, and a synthetic method and application thereof.
The purpose of the invention is realized by the following technical scheme:
the invention adopts a hydrothermal synthesis method, and successfully prepares an example of Ge by exploring synthesis conditions for the first time6V15O48The cluster unit is formed by four zinc amine complexes [ Zn ]2(en)2]4+Germanium vanadium oxygen cluster compound [ Zn (en) (H) with novel two-dimensional layered structure formed by bridging2O)]4[Zn(en)2]2[Ge6V15O48]·4.5H2O (en: ethylenediamine), and the structure of the compound is tested and characterized, and the magnetic performance of the compound is tested and researched.
The two-dimensional layered germanium vanadium oxygen cluster compound has the chemical formula: [ Zn (en)) (H2O)]4[Zn(en)2]2[Ge6V15O48]·4.5H2O, wherein en is ethylenediamine.
The two-dimensional layered germanium vanadium oxygen cluster belongs to an orthorhombic system, the space group is Pbcn, and the unit cell parametersα＝90.00°，β＝90.00°，γ＝90.00°。
The preparation method of the two-dimensional layered germanium vanadium oxygen cluster compound comprises the following steps:
(1) reacting NH4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid and 1,2, 4-triazole are charged into a polytetrafluoroethylene liner, followed by ethylene diamine and H2O, stirring for 20-35 min to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) in an oven with the temperature of 140-180 ℃ (the optimal temperature is 170 ℃) for reaction for 3-6 days (the optimal reaction time is 4 days), and then cooling to room temperature;
(3) washing the product obtained in the step (2) with distilled water, and filtering to obtain brown flaky crystals, namely the two-dimensional layered germanium vanadium oxygen cluster compound.
Wherein, NH in the step (1)4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid, 1,2, 4-triazole, ethylenediamine and H2The molar ratio of O is 1.4-2.0: 1.7-2.2: 3.7-4.3: 1: 1.5-2.1: 25.1-66.9: 931.3-2172.6; the NH4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid, 1,2, 4-triazole, en and H2The optimal molar ratio of O is: 1.68:2.01:4.06:1:1.66:41.78:1551.96.
Although terephthalic acid and 1,2, 4-triazole in the raw materials do not appear in the final crystal structure, the terephthalic acid and the 1,2, 4-triazole can play a role of a template agent in the synthesis process to promote the crystallization of new crystal species, so that the germanium-vanadium-oxygen cluster compound is successfully obtained. The effect of terephthalic acid and 1,2, 4-triazole in a reaction system is discovered by the inventor of the invention accidentally during the experiment, the invention originally intends to make terephthalic acid and 1,2, 4-triazole participate in the reaction and appear in the final crystal structure, the inventor optimizes and groves various experimental conditions, but neither terephthalic acid nor 1,2, 4-triazole appears in the final crystal structure, and the two-dimensional layered germanium vanadium oxygen cluster compound is formed unexpectedly. In contrast, the inventors of the present invention tried to investigate the effects of 1,2, 4-triazole and terephthalic acid in the whole reaction system, and compared that under the condition that other raw materials, the mixture ratio of the raw materials and the reaction conditions are not changed, the two-dimensional layered germanium vanadium oxide cluster of the present invention is not obtained by adding terephthalic acid and 1,2, 4-triazole or only one of terephthalic acid and 1,2, 4-triazole, so that terephthalic acid and 1,2, 4-triazole are not present in the final crystal structure, but they are indispensable parts in the raw materials for synthesizing the two-dimensional layered germanium vanadium oxide cluster, and play a non-negligible role in the structure of the target compound, and in addition, terephthalic acid and 1,2, 4-triazole must be present in the reaction system at the same time, the target cluster compound can be obtained, and if only one or neither of the target cluster compound is added, the target product cannot be obtained.
The two-dimensional layered germanium vanadium oxygen cluster compound is applied to the preparation of magnetic materials.
Compared with the prior art, the invention has the advantages that:
(1) the invention adopts a hydrothermal synthesis method, and successfully prepares an example of Ge by exploring synthesis conditions for the first time6V15O48The cluster unit is formed by four zinc amine complexes [ Zn ]2(en)2]4+Germanium vanadium oxygen cluster compound [ Zn (en) (H) with novel two-dimensional layered structure formed by bridging2O)]4[Zn(en)2]2[Ge6V15O48]·4.5H2O (en: ethylenediamine), and the structure and the magnetic performance of the material are tested and researched, and the research shows that the germanium vanadium oxygen cluster compound has antiferromagnetic property and is a potential magnetic storage material, and the material has potential magnetic application value and can be applied to the preparation of some magnetic materials.
(2) According to the invention, terephthalic acid and 1,2, 4-triazole are combined and applied to a reaction system, so that crystallization of a new crystal species can be promoted, and the germanium vanadium oxide cluster compound disclosed by the invention is successfully synthesized.
Drawings
FIG. 1 is a structural diagram of Compound 1 of the present invention; wherein, the pictures a and b are { [ Zn (en) in the compound 12]2[Ge6V15O48]}8-Cluster club/polyhedron model diagram, Panel c is a dinuclear bridged Complex [ Zn ]2(en)2O2]And (d) is a two-dimensional plan view along the plane c.
FIG. 2 is a view showing the topological structure of Compound 1 of the present invention ({ [ Zn (en)) (H)2O)]4[Ge6V15O48]}4-Polyanion as 4-node).
Figure 3 is an XRD pattern of compound 1 of the present invention.
Fig. 4 is a TG curve of compound 1.
FIG. 5 is an IR spectrum of Compound 1.
Fig. 6 is a temperature swing susceptibility curve for compound 1.
Detailed Description
The invention is described in detail below with reference to the drawings and examples of the specification:
the reagents and instruments required for the present invention are shown in tables 1 and 2, respectively:
TABLE 1 test reagents
TABLE 2 Experimental instruments
Example 1: preparing a two-dimensional layered germanium vanadium oxygen cluster:
the preparation method of the two-dimensional layered germanium vanadium oxygen cluster compound comprises the following steps:
(1) NH is added according to the molar ratio of 1.68:2.01:4.06:1:1.66:41.78:1551.964VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid, 1,2, 4-triazole, en and H2And O is weighed. The mass or volume of each substance in this reaction is: NH (NH)4VO3(0.0351g)、GeO2(0.0376g)、Zn(Ac)2·2H2O (0.1594g), terephthalic acid (0.0298g), 1,2, 4-triazole (0.0205g), en 0.5mL, and H2O 5mL。
(2) Weighing NH4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid and 1,2, 4-triazole were charged to 25mL of a polytetrafluoroethylene liner, followed by ethylene diamine and H2O, stirring for 20-35 min to obtain a mixed solution;
(3) placing the mixed solution obtained in the step (2) in an oven at 170 ℃ for reaction for 4 days, and then cooling to room temperature;
(4) washing and filtering the product obtained in the step (3) by using distilled water to obtain a brown flaky crystal compound 1, namely the two-dimensional layered germanium vanadium oxygen cluster compound;
wherein the yield of the two-dimensional layered germanium vanadium oxide cluster compound (compound 1) is 0.0273 g; yield: 16% by GeO2And (6) counting. Elemental analysis (theoretical) C6.76; n is 7.88; 2.25 percent of H; (Experimental value) C: 7.49; and 7.92 percent of N.
The inventors of the present invention also performed the following experiments, but none of them obtained the target compound two-dimensional layered germanium vanadium oxygen cluster of the present invention:
example 2: terephthalic acid and 1,2, 4-triazole are not added. The other experimental procedures and the amounts of the raw materials except for terephthalic acid and 1,2, 4-triazole were the same as those of example 1. To be weighed NH4VO3、GeO2、Zn(Ac)2·2H2O25 mL of polytetramethyleneIn the vinyl fluoride liner, ethylene diamine and H are subsequently added2O, stirring for 20-35 min to obtain a mixed solution; the obtained mixed solution is put into an oven with the temperature of 170 ℃ for reaction for 4 days, and then is cooled to room temperature, and the two-dimensional layered germanium vanadium oxygen cluster compound of the target compound of the invention is not obtained
Example 3: no terephthalic acid was added. The other experimental procedures and the amounts of the respective raw materials except terephthalic acid were the same as those of example 1. To be weighed NH4VO3、GeO2、Zn(Ac)2·2H2O and 1,2, 4-triazole was charged to 25mL of a polytetrafluoroethylene liner, followed by ethylene diamine and H2O, stirring for 20-35 min to obtain a mixed solution; and placing the obtained mixed solution in an oven at 170 ℃ for reaction for 4 days, and cooling to room temperature to obtain the target compound, namely the two-dimensional layered germanium vanadium oxygen cluster compound.
Example 4: 1,2, 4-triazole is not added; the other experimental procedures and the amounts of the respective raw materials except for 1,2, 4-triazole were the same as those of example 1. To be weighed NH4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid was charged to a 25mL polytetrafluoroethylene liner followed by ethylene diamine and H2O, stirring for 20-35 min to obtain a mixed solution; and placing the obtained mixed solution in an oven at 170 ℃ for reaction for 4 days, and cooling to room temperature to obtain the target compound, namely the two-dimensional layered germanium vanadium oxygen cluster compound.
From the experimental results of examples 2 to 4, it can be seen that although terephthalic acid and 1,2, 4-triazole in the raw materials do not appear in the final crystal structure, they may act as a template agent in the synthesis process to promote crystallization of new crystal species, thereby successfully obtaining the germanium vanadium oxide cluster compound of the present invention. Terephthalic acid and 1,2, 4-triazole are indispensable components in raw materials for synthesizing the two-dimensional layered germanium vanadium oxide cluster compound, play a non-negligible role in the structure of the compound, in addition, the terephthalic acid and the 1,2, 4-triazole must exist in a reaction system at the same time to obtain a target cluster compound, and if only one of the components is added or neither of the components is added, a target product cannot be obtained.
In addition, the present inventors adjusted the amount ratio of the raw materials based on the production method of example 1 (other production methods are the same as example 1) and carried out the following experiment:
example 5:
NH was added at a molar ratio of 1.4:2.2:3.7:1:1.5:66.9:931.34VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid, 1,2, 4-triazole, en and H2And O is weighed. Weighing NH4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid and 1,2, 4-triazole were charged to 25mL of a polytetrafluoroethylene liner, followed by ethylene diamine and H2O, stirring for 20-35 min to obtain a mixed solution; and then placing the obtained mixed solution in an oven at 170 ℃ for reaction for 4 days, cooling to room temperature, washing with distilled water, and filtering to obtain brown flaky crystals, namely the two-dimensional layered germanium vanadium oxygen cluster compound.
Example 6:
NH was added at a molar ratio of 2.0:1.7:4.3:1:2.1:25.1:2172.64VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid, 1,2, 4-triazole, en and H2And O is weighed. Weighing NH4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid and 1,2, 4-triazole were charged to 25mL of a polytetrafluoroethylene liner, followed by ethylene diamine and H2O, stirring for 20-35 min to obtain a mixed solution; and then placing the obtained mixed solution in an oven at 170 ℃ for reaction for 4 days, cooling to room temperature, washing with distilled water, and filtering to obtain brown flaky crystals, namely the two-dimensional layered germanium vanadium oxygen cluster compound.
Example 7:
NH is added according to the molar ratio of 1.5:2.0:4.0:1:2.0:50.0:16004VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid, 1,2, 4-triazole, en and H2And O is weighed. Weighing NH4VO3、GeO2、Zn(Ac)2·2H2O, terephthalic acid and 1,2, 4-triazole were charged to 25mL of a polytetrafluoroethylene liner, followed by ethylene diamine and H2O, stirring for 20-35 min to obtain a mixed solution; and then placing the obtained mixed solution in an oven at 170 ℃ for reaction for 4 days, cooling to room temperature, washing with distilled water, and filtering to obtain brown flaky crystals, namely the two-dimensional layered germanium vanadium oxygen cluster compound.
Although the two-dimensional layered germanium vanadium oxide cluster compound can be obtained by the preparation methods of the embodiments 5 to 7, the yield of the embodiments 5 to 7 is lower than that of the preparation method of the embodiment 1, the obtained product has more impurities, and the crystal form of the crystal is poorer. It can be seen from comparing examples 1 and 5-7 that the strict requirement on the mixture ratio of the raw materials in the synthesis of the crystal directly affects the formation of the crystal or negatively affects other results if the mixture ratio of the raw materials is not proper.
Example 8: crystal structure determination and structure analysis:
from the large amount of the crude crystal (compound 1) synthesized in example 1, single crystals having a clean surface and an appropriate size were selected by a JSZ5B continuous zoom microscope. The picked single crystal is adhered to the top end of the glass fiber by evenly mixed A, B glue, the single crystal is kept in a vertical state and is in the same straight line with the glass fiber, which is beneficial to the centering operation in the X-ray single crystal diffraction experiment, and then the glass fiber is arranged on a crystal carrying platform. The X-ray single crystal diffraction experiments were performed on a Bruker Apex II CCD diffractometer. At 296K temperature, using graphite monochromator and Mo target K alpha rayCollecting diffraction point data in a certain range by using omega-2 theta scanning mode as an X-ray source, and selecting I>2 σ (I) independent diffraction points. Crystallographic data for the compound are given in table 3:
table 3 structural parameters and crystal data for compound 1
Example 9: the compound 1 obtained in example 1 was subjected to crystal property test:
1. x-ray single crystal structural analysis of Compound 1
The diffraction data for X-ray structure analysis was collected on a Bruker Apex II CCD diffractometer; MoK alpha ray, graphite monochromator, radiation wavelength ofThe crystal structure was resolved and refined using the SHELXL-97 package.
The detection result shows that:
the compound 1 belongs to an orthorhombic system, and the space group is Pbcn which is formed by { Ge6V15O48The cluster unit is formed by four zinc amine complexes [ Zn ]2(en)2]4+And four adjacent surrounding cluster units are bridged to form a two-dimensional layer structure. Cluster anion [ Ge ]6V15O48]12-Having D3Symmetry, from 15 VOs5Tetragonal pyramid and three Ge2O7And (3) unit constitution. It can be regarded as three VOs5Tetragonal pyramid and three Ge2O7The two dimerization units are alternately connected into a Ge through a common vertex6V3With Ge as a ring structure fragment of6V3The ring is the center of the plane, and the remaining twelve VOs5The square cones are divided into an upper group and a lower group, and every six VOs5The tetragonal pyramid forms two triangular structure segments respectively through common edges or common vertexes, and then is connected to Ge through common oxygen atom bonds3V3The upper side and the lower side of the ring structure segment form a complete cage-shaped cluster anion [ Ge ]6V15O48]12-. Two [ Zn (en)2]2+The complex is used as a modifying group and is suspended on a cluster anion [ Ge ] through Ge terminal oxygen6V15O48]12-Form a double-supported { [ Zn (en) ]2]2[Ge6V15O48]}8-Clusters (e.g., panels a, b of FIG. 1), followed by four cluster anions per cluster[Zn2(en)2]4+The complex is connected with Ge terminal oxygen of four adjacent cluster units around, and finally a two-dimensional layer with an expanded structure along the c surface is formed (as shown in a diagram d in figure 1). Simplifying each cluster anion to 4 nodes, the whole topology can be regarded as 4 nodes of {4 }4·62Type (as shown in fig. 2).
In this crystal structure, three Zn2+The ions exist in two different coordination modes, one is tetrahedral ZnO of four coordination3N2(Zn1, Zn2) and penta-coordinated tetragonal pyramid ZnON4(Zn 3). Wherein, the four coordination atoms of Zn1 and Zn2 are respectively from two N atoms (Zn-N: ) And two germanium-terminal oxygen atoms (Zn — O:) The five coordinating atoms of Zn3 are derived from four N atoms on the two en ligands (Zn-N:) And one germanium-terminal oxygen atom (Zn — O:)。
all V atoms in the cluster are VO5In the form of a tetragonal pyramid, in which V-OtA range of bond lengths ofV-ObA range of bond lengths ofGe-OtA range of bond lengths ofValence bond calculations (BVS) indicate that all V atoms in the crystal are +4 (4.03-4.15) and all Ge atoms are +4 (4.05-4.11) (Table 4). The valence of Zn atom and all O atoms are +2 and-2 respectively.
TABLE 4 valence bond calculation for Compound 1
2. PXRD analysis for Compound 1
Powder testing of the samples was performed using a Bruker D8 Advance powder diffractometer with CuKalpha radiation at a wavelength of
The compound 1 sample is ground into powder and then subjected to XRD test at normal temperature, the X-ray powder diffraction pattern of the crystalline compound 1 is shown in figure 3, and the simulated diffraction patterns analyzed by comparing X-ray powder diffraction experimental data and single crystal diffraction structure data show that the absorption peak positions of the two patterns are well matched, and only the intensities of diffraction peaks are different, which indicates that the synthesized crystal is pure phase.
3. Thermogravimetric (TG) analysis of Compound 1
Thermal analysis (TGA) was performed using a NETZSCHPC 409 differential scanning calorimeter at N2In the atmosphere, the temperature was raised at a rate of 10 degrees per minute.
The thermogram of the crystalline compound is shown in FIG. 4, which is measured at a temperature rise rate of 10 ℃/min in the range of 20-1000 ℃ under a nitrogen atmosphere. From the weight loss curve, it can be seen that the continuous weight loss between 20-562 ℃ (17.26%) is due to the loss of 8 en molecules in the compound (theoretical weight loss value 17.13%).
4. Fourier transform Infrared Spectroscopy (FT-IR) analysis of Compound 1
Infrared absorption spectroscopy analyzes, characterizes, and quantifies the structure of a substance, primarily by using the principle of the selective absorption characteristics of a substance for electromagnetic radiation in the infrared region.
The measurement conditions were: scanning with a Nicolette is 10 type infrared spectrometer at room temperature by potassium bromide tabletting method to obtain a scanning wave number range of 400-4000cm-1。
The infrared spectrum of compound 1 is shown in figure 5. As can be seen from the figure, at 3345-3310cm-1And 2975-2867cm-1The absorption of (A) is due to NH2And CH2Caused by stretching vibration of the radicals; at 1580 and 1605cm-1And 1340-1458cm-1Absorption of the band is by NH2And CH2Caused by flexural vibration of the radicals; is positioned at 3460 and 3391cm-1The absorption peak is due to OH-Caused by the stretching vibration of (a); at 1015--1The strong absorption peak at the position is attributed to the stretching vibration of V ═ O, and is 890-748cm-1The absorption peak is due to GeO4These conclusions are also consistent with the single crystal structure of the crystal, due to Ge-O stretching vibrations in the tetrahedron.
5. Magnetic assay of Compound 1
Magnetic testing of the samples was performed on a Quantum Design SQUID VSM magnetometer. The magnetic field intensity is 1000Oe, and the test temperature is 2-300K.
The invention researches the temperature-changing magnetic susceptibility curve of the compound 1 under the external magnetic field 1KOe, as shown in figure 6, in chi%MT is plotted against T, and the measurement temperature ranges from 2 to 300K. As the temperature decreases, χMThe T value is slowly reduced to the minimum value of 0.52cm when the T value is 2K3 K mol-1The magnetic behavior shows that the tetravalent vanadium ions in the compound have antiferromagnetic interaction, wherein the compound conforms to Curie-Weiss law chi/(T-theta) within the range of 2-127K, and the Curie constant of the compound is 1.17cm3·mol-1K and the Curie temperature theta is-7.43K, and the existence of antiferromagnetic property in the compound is further proved, so that the material has potential magnetic application value.
6. Elemental analysis
C. The H, N content analysis was done using an Elementar variao EL III elemental analyzer. The elemental analysis results were: elemental analysis (theoretical) C6.76; n is 7.88; 2.25 percent of H; (Experimental value) C: 7.49; and 7.92 percent of N.
7. Conclusion
The invention adopts a hydrothermal synthesis method to successfully synthesize one example of two [ Zn (en) ]for the first time2]2+The two-dimensional layered germanium vanadium oxygen cluster compound supported by the complex is recorded and analyzed in the structure through a single crystal diffractometer, and the structure is shown in the specification of V18O52On the basis of the cluster, three Ge clusters are respectively arranged2O7Dimer substitution of three VOs5Tetragonal pyramid formed { Ge6V15O48Cluster, two [ Zn (en) ]2]2+The complex is taken as a modifying group to be hung outside the cluster, and then four zinc-amine complexes [ Zn ] are used2(en)2]4+Bridging to form a new two-dimensional layer structure. The XRD spectrum shows that the compound is a pure phase structure; the structural characteristics of the compound are further determined by the analysis results of thermogravimetric analysis and infrared spectrogram; magnetic tests show that the crystal has an antiferromagnetic effect and is a potential magnetic storage material.
