CN108948372B - Mn-based polycarboxylic acid coordination polymer magnetic material and preparation method thereof - Google Patents

Mn-based polycarboxylic acid coordination polymer magnetic material and preparation method thereof Download PDF

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CN108948372B
CN108948372B CN201811040832.0A CN201811040832A CN108948372B CN 108948372 B CN108948372 B CN 108948372B CN 201811040832 A CN201811040832 A CN 201811040832A CN 108948372 B CN108948372 B CN 108948372B
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杨庆凤
李建华
魏海文
赖小勇
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Abstract

The invention relates to a magnetic material of a Mn-based polycarboxylic acid coordination polymer, which is prepared from Mn (H)2pimdc)2(phen)·H2O is a structural unit, and is bridged into a one-dimensional chain structure coordination polymer through a protonated 2-propyl-5, 6-imidazole dicarboxylic acid ligand, and the molecular formula of the coordination polymer is [ Mn (H)2pimdc)2(phen)·H2O]nIn which H is2pimdc is protonated 2-propyl-5, 6-imidazoledicarboxylic acid, phen is 1, 10-phenanthroline. Meanwhile, the invention also discloses a preparation method of the magnetic material. The invention has good water stability.

Description

Mn-based polycarboxylic acid coordination polymer magnetic material and preparation method thereof
Technical Field
The invention relates to the technical field of new materials, in particular to a magnetic material of a polycarboxylic acid coordination polymer based on Mn and a preparation method thereof.
Background
Coordination polymers have developed rapidly in the fields of chemistry and material science over the past few decades. The coordination polymer is formed by organic ligands and metal ions through self-assembly and completely or partially by coordination bonds to form a network structure with 0-D, 1-D, 2-D or 3-D. Due to the novel framework structure, topological structure and good performance of the coordination polymer, the advantages of inorganic materials and organic materials are combined, and the potential application of the coordination polymer in the aspects of optics, magnetics, catalysis, gas storage and the like becomes a hotspot of research. Because the ligand and the metal ion have higher affinity, the high-dimensional coordination polymer is easier to synthesize, and compared with the traditional high-dimensional coordination polymer, the three-dimensional supermolecular structure of the low-dimensional coordination polymer becomes a research hotspot in the field of crystal engineering. Particularly, the low-dimensional coordination polymer has great application value in recent years as a molecular-based magnetic material. For example, single molecule magnets have been extensively studied because the magnetic system provides a good model for understanding the magnetic exchange interaction at the molecular level. The molecular magnet is a compound synthesized by paramagnetic metal ions and organic bridging ligands in a self-assembly and assembly control mode. When reaching its critical temperature, the molecular magnet will have a spontaneous magnetization behavior.
Since the first co (ii) -based single molecule magnet reports, researchers have continually synthesized co (ii) -based SMMs with high energy barriers. In recent years, due to the diversity of coordination modes, the design and synthesis of low dimensional coordination polymers by selecting metal central ions with specific geometrical configurations and organic ligands for self-assembly reaction have become one of the current research hotspots, and many aromatic polycarboxylic acids and N/O donor bridging ligands are applied to the construction of coordination polymers. For example, iron and cobalt based low dimensional coordination polymer magnetic materials (Wei H. W, Yang Q. F, Lai X. Y, Wang X. Z, Yang T. L, Hou Q, Liu X. Y, Field-Induced Slow Relaxation of the Magnetization in a discrete Octahedral monomer High-Spin Co (II) Complex).CrystEngComm2018(7), 20: 962 and 968) indicated that appropriate coordination sites and effective control of the distance between the metal centers of the complexes facilitate the obtainment of mononuclear compounds.
At present, there are few reports on coordination polymers based on aromatic polycarboxylic acid ligands, but since both N and O atoms in the aromatic polycarboxylic acid molecule can act as donors to coordinate with the metal center, most are high-dimensional coordination polymers, which is not favorable for the research of magnetic materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing a Mn-based polycarboxylic acid coordination polymer magnetic material with good water stability.
The invention also provides a preparation method of the Mn-based polycarboxylic acid coordination polymer magnetic material.
In order to solve the above problems, the present invention provides a Mn-based polycarboxylic acid coordination polymer magnetic material, which is characterized in that: the material is Mn (H)2pimdc)2(phen)·H2O is a structural unit, and is bridged into a one-dimensional chain structure coordination polymer through a protonated 2-propyl-5, 6-imidazole dicarboxylic acid ligand, and the molecular formula of the coordination polymer is [ Mn (H)2pimdc)2(phen)·H2O]nIn which H is2pimdc is protonated 2-propyl-5, 6-imidazoledicarboxylic acid, phen is 1, 10-phenanthroline.
The preparation method of the Mn-based polycarboxylic acid coordination polymer magnetic material comprises the following steps:
first, Mn (CH)3COO)2·4H2O, 2-propyl-5, 6-imidazole dicarboxylic acid, 1, 10-phenanthroline and acetonitrile in water according to the proportion of 0.1-0.3 mmol: 0.1-0.3 mmol: 0.1-0.3 mmol: mixing 9-12 mL of the mixture, and stirring at room temperature for 2-4 hours to obtain a mixture;
adjusting the pH value of the mixture to 3-6 by using an acid solution or an alkali solution, then placing the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 60-80%, placing the reaction kettle into an oven with the temperature of 140-170 ℃, and heating and crystallizing the reaction kettle for 3-6 days under the action of self pressure; turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain bright yellow blocky crystals;
and washing the bright yellow blocky crystal by distilled water for 3 times, and drying at 40-60 ℃ for 3-6 h to obtain the Mn-based polycarboxylic acid coordination polymer magnetic material.
The acetonitrile water solution in the step is prepared by mixing acetonitrile and water according to a ratio of 2-4 mL: 6-10 mL of mixed liquid.
The acid solution in the step II is dilute hydrochloric acid with the concentration of 1-3 mol/L.
The step II is to use an alkali solution as a potassium hydroxide solution with the concentration of 1-3 mol/L.
Compared with the prior art, the invention has the following advantages:
1. the product obtained by the invention belongs to an orthorhombic system, and the space group isPbcaThe unit cell parameters are:a = 19.3310(5) Å，b = 9.0400(2) Å，c = 21.3243(5) Å，α =β=γ = 90°the asymmetric unit contains a crystallographically independent manganese ion, two 2-propyl-5, 6-imidazole dicarboxylic acid ligands and a 1, 10-phenanthroline ligand; each asymmetric unit passing through the O atom and the N atom of the 2-propyl-5, 6-imidazole dicarboxylic acid ligandThe coordination of the proton and Mn ion forms a one-dimensional chain, and the one-dimensional chain is followed by intermolecular hydrogen bondcThe two-dimensional layers form a three-dimensional supermolecular structure through pi & phi stacking; in three-dimensional supramolecular structures, there are edgescOne structure similar to a spiral chain can be seen in the axial direction when viewed fromaShaft andbwhen viewed in the axial direction, that is caused by the 1, 10-phenanthroline ligand coordinated to the Mn ion on both sides of the center (see FIGS. 1 to 3).
The product obtained by the invention was analyzed for its thermal stability by Setsys 16, Setsys, Setam, France (see FIG. 4), and it can be seen that the thermogravimetric curve of the compound shows a two-step weight loss process. The first step starts at 160 ℃ and ends at 350 ℃, which can be attributed to the removal of the coordinated water molecules. The second step is from 350 ℃ to 740 ℃, and the part is attributed to the decomposition of the organic framework.
The product obtained by the invention is tested by a Quantum Design SQUID magnetometer MPMS-XL type magnetometer under the conditions that the applied field strength is 1000 Oe and the temperature test interval is 2-300K (see figure 5), and the curve change trend shows that the coordination polymer has weak antiferromagnetism. Fitting magnetic susceptibility data of two compounds in a full temperature interval by adopting Curie-Weiss law to obtain the magnetic susceptibility of the polymerθ = -9.09 K，C = 6.33 cm3 mol-1. The results of the fitting indicate that the polymer has weak antiferromagnetic behavior.
2. The invention adopts a hydrothermal synthesis method, uses 2-propyl-5, 6-imidazole dicarboxylic acid and 1, 10-phenanthroline to obtain Mn2+The obtained target product has good water stability and can be placed in the air for a long time without deterioration; in addition, imidazole as a ligand of the triatomic like compound has good electron transmission capability, is an excellent ligand for constructing a molecular magnet, and can be applied to the field of preparation of monomolecular magnets.
3. The synthesis reaction of the invention is environment-friendly, simple and feasible, has low cost, the yield of the obtained product is about 50 percent, and the invention is easy for large-scale industrial production.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a one-dimensional chain diagram of a transition metal Mn1 in the crystal structure of a polycarboxylic acid-containing manganese coordination polymer magnetic material obtained in example 1 of the present invention.
FIG. 2 is a three-dimensional supramolecular structure diagram of a manganese coordination polymer magnetic material containing polycarboxylic acid obtained in example 1 of the present invention.
FIG. 3 is an infrared spectrum of a polycarboxylic acid-containing manganese coordination polymer magnetic material obtained in example 1 of the present invention.
FIG. 4 is a graph showing the thermogravimetric analysis of the magnetic material of manganese coordination polymer containing polycarboxylic acid obtained in example 1 of the present invention.
FIG. 5 is a DC temperature-changing magnetic susceptibility curve diagram of the manganese coordination polymer magnetic material containing polycarboxylic acid obtained in example 1 of the present invention.
Detailed Description
A magnetic Mn-based polycarboxylic acid coordination polymer material is prepared from Mn (H)2pimdc)2(phen)·H2O is a structural unit, and is bridged into a one-dimensional chain structure coordination polymer through a protonated 2-propyl-5, 6-imidazole dicarboxylic acid ligand, and the molecular formula of the coordination polymer is [ Mn (H)2pimdc)2(phen)·H2O]nIn which H is2pimdc is protonated 2-propyl-5, 6-imidazoledicarboxylic acid, phen is 1, 10-phenanthroline.
Embodiment 1 a method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material, comprising the steps of:
first, Mn (CH)3COO)2·4H2O (24.5 mg), 2-propyl-5, 6-imidazole dicarboxylic acid (42 mg), 1, 10-phenanthroline (39.6 mg), acetonitrile in water in an amount of 0.1 mmol: 0.2 mmol: 0.2 mmol: after mixing 10 mL of the mixture, the mixture was stirred at room temperature for 3 hours to obtain a mixture.
Wherein: the acetonitrile water solution refers to acetonitrile and water, wherein the acetonitrile and the water are mixed according to the weight ratio of 2 mL: 8 mL of a mixture obtained by mixing the components in a volume ratio.
Adjusting the pH value of the mixture to 3 by using an acid solution or an alkali solution, filling the mixture into a 15 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 67 percent, putting the reaction kettle into a 160 ℃ drying oven, and heating and crystallizing the reaction kettle for 4 days under the action of self pressure; and (5) turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain bright yellow blocky crystals.
Wherein: the acid solution is dilute hydrochloric acid with the concentration of 1 mol/L. The alkaline solution is potassium hydroxide solution with the concentration of 1 mol/L.
Washing the bright yellow blocky crystal by distilled water for 3 times, and drying at 40 ℃ for 4 hours to obtain the Mn-based polycarboxylic acid coordination polymer magnetic material. The yield was 50%.
The resulting crystals were subjected to a Siemens SMART CCD diffractometer to collect diffraction data on a molybdenum target MoK α rays monochromated with graphite (λ = 0.71073 a) in an ω -scan mode at a 293 (2) K temperature. The single crystal structure analysis was performed by using the SHELXTL-97 program. The position of metal atoms is determined by a direct method, then all non-hydrogen atom coordinates are obtained by a difference function method and a least square method, and anisotropy correction is carried out on the non-hydrogen atoms to obtain the coordination polymer magnetic material with the structure of [ Mn (H)2pimdc)2(phen)·H2O]n. Table 1 shows the main crystallographic data of the coordination polymer. FIGS. 1 to 2 are structural diagrams made by a conventional crystal mapping software based on the measurement results. FIG. 3 is an infrared spectrum of the coordination polymer obtained by tabletting with KBr and measuring with a Bruker Tensor 27 infrared spectrometer within a range of 400 to 4000 cm-1.
TABLE 1
Figure 637539DEST_PATH_IMAGE001
Embodiment 2 a method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material, comprising the steps of:
first, Mn (CH)3COO)2·4H2O (24.5 mg), 2-propyl-5, 6-imidazole dicarboxylic acid (42 mg), 1, 10-phenanthroline (19.8 mg), acetonitrile in water in an amount of 0.1 mmol: 0.2 mmol: 0.1 mmol: after mixing in a proportion of 12 mL, the mixture was stirred at room temperature for 4 hours to obtain a mixture.
Wherein: the acetonitrile aqueous solution refers to the mixture of acetonitrile and water according to the ratio of 3 mL: 9 mL of the mixture was mixed at a volume ratio.
Adjusting the pH value of the mixture to 4 by using an acid solution or an alkali solution, filling the mixture into a 15 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 80 percent, putting the reaction kettle into a 170 ℃ drying oven, and heating and crystallizing the reaction kettle for 3 days under the action of self pressure; and (5) turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain bright yellow blocky crystals.
Wherein: the acid solution is dilute hydrochloric acid with the concentration of 2 mol/L. The alkaline solution is potassium hydroxide solution with the concentration of 2 mol/L.
Washing the bright yellow blocky crystal by distilled water for 3 times, and drying at 50 ℃ for 3 hours to obtain the Mn-based polycarboxylic acid coordination polymer magnetic material. The yield was 53%.
The resulting crystals were subjected to a Siemens SMART CCD diffractometer to collect diffraction data on a molybdenum target MoK α rays monochromated with graphite (λ = 0.71073 a) in an ω -scan mode at a 293 (2) K temperature. The single crystal structure analysis was performed by using the SHELXTL-97 program. The position of metal atoms is determined by a direct method, then all non-hydrogen atom coordinates are obtained by a difference function method and a least square method, and anisotropy correction is carried out on the non-hydrogen atoms to obtain the coordination polymer magnetic material with the structure of [ Mn (H)2pimdc)2(phen)·H2O]n. The main crystallographic data and infrared spectrum of the coordination polymer fluorescent material are the same as those of example 1.
Embodiment 3 a method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material, comprising the steps of:
first, Mn (CH)3COO)2·4H2O (49 mg), 2-propyl-5, 6-imidazole dicarboxylic acid (42 mg), 1, 10-phenanthroline, acetonitrile in water in an amount of 0.2 mmol: 0.2 mmol: 0.1 mmol: after mixing at a ratio of 9 mL, the mixture was stirred at room temperature for 2 hours to obtain a mixture.
Wherein: the acetonitrile aqueous solution refers to the mixture of acetonitrile and water according to the ratio of 3 mL: 6 mL of a mixture obtained by mixing the components in a volume ratio.
Adjusting the pH value of the mixture to 6 by using an acid solution or an alkali solution, filling the mixture into a 15 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 60 percent, putting the reaction kettle into a 150 ℃ drying oven, and heating and crystallizing the reaction kettle for 5 days under the action of self pressure; and (5) turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain bright yellow blocky crystals.
Wherein: the acid solution is dilute hydrochloric acid with the concentration of 3 mol/L. The alkaline solution is potassium hydroxide solution with the concentration of 3 mol/L.
Washing the bright yellow blocky crystal by distilled water for 3 times, and drying at 60 ℃ for 6 hours to obtain the Mn-based polycarboxylic acid coordination polymer magnetic material. The yield was 45%.
The resulting crystals were subjected to a Siemens SMART CCD diffractometer to collect diffraction data on a molybdenum target MoK α rays monochromated with graphite (λ = 0.71073 a) in an ω -scan mode at a 293 (2) K temperature. The single crystal structure analysis was performed by using the SHELXTL-97 program. The position of metal atoms is determined by a direct method, then all non-hydrogen atom coordinates are obtained by a difference function method and a least square method, and anisotropy correction is carried out on the non-hydrogen atoms to obtain the coordination polymer magnetic material with the structure of [ Mn (H)2pimdc)2(phen)·H2O]n. The main crystallographic data and infrared spectrum of the coordination polymer magnetic material are the same as those of example 1.
Embodiment 4 a method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material, comprising the steps of:
first, Mn (CH)3COO)2·4H2O (49 mg), 2-propyl-5, 6-imidazole dicarboxylic acid (21 mg), 1, 10-phenanthroline (19.8 mg), acetonitrile in water in an amount of 0.2 mmol: 0.1 mmol: 0.1 mmol: after mixing at a ratio of 10 mL, the mixture was stirred at room temperature for 2 hours to obtain a mixture.
Wherein: the acetonitrile in water is acetonitrile and water, and the ratio of acetonitrile to water is 2L: 8L of the mixture was mixed at a volume ratio.
Adjusting the pH value of the mixture to 5 by using an acid solution or an alkali solution, filling the mixture into a 15 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 67 percent, putting the reaction kettle into a 140 ℃ drying oven, and heating and crystallizing the reaction kettle for 5 days under the action of self pressure; and (5) turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain bright yellow blocky crystals.
Wherein: the acid solution is dilute hydrochloric acid with the concentration of 3 mol/L. The alkaline solution is potassium hydroxide solution with the concentration of 3 mol/L.
Washing the bright yellow blocky crystal by distilled water for 3 times, and drying at 60 ℃ for 6 hours to obtain the Mn-based polycarboxylic acid coordination polymer magnetic material. The yield was 54%.
The resulting crystals were subjected to a Siemens SMART CCD diffractometer to collect diffraction data on a molybdenum target MoK α rays monochromated with graphite (λ = 0.71073 a) in an ω -scan mode at a 293 (2) K temperature. The single crystal structure analysis was performed by using the SHELXTL-97 program. The position of metal atoms is determined by a direct method, then all non-hydrogen atom coordinates are obtained by a difference function method and a least square method, and anisotropy correction is carried out on the non-hydrogen atoms to obtain the coordination polymer magnetic material with the structure of [ Mn (H)2pimdc)2(phen)·H2O]n. The main crystallographic data and infrared spectrum of the coordination polymer magnetic material are the same as those of example 1.
Embodiment 5 a method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material, comprising the steps of:
first, Mn (CH)3COO)2·4H2O (49 mg), 2-propyl-5, 6-imidazole dicarboxylic acid (21 mg), 1, 10-phenanthroline (39.6 mg), acetonitrile in water in an amount of 0.2 mmol: 0.1 mmol: 0.2 mmol: after mixing in a proportion of 12 mL, the mixture was stirred at room temperature for 2 hours to obtain a mixture.
Wherein: the acetonitrile aqueous solution is prepared by mixing acetonitrile and water according to the weight ratio of 3L: 9 mL of the mixture was mixed at a volume ratio.
Adjusting the pH value of the mixture to 6 by using an acid solution or an alkali solution, filling the mixture into a 15 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 80 percent, putting the reaction kettle into a 150 ℃ drying oven, and heating and crystallizing the reaction kettle for 3 days under the action of self pressure; and (5) turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain bright yellow blocky crystals.
Wherein: the acid solution is dilute hydrochloric acid with the concentration of 3 mol/L. The alkaline solution is potassium hydroxide solution with the concentration of 3 mol/L.
Washing the bright yellow blocky crystal by distilled water for 3 times, and drying at 60 ℃ for 6 hours to obtain the Mn-based polycarboxylic acid coordination polymer magnetic material. The yield was 56%.
The resulting crystals were subjected to a Siemens SMART CCD diffractometer to collect diffraction data on a molybdenum target MoK α rays monochromated with graphite (λ = 0.71073 a) in an ω -scan mode at a 293 (2) K temperature. The single crystal structure analysis was performed by using the SHELXTL-97 program. The position of metal atoms is determined by a direct method, then all non-hydrogen atom coordinates are obtained by a difference function method and a least square method, and anisotropy correction is carried out on the non-hydrogen atoms to obtain the coordination polymer magnetic material with the structure of [ Mn (H)2pimdc)2(phen)·H2O]n. The main crystallographic data and infrared spectrum of the coordination polymer magnetic material are the same as those of example 1.
Embodiment 6 a method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material, comprising the steps of:
first, Mn (CH)3COO)2·4H2O (73.5 mg), 2-propyl-5, 6-imidazole dicarboxylic acid (63 mg), 1, 10-phenanthroline (59.4 mg), acetonitrile in water in an amount of 0.3 mmol: 0.3 mmol: 0.3 mmol: after mixing at a ratio of 6 mL, the mixture was stirred at room temperature for 2 hours to obtain a mixture.
Wherein: the aqueous acetonitrile solution is prepared by mixing acetonitrile and water according to the weight ratio of 4L: 10 mL of the mixture was mixed at a volume ratio.
Adjusting the pH value of the mixture to 6 by using an acid solution or an alkali solution, filling the mixture into a 15 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 60 percent, putting the reaction kettle into a 150 ℃ drying oven, and heating and crystallizing the reaction kettle for 6 days under the action of self pressure; and (5) turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain bright yellow blocky crystals.
Wherein: the acid solution is dilute hydrochloric acid with the concentration of 3 mol/L. The alkaline solution is potassium hydroxide solution with the concentration of 3 mol/L.
Washing the bright yellow blocky crystal by distilled water for 3 times, and drying at 80 ℃ for 5 hours to obtain the Mn-based polycarboxylic acid coordination polymer magnetic material. The yield was 53%.
The resulting crystals were subjected to a Siemens SMART CCD diffractometer to collect diffraction data on a molybdenum target MoK α rays monochromated with graphite (λ = 0.71073 a) in an ω -scan mode at a 293 (2) K temperature. The single crystal structure analysis was performed by using the SHELXTL-97 program. The position of metal atoms is determined by a direct method, then all non-hydrogen atom coordinates are obtained by a difference function method and a least square method, and anisotropy correction is carried out on the non-hydrogen atoms to obtain the coordination polymer magnetic material with the structure of [ Mn (H)2pimdc)2(phen)·H2O]n. The main crystallographic data and infrared spectrum of the coordination polymer magnetic material are the same as those of example 1.

Claims (5)

1. A magnetic material of a Mn-based polycarboxylic acid coordination polymer is characterized in that: the material is Mn (H)2pimdc)2(phen)·H2O is a structural unit, and is bridged into a one-dimensional chain structure coordination polymer through a deprotonated 2-propyl-4, 5-imidazole dicarboxylic acid ligand, and the molecular formula of the coordination polymer is [ Mn (H)2pimdc)2(phen)·H2O]nIn which H is2pimdc-1Is deprotonated 2-propyl-4, 5-imidazole dicarboxylic acid, phen is 1, 10-phenanthroline, the polymer magnetic material is an orthorhombic system, and the space group isPbcaThe unit cell parameters are:a = 19.3310(5) Å，b = 9.0400(2) Å，c = 21.3243(5) Å，α =β=γ = 90°。
2. the method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material according to claim 1, comprising the following steps:
first, Mn (CH)3COO)2·4H2O, 2-propyl-4, 5-imidazole dicarboxylic acid, 1, 10-phenanthroline and acetonitrile in water according to the proportion of 0.1-0.3 mmol: 0.1-0.3 mmol: 0.1-0.3 mmol: mixing 9-12 mL of the mixture, and stirring at room temperature for 2-4 hours to obtain a mixture;
adjusting the pH value of the mixture to 3-6 by using an acid solution or an alkali solution, then placing the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 60-80%, placing the reaction kettle into an oven with the temperature of 140-170 ℃, and heating and crystallizing the reaction kettle for 3-6 days under the action of self pressure; turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain bright yellow blocky crystals;
and washing the bright yellow blocky crystal by distilled water for 3 times, and drying at 40-60 ℃ for 3-6 h to obtain the Mn-based polycarboxylic acid coordination polymer magnetic material.
3. A method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material according to claim 2, characterized in that: the acetonitrile water solution in the step is prepared by mixing acetonitrile and water according to a ratio of 2-4 mL: 6-10 mL of mixed liquid.
4. A method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material according to claim 2, characterized in that: the acid solution in the step II is dilute hydrochloric acid with the concentration of 1-3 mol/L.
5. A method for preparing a Mn-based polycarboxylic acid coordination polymer magnetic material according to claim 2, characterized in that: the step II is to use an alkali solution as a potassium hydroxide solution with the concentration of 1-3 mol/L.
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Title
Field-induced slow relaxation of magnetization in a distorted octahedral mononuclear high-spin Co(Ⅱ) complex;Hai-Wen Wei et al.;《CrystEngComm》;20180108;第20卷;第963页"合成分析"部分 *
The first one-dimensional manganese polymer containing 4,5-dicarboxyimidazole:solvothermal synthesis, crystal structure and magnetic behavior of [Mn(phen)(Hdcbi)]n(H3dcbi = 4,5-dicarboxyimidazole, phen =1,10-phenanthroline);Xiaofeng Zhang et al.;《Inorg. Chem. Commun.》;20040412;第7卷;全文 *

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