CN108586765A - A kind of manganese Metal organic framework material and its preparation method and application - Google Patents

A kind of manganese Metal organic framework material and its preparation method and application Download PDF

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CN108586765A
CN108586765A CN201810421798.5A CN201810421798A CN108586765A CN 108586765 A CN108586765 A CN 108586765A CN 201810421798 A CN201810421798 A CN 201810421798A CN 108586765 A CN108586765 A CN 108586765A
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organic framework
metal organic
manganese metal
framework material
manganese
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CN108586765B (en
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卢丽萍
李少东
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Shanxi University
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene

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Abstract

The present invention provides a kind of manganese Metal organic framework materials and its preparation method and application, and molecular formula is：[Mn2(μ4‑Hcpota)(μ3‑Hcpota)(μ2‑bib)2(H2O)]n,H3Cpota indicates that 2 (4 carboxyphenoxy) terephthalic acid (TPA)s, bib indicate the double imidazoles benzene of Isosorbide-5-Nitrae.The material is made by hydrothermal method：By MnCl2·4H2O、H3Cpota, bib and KOH in molar ratio (2:1:2:2~3) it is placed in polytetrafluoroethylene (PTFE) reactor, water is placed in reactor, control compactedness is between 60% 80%, after stirring 30 minutes, with 140 DEG C of reaction 72h in hydrothermal reaction kettle.It is cooled to room temperature by Temperature fall, obtains colourless bulk crystals, after being washed with distilled water, vacuum drying.The manganese Metal organic framework material crystal structure is comprising one-dimensional manganese Metal chain secondary structure unit [Mn2(COO)3(H2O 3-dimensional metal organic framework material)].The manganese Metal organic framework material has good thermal stability, and there are antiferromagnetic interactions for Mn (II) interionics in the material, can be used as potential molecular magnet material.

Description

A kind of manganese Metal organic framework material and its preparation method and application
Technical field
The present invention relates to transition metal organic framework materials, more particularly to a kind of to be based on transition metal manganese (II) and 2- (4- Carboxyphenoxy) terephthalic acid (TPA) ligand 1, the organic three-dimensional bone of the metal with antiferromagnetic interaction that the bis- imidazoles benzene of 4- are constructed Frame material and its preparation method and application.
Background technology
The material that certain mode is reacted can be made to magnetic field is known as magnetic material.Molecular magnetic materials are that one kind passes through chemistry Method forms free radical or paramagnetic ion (mainly having transition metal ions and rare earth ion) and diamagnetic ligand combination Magnetic compound.Molecular magnetic materials light, structure change with small, opposite conventional magnet density compared with conventional magnet The features such as diversified, easily processed into type.Molecular magnetic materials it is widely used.Mainly utilize its various magnetic characteristic and special Element or device is made in effect；Some strength is generated for storing, transmitting and conversion of electromagnetic energy and information, or in particular space With the magnetic field of distribution；Sometimes (such as magnetic liquid) is directly also utilized with the natural form of material.Magnetic material is in electronic technology There is important role in field and other science and technology fields.Molecular magnetic materials can use the method for chemistry to the knot of molecule Structure is modified and is cut, and then changes the diversification that its magnetism realizes magnetic diversity and application of function.Therefore, it builds Stable structure, the molecular magnet of function admirable are the hot spots of molecule magnetics and materials science field research.
Invention content
It is an object of the invention to be based on the above-mentioned state of the art, a kind of manganese Metal organic framework material and its preparation side are provided The application of method as well as magnetic material.
A kind of manganese Metal organic framework material (Mn (II)-MOF) provided by the invention, molecular formula is：[Mn2(μ4- Hcpota)(μ3-Hcpota)(μ2-bib)2(H2O)]n, wherein H3Cpota indicates 2- (4- carboxyphenoxies) terephthalic acid (TPA), Bib indicates the bis- imidazoles benzene of 1,4-.Structural formula is：
The crystal category anorthic system of Mn (the II)-MOF materials, space group P-1, cell parameter are： α=99.939 (1) °, β=96.406 (1) °, γ =97.933 (1) °.The material have be connected with cis- suitable pattern by carboxylate oxygen atoms by adjacent manganese atom formed it is one-dimensional Manganese Metal chain secondary structure unit [Mn2(COO)3(H2O)].Mn atoms are all octahedral coordination environment in the material.Wherein Mn1 It is coordinated respectively from four O atoms in four different carboxylic acids and two N from two different bis- imidazoles benzene of 1,4-；Mn2 points Not with the O atom in three different carboxylic acids, a water of coordination molecule and two N Atomic coordinates.Mn-O bond distance is ranging fromMn-N bond distance is ranging fromMn2...2(μ1,3-O, O) ... Mn1 and Mn1... (μ1,3- O, O) distance of (O-H...O) ... between Mn2 be respectively 4.723 (1) andX Ray powder diffraction confirms Mn (the II)-MOF crystal prototype stable homogeneous.
The preparation method of Mn (II)-MOF materials provided by the invention, includes the following steps：
(1) in molar ratio by manganese chloride, 2- (4- carboxyphenoxies) terephthalic acid (TPA), the bis- imidazoles benzene of 1,4- and potassium hydroxide (2:1:2:2~3) it is placed in polytetrafluoroethylene (PTFE) reactor；
(2) plus water is in the reactor, and control compactedness is in 60%-80%；
(3) after stirring 30 minutes, this polytetrafluoroethylene (PTFE) reactor is placed in stainless steel cauldron and is sealed, at 140 DEG C React 72h；Then cool down 10 DEG C per hour until room temperature, you can colourless bulk crystals are precipitated, it is dry to be washed with distilled water rear vacuum It is dry, yield 60%.
The manganese chloride, 2- (4- carboxyphenoxies) terephthalic acid (TPA), the bis- imidazoles benzene of 1,4- and the best of potassium hydroxide rub You are than being 2:1:2:2.
Advantages of the present invention and effect：
The present invention Mn (II)-MOF materials be to be obtained under hydrothermal synthesizing condition, reparation technology is simple, yield, purity compared with It is high.Thermogravimetric analysis shows that structure is decomposed at 300 DEG C or more, and practical temperature range is at 300 DEG C or less.
Mn (II)-MOF materials provided by the invention are to be based on 2- (4- carboxyphenoxies) terephthalic acid (TPA) (H3Cpota) and Bis- imidazoles benzene (bib) ligands of 1,4- are constructed.H3Two phenyl ring in cpota ligands can be turned around intermediate oxygen atom It is dynamic so that H3Cpota ligands can take a variety of coordination modes.In this material, H3Cpota ligands take two different Coordination mode (Fig. 2), the H of both different coordination modes3Cpota ligands connect adjacent metal manganese ion and have constructed one-dimensional manganese Metallic bond secondary structure unit, the one-dimensional manganese Metal chain secondary structure unit pass through Hcpota2-Ligand connects to be formed with bib ligands Three-dimensional structure.
Show that there are antiferromagnetic between manganese ion in the material by variable temperature magnetic susceptibility experimental data under 1000Oe external magnetic fields Interaction, can be used as molecular magnetic materials.
Description of the drawings
The crystal structure asymmetric cell figure of Fig. 1 Mn of the present invention (II)-MOF materials
H in Fig. 2 Mn of the present invention (II)-MOF materials3Two different coordination modes of cpota ligands
X-ray powder diffraction figure of Fig. 3 Mn of the present invention (II)-MOF materials in 298K
The thermogram of Fig. 4 Mn of the present invention (II)-MOF materials
Variable temperature magnetic susceptibility curve graph of Fig. 5 Mn of the present invention (II)-MOF materials under 1000Oe external magnetic fields
Specific implementation mode
Embodiment 1
Weigh 0.1mmol H3Cpota, 0.2mmol bib and 0.2mmol MnCl2·4H2H containing 6mL is added in O2O's In 13mL polyfluortetraethylene pipes, a concentration of 0.2mol KOH of 1mL are slowly dropped in the mixture in stirring, and continue to stir It mixes 30 minutes.This polyfluortetraethylene pipe is sealed in stainless steel cauldron, after heating 72h at 140 DEG C, is naturally cooling to room Temperature, you can be precipitated without bulk crystals, after being washed with distilled water and dry, yield 60%.Elemental analysis：Theoretical value：C 56.40, H 3.31, N 9.75%；Experiment value:C 56.48, H 3.28, N 9.92%.
Mn (II)-MOF material structures measure：
Crystal structure determination uses X-ray diffraction, passes through graphite monochromator monochrome with Bruker D8Venture detectors The Mo-K alpha rays of change, scan mode ω, the temperature for collecting data are 298 (2) K.Initial data uses after SAINT is restored SADABS carries out absorption correction.Crystal structure is solved by SHELXL-2016 direct methods.The detailed detailed crystal of axonometry is surveyed For fixed number according to being shown in Table 1, crystal structure asymmetric cell is shown in Fig. 1.
The crystallographic data of 1 manganese Metal organic framework material of table
Powder diffraction：
X-ray powder diffraction result obtain experimental diffraction collection of illustrative plates with simulation collection of illustrative plates it is consistent, show the present invention manganese Metal have Machine framework material object is mutually uniform, sees Fig. 3.
The thermogravimetric analysis of the material：
Thermal gravimetric analysis results show that metal-organic framework materials agent structure at 300 DEG C or more is decomposed, explanation The material has good thermal stability, sees Fig. 4.
The magnetic property of Mn (II)-MOF materials：
Variable temperature magnetic susceptibility curve is as shown in figure 5, it can be seen from the figure that material Effect magnetic moment in room temperature is 5.66 glass That magneton, does not couple the room temperature Effect magnetic moment (5.92 Bohr magneton) of Mn (II) ion close to single independence.With temperature It reduces, Effect magnetic moment first slowly reduces, and is then rapidly reduced in low-temperature region, 2.79 Bohr magneton of minimum value is reached in 2K. It is fitted χ using Curie-Weiss lawm -1- T can obtain C=4.12cm3mol-1K, θ=- 6.11K, θ<0 proves the material There is antiferromagnetic interactions for manganese metal interionic.

Claims (4)

1. a kind of manganese Metal organic framework material, which is characterized in that structural formula is：
2. a kind of preparation method of manganese Metal organic framework material described in claim 1, which is characterized in that including walking as follows Suddenly：
(1) by manganese chloride, 2- (4- carboxyphenoxies) terephthalic acid (TPA), the bis- imidazoles benzene of 1,4- and potassium hydroxide in molar ratio 2:1: 2:2~3 are placed in polytetrafluoroethylene (PTFE) reactor；
(2) water is placed in above-mentioned reactor, control compactedness is in 60%-80%；
(3) after stirring 30 minutes, this reactor is placed in stainless steel cauldron and is sealed, reacts 72h at 140 DEG C；Then certainly So cooling is until room temperature, you can colourless bulk crystals are precipitated, are dried in vacuo after being washed with distilled water.
3. a kind of preparation method of manganese Metal organic framework material described in claim 2, which is characterized in that the manganese chloride, The molar ratio 2 of 2- (4- carboxyphenoxies) terephthalic acid (TPA), 1,4- bis- imidazoles benzene and potassium hydroxide:1:2:2.
4. manganese Metal organic framework material as described in claim 1 is used as molecular magnetic materials.
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CN112175196A (en) * 2020-10-16 2021-01-05 山西大学 Preparation method and application of two-dimensional binuclear manganese coordination polymer
CN112759769A (en) * 2020-12-29 2021-05-07 山西大学 Hexa-nuclear copper coordination polymer and preparation method and application thereof

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CN112759769A (en) * 2020-12-29 2021-05-07 山西大学 Hexa-nuclear copper coordination polymer and preparation method and application thereof

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