CN117550966A - Novel manganese tetranuclear structure metal complex, and preparation method and application thereof - Google Patents
Novel manganese tetranuclear structure metal complex, and preparation method and application thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 52
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 30
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims abstract description 15
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000696 magnetic material Substances 0.000 claims abstract description 11
- OMPLWOKOQNOVCD-UHFFFAOYSA-N 2-[3,5-bis(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC(OCC(O)=O)=CC(OCC(O)=O)=C1 OMPLWOKOQNOVCD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910001437 manganese ion Inorganic materials 0.000 claims description 10
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000005291 magnetic effect Effects 0.000 abstract description 32
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000012827 research and development Methods 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 18
- 238000010586 diagram Methods 0.000 description 13
- 230000003993 interaction Effects 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000005290 antiferromagnetic effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- 241000238366 Cephalopoda Species 0.000 description 2
- 229910018663 Mn O Inorganic materials 0.000 description 2
- 229910003176 Mn-O Inorganic materials 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- 101100378877 Caenorhabditis elegans allo-1 gene Proteins 0.000 description 1
- 230000005343 Curie-Weiss law Effects 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000212749 Zesius chrysomallus Species 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 230000005316 antiferromagnetic exchange Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
- C07C59/70—Ethers of hydroxy-acetic acid, e.g. substitutes on the ring
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
The invention relates to a metal coordination compound, in particular to a novel manganese tetranuclear structure metal complex, a preparation method and application thereof, wherein the chemical general formula of the complex is [ Mn ] 2 (μ 3 ‑OH)Mn 0.5 Mn 0.5 (tbac) 2 ] n ·2H 2 O, where H 3 tbac = 1,3, 5-tris (carboxymethoxy) benzene; the preparation method comprises the following steps: will H 3 Putting tbac in a reaction kettle, adding a mixed solvent, stirring at room temperature for 30min, adding manganese acetate tetrahydrate, continuously stirring until the manganese acetate tetrahydrate is completely dissolved, regulating the pH value to 7-8, continuously stirring for 30min, sealing the reaction kettle, placing the reaction kettle at a constant temperature of 160 ℃ for reaction, and cooling after the reactionAnd (3) cooling to room temperature, filtering, and washing to obtain blocky yellow crystals, namely the novel manganese tetranuclear structure metal complex. The obtained complex has good thermal stability and magnetic property, and provides theoretical basis and experimental basis for in-depth research and development of Mn complex molecule-based magnetic materials.
Description
Technical Field
The invention relates to a metal coordination compound, in particular to a novel manganese tetranuclear structure metal complex, a preparation method and application thereof.
Background
With the increasing demand of people for various high and new technologies, magnetic materials gradually develop into modern magnetic storage materials, magnetic wave absorbing materials, magnetic induction materials, magnetic sensitive materials and the like. The molecular-based magnet has the advantages of high transparency, non-conductivity, low density, easy processing, high magnetic capacity, low magnetic consumption ratio and the like, is various in ligand design, can obtain various molecular-based magnets, can purposefully modify the structure of the ligand by researching the relation between the structure and the performance of the complex, further improves the performance of the complex, improves the magnetic performance of the molecular-based magnet, and is suitable for being used as electromagnetic shielding materials, aerospace materials, information storage materials, biocompatible materials and the like.
Bistable molecular magnetic materials are one of the hot spots of current molecular magnetic material research, including temperature-responsive magnetic bistable materials and magnetic bistable materials that respond to external magnetic fields, with spin-cross complexes and single-molecule magnets being the most widely studied. The spin cross complex can realize bistable state phenomenon regulated and controlled by external factors such as temperature, pressure, optical radiation and the like near room temperature, is the molecular-based magnetic material closest to practical application, and has potential application value in the aspects of molecular switch, sensing, information storage and the like. The single-molecule magnet is a nano-size molecular magnetic material, has the characteristics of easy processing, low density, chemical solubility and the like, and has potential application value in the fields of ultrahigh-density information storage, quantum computers, spintronics and the like because the single-molecule magnet can keep magnetization property and has slow magnetic relaxation behavior after an external magnetic field is removed. TransitionThe metal Co (II) and the rare earth metal Dy (III) have unquenched orbital angular momentum and strong magnetic anisotropy, and are the optimal carriers for constructing high-performance single-molecule magnets. In recent years, scientists are no longer satisfied with independently researching spin-cross and single-molecule magnets, but choose to design and synthesize novel ligands, and combine the two properties to synthesize a spin-cross-single-molecule magnet bifunctional complex. At present, the two properties are combined to synthesize a spin cross-single molecular magnet bifunctional complex, which is rarely reported, and the flexible aromatic carboxylic acid 1,3, 5-tri (carboxymethoxy) benzene (H) with flexibly changeable coordination modes is not related 3 tbac) is a directional ligand, and a novel molecular-based magnetic material of Mn complex is constructed.
Disclosure of Invention
The invention aims at: aiming at the problems, a novel manganese tetranuclear structure metal complex, a preparation method and application thereof are provided.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
novel manganese tetranuclear structure metal complex with chemical general formula of [ Mn ] 2 (μ 3 -OH)Mn 0.5 Mn 0.5 (tbac) 2 ] n ·2H 2 O, where H 3 tbac = 1,3, 5-tris (carboxymethoxy) benzene; the complex belongs to a triclinic system, the space group is P ī, and each manganese ion is in a hexacoordinated coordination environment to form an octahedral configuration;
the preparation method of the novel manganese tetranuclear structure metal complex is characterized by comprising the following steps of:
will H 3 Putting tbac into a reaction kettle, adding a mixed solvent, stirring for 30min at room temperature, adding manganese acetate tetrahydrate, continuously stirring until the manganese acetate tetrahydrate is completely dissolved, adjusting the pH value to 7-8, continuously stirring for 30min, then sealing the reaction kettle, putting the reaction kettle at 160 ℃ for constant temperature reaction, cooling to room temperature after the reaction, filtering, and washing to obtain blocky yellow crystals, namely the novel manganese tetranuclear structure metal complex.
In the above preparation method, preferably, the H 3 Moles of tbac, manganese acetate tetrahydrateThe ratio was 1:1.
In the above preparation method, preferably, the mixed solvent is a mixed solution formed by mixing water and ethanol according to a volume ratio of 9:4 or 2:1.
In the above preparation method, preferably, the pH is adjusted with a triethylamine solution.
In the above preparation method, the constant temperature reaction time is preferably 4 to 5 days.
The invention also provides application of the novel manganese tetranuclear structure metal complex in preparing a molecular-based magnetic material.
In summary, due to the adoption of the technical scheme, the invention has the following beneficial effects:
the invention selects flexible aromatic carboxylic acid 1,3, 5-tri (carboxymethoxy) benzene (H) with flexible and changeable coordination modes 3 tbac) is a directional ligand, and reacts with manganese acetate tetrahydrate by a solvothermal method to generate a tetranuclear metal complex with novel structure, the preparation method is simple, the operation is convenient, the raw materials are easy to obtain, the conditions are mild, the yield is high, the obtained complex has good thermal stability and magnetic properties, and magnetic researches show that the magnetic properties of the complex are expressed as antiferromagnetic coupling between adjacent metal ions in clusters, so that theoretical basis and basis are provided for the subsequent design and synthesis of molecular-based magnetic materials with special magnetic properties.
Drawings
FIG. 1 is a crystal structure diagram of the novel manganese tetranuclear structure metal complex of the present invention.
FIG. 2 is a coordination polyhedron diagram of the central ion of the novel manganese tetranuclear structure metal complex of the present invention.
FIG. 3 is a three-dimensional stacking diagram of the novel manganese tetranuclear structure metal complex of the present invention.
FIG. 4 is a graph of thermogravimetric and differential thermogravimetric curves of the novel manganese tetranuclear structured metal complex of the present invention.
FIG. 5 is a surface interaction diagram of the novel manganese tetranuclear structured metal complex of the present invention.
FIG. 6 is a diagram of a surface effect two-dimensional fingerprint area of the novel manganese tetranuclear structure metal complex of the present invention.
FIG. 7 is a diagram of χ of a novel manganese tetranuclear structured metal complex of the present invention m –T、χ m T-T graph.
FIG. 8 is a χm of a novel manganese tetranuclear structured metal complex of the invention -1 -T-plot.
Fig. 9 is an M-H plot of the novel manganese tetranuclear structured metal complex of the present invention at a temperature t=2k.
FIG. 10 is a graph of the alternating susceptibility of the novel manganese tetranuclear structured metal complexes of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples in order to more clearly illustrate the present invention.
The invention provides a novel manganese tetranuclear structure metal complex, the chemical general formula of which is [ Mn ] 2 (μ 3 -OH)Mn 0.5 Mn 0.5 (tbac) 2 ] n ·2H 2 O, where H 3 tbac = 1,3, 5-tris (carboxymethoxy) benzene; the crystal structure diagram of the complex is shown in fig. 1, the coordination polyhedron diagram of the central ion of the complex is shown in fig. 2, and the three-dimensional stacking diagram of the complex 1 is shown in fig. 3.
In the embodiment, 1,3, 5-tri (carboxymethoxy) benzene is taken as a directional ligand, and reacts with manganese acetate tetrahydrate by a solvothermal method to generate a tetranuclear metal complex with a novel structure.
The complex belongs to a triclinic system, the space group is P ī, each manganese ion is in a hexacoordinated coordination environment to form an octahedral configuration, and the molecules are piled up to form a three-dimensional structure through ligand oxygen bridging and pi-pi action of benzene rings.
The experimental apparatus and reagents used in the examples of the present invention were as follows:
experimental instrument: agilent G8910A CCD single crystal diffractometer (Agilent corporation, USA), perkin-Elmer 240Q element analyzer (Perkin Elmer Co., ltd.) Spectrum 65 Fourier transform infrared spectrometer (Perkin Elmer corporation, USA), RF-5301PC fluorescence photometer (Shimadzu corporation, japan); XTL-220 microscope (Shanghai Tian province instruments Co., ltd.), UV-8000 ultraviolet visible spectrophotometer (Shanghai Yuan Jiedu instruments Co., ltd.), HQT-4 full-automatic microcomputer differential calorimeter (Beijing Heng Jiujiu scientific instrument Co., ltd.), MPMS SQUID magnetometer magnetic measurement system (Quantum Design Co., ltd., U.S.A.)
Experimental reagent: the chemical reagents and medicines used in the experiment are all analytically pure reagents, 1,3, 5-tri (carboxymethoxy) benzene (Jinan He Zhi Ji Cheng Ji Co., ltd.), manganese acetate tetrahydrate, triethylamine, sodium hydroxide, absolute ethyl alcohol and DMF (Xie Long chemical Co., ltd.).
In some embodiments of the present invention, there is also provided a method for preparing the above novel manganese tetranuclear structure metal complex, comprising the steps of: will H 3 Putting tbac into a reaction kettle, adding a mixed solvent, stirring for 30min at room temperature, adding manganese acetate tetrahydrate, continuously stirring until the manganese acetate tetrahydrate is completely dissolved, adjusting the pH value to 7-8, continuously stirring for 30min, then sealing the reaction kettle, putting the reaction kettle at 160 ℃ for constant temperature reaction, cooling to room temperature after the reaction, filtering, and washing to obtain blocky yellow crystals, namely the novel manganese tetranuclear structure metal complex.
In the above preparation method, preferably, the H 3 the molar ratio of tbac to manganese acetate tetrahydrate is 1:1.
In the above preparation method, preferably, the mixed solvent is a mixed solution formed by mixing water and ethanol according to a volume ratio of 9:4 or 2:1.
In the above preparation method, preferably, in the above preparation method, the pH value is adjusted with a triethylamine solution.
In the above preparation method, the constant temperature reaction time is preferably 4 to 5 days.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
1. Synthesis of Complex
Example 1:
will H 3 tbac (0.0750 g,0.25 mmoL) was placed in a reaction vessel (30 mL), a mixed solvent consisting of 9mL of water and 4mL of ethanol was added, and stirred at room temperature for 30min, manganese acetate tetrahydrate (0.0613 g,0.25 mmol) was added, and stirring was continuedStirring for 1h until the mixture is completely dissolved, regulating the pH value to 7 by using a triethylamine solution, continuously stirring for 30min, sealing the reaction kettle, placing the reaction kettle in a 160 ℃ incubator for reaction for 5 days, cooling to room temperature after the reaction, filtering and washing to obtain clean blocky yellow crystals. Yield 0.081g, 71.6% (H) 3 TB-based calculation).
Example 2:
will H 3 tbac (0.0750 g,0.25 mmoL) was placed in a reaction vessel (30 mL), a mixed solvent composed of 10mL of water and 5mL of ethanol was added, stirring was performed at room temperature for 30min, manganese acetate tetrahydrate (0.0613 g,0.25 mmoL) was added, stirring was continued for 1h until complete dissolution, pH was adjusted to 8 with triethylamine solution, stirring was continued for 30min, then the reaction vessel was sealed and placed in a 160℃incubator for 4 days, after the reaction, cooled to room temperature, filtered, and washed to obtain clean block-shaped yellow crystals.
2. Confirmation of Complex
The structures of the complexes were characterized by infrared absorption spectrum (IR), elemental analysis and X-ray single crystal diffraction using the blocky yellow crystals prepared in example 1 and example 2, and the results were as follows:
infrared data: IR (KBr): 3448 1605, 1429, 1320, 1264, 1160, 1083, 941, 818, 732, 676, 590cm -1 。
The complex is 3448cm -1 The absorption peak is attributed to the hydroxyl (-OH) peak of the water molecule; at 1605cm -1 The absorption peak at the position is the characteristic peak of carbonyl (C=O) on carboxyl, and the characteristic peak of benzene ring skeleton (C=C) appears in 1429cm -1 、1320cm -1 At 676cm -1 The Mn-O absorption peak is shown, which indicates that the carbonyl group in the ligand coordinates with the metal manganese ion during the reaction. The out-of-plane bending peak of C-H on the benzene ring appears at 818cm -1 The method comprises the steps of carrying out a first treatment on the surface of the Characteristic peak of methyl on benzene ring is 732cm -1 The method comprises the steps of carrying out a first treatment on the surface of the Complex 676cm -1 The characteristic coordination peak of Mn-O appears, which indicates that the ligand is successfully coordinated with the metal ion.
Elemental analysis: c,35.47; h,2.86. Theoretical value (C) 24 H 23 Mn 3 O 21 ，Mr＝812.24)：C，35.49；H，2.85。
Crystallographic data: the chemical formula of the complex is C 24 H 23 Mn 3 O 21 The data of the crystallographic parameters, the major bond lengths and the bond angles, etc. belonging to the triclinic system, P ī space group are shown in tables 1, 2 and 3, respectively.
Table 1 Crystal parameter Table of the Complex
Table 1 Crystal data and structure refinements for complex
Note that: [ a ]]R 1 ＝Σ||F o |–|F c ||/Σ|F o |.[b]wR 2 ＝[Σw(|F o 2 |–|F c 2 |) 2 /Σw(|F o 2 |) 2 ] 1/2 .
Table 2 partial bond lengths of the complexes
Table 2 Selected bond lengthsfor complex
TABLE 3 partial bond angles of complexes
Table 3 Selected bond angles[°]for complex
Note that: (i) -x+2, -y+1, -z+1; (ii) -x+2, -y, -z+1; (iii) x, y+1, z; (iv) -x+2, -y+1, -z; (v) x, y, z+1; (vi) x, y+1, z-1; (vii) -x+2, -y, -z; (viii) x, y-1, z; (ix) x, y-1, z+1; (x) x, y, z-1.
FIG. 1 shows the crystal structure of the complex, and as can be seen from FIG. 1, the complex is composed of two Mn' s II Two Mn III One bridged hydroxyl anion, two tbac 3- A ligand and two solvent water molecules. In the structure of the complex, the occupancy of four metal manganese ions is different, the occupancy of Mn1 and Mn3 is 0.5, and the occupancy of Mn2 and Mn4 is 1. Each manganese ion is in a hexacoordinated coordination environment, forming an octahedral configuration. Mn1 and Mn3 are coordinated identically, with Mn1 being exemplified by five oxygen atoms of Mn1 and four multidentate ligands And one mu 3 -OH oxygen bridging atoms (mn1—o19=2.010 (3), symmetrical codes (i) x+1, y, z, (ii) -x+2, -y, -z) coordinated to form hexahedral MnO 6 Configuration. The coordination of Mn2 and Mn4 is the same, taking Mn2 as an example, mn2 is +.> And two mu 3 -OH oxygen bridging atom->Symmetric code: (iii) -x+2, -y, -z+1; (iv) x, y, z+1) coordinates to form hexahedral MnO 6 Configuration.
FIG. 2 is a graph of a coordination polyhedron of the manganese center ion of the complex, mn1 being in a coordination octahedron with equatorial planes of O11, O19, O14, respectively i And O18 ii The composition, best square plane equation: -0.0263x +0.8544y-0.5189 z= -1.1767, the average deviation of four O atoms from the plane on the equatorial plane is allO1，O15 i Are the two vertices of the octahedron, which are separated from the plane by the distance +.>And->The center manganese ion is deviated from the plane by the distance ofBoth Mn1 and Mn3 are octahedral configurations forming a distortion. The equatorial plane of the coordination octahedron where Mn2 is located is defined by O4, O4 respectively ii 、O18 ii And O18 iv The composition, best square plane equation: -0.8738x+0.0012y-0.4863 z= -13.7764, four O atoms on the equatorial plane having an average off-plane value of 0, O19 iii Are the two vertices of the octahedron, which are both at a distance from the plane +.>And the distance of the central manganese ion from the plane is also 0, mn2 and Mn4 form a regular octahedral configuration by coordination with oxygen atoms.
FIG. 3 is a three-dimensional stacking diagram of the complex, wherein chains are orderly stacked into a three-dimensional structure through ligand oxygen bridging and pi.pi action of ligand benzene rings.
3. Thermodynamic stability property test of complexes
Adopts a HQT-4 type full-automatic microcomputer differential calorimeter, and the pure phase crystal of the complex is in N 2 The thermal stability of the complex was determined by increasing it from 25℃to 900℃at a rate of 10℃per minute under an atmosphere.
FIG. 4 is a graph showing the TG/DTG curve of the novel manganese tetranuclear structure metal complex synthesized by the invention. As can be seen, the complexes are at 171 to 568 ℃The weight of each tetranuclear cluster compound is not changed basically, the whole frame structure of the complex starts to be pyrolyzed from 171 ℃, and the ligand is completely lost at 568 ℃, and the theory is that: 67.53%, actually 65.16%; the final residue may be manganese oxide MnO 2 And Mn of 3 O 4 . A peak appears on the differential thermogravimetric DTG curve at about 378 ℃ and is very intense, indicating that the tetranuclear manganese cluster has the greatest rate of weight loss at high temperatures.
4. Hirshfeld surface analysis
The method comprises the steps of taking a crystal parameter cif file of a complex as a data source, calculating the distribution condition of the surface acting force of a complex molecule Hirshfeld through a crystal Explorer 3.1 program, visually drawing different intermolecular interactions on the three-dimensional molecular surface of a crystal structure to obtain Dnorm, shape index and Curvedness diagrams, and calculating a 2D fingerprint diagram to quantitatively analyze the property and type of the surface acting force between molecules in the crystal.
FIG. 5 shows the surface interaction diagram of the complex, in FIG. 5 the extent of the Dnorm surface on the left isShape index and curvature Curvednes are in +.>And->Within the range. The bright red spots on the Dnorm surface represent strong surface forces, such as hydrogen bonding and van der waals forces, of the complex molecules where they exist. The bright yellow irregular pattern in the Shape index graph represents pi.pi.action among molecules, and the Curvedness (curvature) graph is used for measuring the deformation degree of the molecular surface in the crystal due to the interaction among the molecules, and the flat and sharp areas respectively mean lower deformation degree and higher deformation degree, and the deformation degree of the molecular surface is divided by different intermolecular forces around the moleculesSeparated into different regions.
The results of quantitative analysis of the nature and type of surface forces between molecules inside the crystal are summarized in a 2D fingerprint, as shown in fig. 6. The O.cndot.H effect in the complex molecule takes the dominant effect of 31.2%, and is uniformly distributed in the middle part in the fingerprint region, which means weak effects such as close contact and Van der Waals force in the complex. The force occupancy of H.H was 20.5%, which is a conventional intramolecular hydrogen bond in the complex molecule, and the ratio of C.H/H.C was 10.2%.
5. Magnetic testing
Using MPMS SQUID magnetometer magnetic measurement system (Quantum Design company, USA) to measure the relation between the molar susceptibility and temperature change of the pure phase crystal of the complex under the direct current external magnetic field with the temperature of 2-300K and 1000 Oe; under the condition of 2K, the change relation of the magnetization intensity M along with the magnetic field intensity H is measured; and in the temperature range of 2-20K, the dependence of alternating current magnetic susceptibility and frequency is carried out under the conditions of 100Hz and 997 Hz.
The pure phase crystal of the complex is scanned to obtain χ under the conditions of temperature range of 2-300K and 1000Oe DC external magnetic field m -T and χ m T-T curve, as shown in FIG. 7. For tetranuclear manganese unit, χ m T is 10.93cm at 300K 3 Kmol –1 This value is 6.94cm above that of a tetranuclear manganese unit without interaction 3 Kmol –1 High, suggesting orbital contribution of distorted octahedral Mn2 ions. As the temperature decreases, χ m T value decreases to a minimum of 8.10cm at 1.99K 3 Kmol –1 The method comprises the steps of carrying out a first treatment on the surface of the As the temperature continues to decrease, χ m T increases rapidly to a maximum of 9.91cm at 1.99K 3 Kmol –1 . This magnetic behavior suggests that within the tetranuclear cluster, antiferromagnetic coupling exists between manganese ions, χ at low temperature m The abrupt increase in T may be due to zero-field splitting (ZFS) in the ground state, the Zeeman effect or intermolecular antiferromagnetic interactions [26] . Chi above 50K m –1 The T curve was followed by a Curie-Weiss law (χ=c/(T- θ)), linear fit to a Weiss constant θ= -11.08K, and Curie constant c=11.11 cm –1 Kmol –1 As shown in fig. 8. Negative Weiss constants also suggest that antiferromagnetic interactions exist between adjacent manganese ions within a cluster.
Fig. 9 is an M-H plot of the complex at temperature t=2k, and it can be seen that the magnetization (M) increases nearly linearly with H when the external field H is small; at H>After 2T, the magnetization (M) increases slowly, M being 9.38Nbeta.mol at 7T -1 Below the assumption g=2, s T 10nβ·mol when=5 -1 . Implying that M does not reach saturation or that part of the electrons occupy the excited state, which results in a lower ground state spin.
FIG. 10 is a graph of the AC magnetic susceptibility of the complex showing the AC magnetic susceptibility curves of the complex at temperatures of 2-15K and frequencies of 100Hz and 997Hz, indicating that neither the real nor the imaginary part of the AC magnetic susceptibility shows frequency dependence nor peaks in this temperature range. These magnetisms indicate that antiferromagnetic exchange interactions are present within the complex cluster.
The test results show that the invention synthesizes the [ Mn ] with novel structure by taking 1,3, 5-tri (carboxymethoxy) benzene as the directional ligand 2 (μ 3 -OH)Mn 0.5 Mn 0.5 (tbac) 2 ] n ·2H 2 O complexes. The complex is a triclinic system, P ī space group, four metal Mn ions in a structural unit are bridged with mu 3 -OH, ligand H 3 tbac oxygen atom coordination forms MnO respectively 6 The octahedral configuration of (2) is orderly stacked into a three-dimensional structure through ligand oxygen bridging and benzene ring pi … pi stacking action in the ligand. Meanwhile, the complex has good thermal stability. The Hirshfeld surface analysis result shows that the surface of the complex molecule has strong O … H, H … H hydrogen bonds and pi … pi action among molecules. The magnetic research shows that the magnetic property of the complex is expressed as antiferromagnetic coupling between adjacent metal ions in a cluster, and provides theoretical basis and basis for the subsequent design and synthesis of the molecular-based magnetic material with special magnetic property.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (7)
1. A novel manganese tetranuclear structure metal complex is characterized in that the chemical general formula of the complex is [ Mn ] 2 (μ 3 -OH)Mn 0.5 Mn 0.5 (tbac) 2 ] n ·2H 2 O, where H 3 tbac = 1,3, 5-tris (carboxymethoxy) benzene;
the complex belongs to a triclinic system, the space group is P ī, and each manganese ion is in a hexacoordinated coordination environment to form an octahedral configuration; the crystallographic parameters of the complexes are shown in table 1 below, the primary bond length data are shown in table 2 below, and the primary bond angle data are shown in table 3 below:
table 1 Crystal parameters of the complexes
R 1 ＝Σ||F o |–|F c ||/Σ|F o |；wR 2 ＝[Σw(|F o 2 |–|F c 2 |) 2 /Σw(|F o 2 |) 2 ] 1/2
TABLE 2 principal bond lengths of the complexes
TABLE 3 principal bond angles of the complexes
Symmetric code: (i) x+1, y, z; (ii) -x+2, -y, -z; (iii) -x+2, -y, -z+1; (iv) x, y, z+1; (v) -x+1, -y, -z+1;
(vi)-x+1,-y,-z；(vii)x-1,y,z；(viii)x,y,z-1。
2. the method for preparing a novel manganese tetranuclear structure metal complex according to claim 1, comprising the steps of:
will H 3 Putting tbac into a reaction kettle, adding a mixed solvent, stirring for 30min at room temperature, adding manganese acetate tetrahydrate, continuously stirring until the manganese acetate tetrahydrate is completely dissolved, adjusting the pH value to 7-8, continuously stirring for 30min, then sealing the reaction kettle, putting the reaction kettle at 160 ℃ for constant temperature reaction, cooling to room temperature after the reaction, filtering, and washing to obtain blocky yellow crystals, namely the novel manganese tetranuclear structure metal complex.
3. The preparation method according to claim 2, characterized in that: the H is 3 the molar ratio of tbac to manganese acetate tetrahydrate is 1:1.
4. The preparation method according to claim 2, characterized in that: the mixed solvent is a mixed solution formed by mixing water and ethanol according to the volume ratio of 9:4 or 2:1.
5. The preparation method according to claim 2, characterized in that: the pH was adjusted with triethylamine solution.
6. The preparation method according to claim 2, characterized in that: the constant temperature reaction time is 4-5 days.
7. The use of a novel manganese tetranuclear structure metal complex according to claim 1 in the preparation of molecular-based magnetic materials.
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