CN107286099A - Zn complex and its application that one kind is constructed based on 4 (2 methylimidazole) benzoic acid - Google Patents
Zn complex and its application that one kind is constructed based on 4 (2 methylimidazole) benzoic acid Download PDFInfo
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- CN107286099A CN107286099A CN201610910466.4A CN201610910466A CN107286099A CN 107286099 A CN107286099 A CN 107286099A CN 201610910466 A CN201610910466 A CN 201610910466A CN 107286099 A CN107286099 A CN 107286099A
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- complex
- methylimidazole
- benzoic acid
- constructed based
- hmiba
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- YXCKVAOCQSIOIM-UHFFFAOYSA-N benzoic acid 2-methyl-1H-imidazole Chemical compound C(C1=CC=CC=C1)(=O)O.CC=1NC=CN1 YXCKVAOCQSIOIM-UHFFFAOYSA-N 0.000 title abstract 4
- 239000011701 zinc Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- XQYAEIDOJUNIGY-UHFFFAOYSA-N (2-iodo-5-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(I)C(B(O)O)=C1 XQYAEIDOJUNIGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 229910003460 diamond Inorganic materials 0.000 claims description 5
- 239000010432 diamond Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 22
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002178 crystalline material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012229 microporous material Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- -1 carboxy arenes Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 4
- 150000001455 metallic ions Chemical class 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241001120493 Arene Species 0.000 description 1
- 241000638935 Senecio crassissimus Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The invention belongs to organic and Inorganic synthese technical field, specifically a kind of Zn complex constructed based on 4 (2 methylimidazole) benzoic acid and its application.The crystal molecule formula is [Zn (MIBA)2]n, wherein, HMIBA is negative one valency anion ligand 4 (2 methylimidazole) benzoic acid with structure shown in formula 1, belongs to rhombic system, P4ncSpace group, cell parameterβ=90 °.The crystalline material of the complex is synthesized using solvent thermal reaction, it is node of the logical zinc ion as one four connection, and the interspersed microcellular structure of three-dimensional quadruple is constituted by the bridging of bridge ligand 4 (2 methylimidazole) benzoic acid.The crystalline material of complex of the present invention has the advantages that adsorptivity and fluorescence property.The crystalline microporous material of the invention has important application based on good fluorescence and adsorptivity in fields such as petrochemical industry, fine chemistry industries.
Description
Technical field
It is specifically a kind of to be based on 4- (2-methylimidazole) benzene first the invention belongs to organic and Inorganic synthese technical field
Zn complex and its application that acid is constructed.
Background technology
Carbon dioxide (CO2) as the principal element of greenhouse effects is caused, the side such as storage, separation and conversion to its gas
The research in face has got more and more people's extensive concerning.In recent years, a kind of novel porous materials -- metal organic framework compound due to
Its because with specific surface area is big, voidage is big, structure composition is various and heat endurance is good the features such as, and in CO2Gas is stored
With the potential application in separation, the study hotspot of Material Field is adsorbed and stored as gas molecule.
At present, the research work in terms of the absorption of metal-organic framework chemical compound gas is concentrated mainly on many carboxy arenes of rigidity
Fragrant acid contains with central metallic ions, bridging Nitrogen-Containing Heterocyclic Ligand and central metallic ions or many carboxyl aromatic acids of rigidity and bridging
The metal-organic framework compound that n-heterocyclic ligand is constructed as mixed ligand and central metallic ions.It is relative with it is above-mentioned several
Metal-organic framework compound constructs type, is constructed based on carboxyl, the multi-functional organic ligand of nitrogen heterocyclic ring and central metallic ions
The storage research of coordination polymer and its correlation energy source material is delayed a lot.In addition, central atom has machine frame for divalent zinc
Frame compound, due to its d10Configuration electron configuration, the organic framework compounds of divalent zinc have huge application on luminescent properties
Prospect.
In general, the suitable ratio containing carboxyl and the multi-functional part of nitrogen heterocyclic ring, adjustment part and metal ion is selected
Example and reaction temperature, are the effective means of synthesizing new porous material.Different reaction conditions are attempted, is parsed, inhaled by monocrystalline
Attached property is determined, to filter out the porous material with absorption property.Therefore by exploring the aperture of Porous materials, comparing table
There is the porous material of application value in the inner link of area, hole occupation rate and absorption property, searching system, do not only have
Help the development of Coordinative Chemistry, the research for novel porous materials in fields such as gas absorption, ion exchange, catalysis also all has
There is important Research Significance.
The content of the invention
Present invention aims at provide a kind of Zn complex constructed based on 4- (2-methylimidazole) benzoic acid and its application.
To achieve the above object, the present invention use technical scheme for：
The Zn complex that one kind is constructed based on 4- (2-methylimidazole) benzoic acid, complex is with the three-dimensional quadruple of single node
Interspersed diamond topological structure, chemical expression is [Zn (MIBA)2]n, wherein, HMIBA is the negative one with structure shown in formula 1
Valency anion ligand 4- (2-methylimidazole) benzoic acid；
The complex belongs to rhombic system, and space group is P4nc,Cell parameter is a=14.1883 (6), b=14.1868
(6), c=13.5156 (8), α=β=γ=90.00,
The preparation method for the Zn complex that one kind is constructed based on 4- (2-methylimidazole) benzoic acid, will using solvent-thermal method
Divalent zinc salt, 4- (2-methylimidazole) benzoic acid, inorganic base and DMF react 3~5 days at 100~130 DEG C, cool after reaction
To room temperature, chemical expression is produced for [Zn (MIBA)2]nComplex.
Specially by 4- (2-methylimidazole) benzoic acid (HMIBA), inorganic base and divalent zinc salt 0.0001- in molar ratio
0.0004:0.0001-0.0002:0.0001-0.0003 ratio mixing, is dissolved in excessive DMF after mixing and obtains mixing molten
Liquid, the mixed liquor is carried out under 100~130 DEG C of temperature environment after the completion of solvent thermal reaction, solvent thermal reaction, natural cooling
Crystal is separated out, is washed through deionized water after drying, produces complex.
The mixed solution is increased to 100-130 in sealed autoclave with 6-10 DEG C per hour of heating rate
DEG C temperature environment under carry out solvent thermal reaction 72-96h.
The inorganic base is one or more in potassium hydroxide, sodium hydroxide, lithium hydroxide；Divalent zinc salt be zinc chloride,
Zinc acetate or zinc nitrate hexahydrate.
The application for the Zn complex that one kind is constructed based on 4- (2-methylimidazole) benzoic acid, the complex is in gas absorption
Or the application in fluorescent material.
The mono-crystalline structures use single crystal diffractometer, using by graphite monochromatised Mo-K alpha rays
For incident radiation, point diffraction is collected with ω -2 θ scan modes, cell parameter is obtained by least square refinement, from difference Fu
Vertical leaf electron-density map solves the crystallographic data of single crystal data table complex using software.
The predominant crystal data of the complex of table 1
R1=∑ (| | Fo|-|Fc||)/∑|Fo| wR2=[∑ w (Fo 2-|Fc 2)2/∑w(Fo)2]1/2
The basic structure for the multi-functional Zn complex that the organic ligand is constructed is that the three-dimensional micropore of a single node is bored
Stone topological structure, zinc ion be four-coordination coordination environment, each zinc ion respectively with two 4- (2-methylimidazole) benzoic acid
Two nitrogen-atoms coordination in carboxyl negative oxygen ion, two two 4- (2-methylimidazole) benzoic acid parts in part, with zinc
Ion connects to form three-dimensional as the node of four connections by the bridging of part in two 4- (2-methylimidazole) benzoic acid parts
Diamond topological structure.The identical independent diamond topological structure of aforementioned four ultimately forms a three-dimensional by mutually interting
The interspersed microcellular structure of quadruple.
Beneficial effects of the present invention：
The present invention is obtained with 4- (2-methylimidazole) benzoic acid (HMIBA) as part, and ion has single-unit centered on zinc
The complex of point, three-dimensional diamond topological structure, i.e. 4- (2-methylimidazole) zinc benzoates complex [Zn (MIBA)2]n(1)
(HMIBA is negative one valency anion ligand 4- (2-methylimidazole) benzoic acid).The complex remains to be stabilized at 370 DEG C, tool
There is good heat endurance, complex of the present invention is excited at 240nm in addition, an emission peak is obtained at 392nm, intensity reaches
To the fluorescence property stable with strong.It can be used as special high temperature resistant fluorescent material.The present invention is using one pot of solvent heat
Reaction can prepare the Zn complex of multi-functional organic ligand regulation and control, and the preparation method has process simple, easy to operate,
The advantages of yield height and good reproducibility.
Brief description of the drawings
Fig. 1 is zinc in the Zn complex that 4- (2-methylimidazole) benzoic acid (HMIBA) prepared by the embodiment of the present invention is constructed
Coordination context diagram.
Fig. 2 is that the Zn complex that 4- (2-methylimidazole) benzoic acid (HMIBA) prepared by the embodiment of the present invention is constructed is three-dimensional
Space structure figure.
Fig. 3 is the Zn complex quadruple that 4- (2-methylimidazole) benzoic acid (HMIBA) prepared by the embodiment of the present invention is constructed
Interspersed structure chart.
Fig. 4 is the Zn complex powder that 4- (2-methylimidazole) benzoic acid (HMIBA) prepared by the embodiment of the present invention is constructed
X-ray diffraction pattern.
Fig. 5 is the Zn complex thermogravimetric that 4- (2-methylimidazole) benzoic acid (HMIBA) prepared by the embodiment of the present invention is constructed
Curve map.
Fig. 6 is the Zn complex constructed of 4- (2-methylimidazole) benzoic acid (HMIBA) for preparing of the embodiment of the present invention to two
The absorption figure of carbon oxide gas
Fig. 7 is the Zn complex solid-state that 4- (2-methylimidazole) benzoic acid (HMIBA) prepared by the embodiment of the present invention is constructed
Fluorescence spectrum.
Embodiment
Following examples are intended to further illustrate present invention, rather than limit the scope of the invention.
Crystal molecule formula of the present invention is [Zn (MIBA)2]n, in, HMIBA is the negative univalent anion with structure shown in formula 1
Part 4- (2-methylimidazole) benzoic acid, belongs to rhombic system, P4ncSpace group, cell parameter β=90 °.The crystalline material has been synthesized using solvent thermal reaction, it
It is the node for leading to zinc ion as one four connection, connects to be formed by the bridging of bridge ligand 4- (2-methylimidazole) benzoic acid
The interspersed microcellular structure of three-dimensional quadruple.
Embodiment 1
By 4- (2-methylimidazole) benzoic acid (20.2mg, 0.1mmol), potassium hydroxide (5.6mg, 0.1mmol) and nitric acid
Zinc (23.6mg, 0.1mmol) is soluble in water, in the reactor of inclosure, and 110 DEG C, maintenance are heated to 10 DEG C per hour of speed
This temperature 3 days, is then naturally cooling to room temperature, is washed with DMF, and colourless bulk crystals are can obtain after being filtered through filter paper, obtains
Crystal product be placed on constant temperature 3 hours in 80 DEG C of baking ovens, obtain target product yield about 65%.Main infrared absorption peak is
3435 (m), 3121 (m), 1618 (s), 1528 (m), 1373 (s), 1122 (m), 1072 (m), 845 (m), 774 (m)
The Zn complex further characterization of the obtained mixing organic ligand regulation and control of Example 1, its process is as follows：
(1) crystal structure determination of complex
Suitable dimension is chosen under the microscope carries out X-ray at room temperature for 0.32mm × 0.30mm × 0.28mm crystal
Single crystal diffraction is tested.Using by graphite monochromatised Mo-K alpha rays For incident radiation, swept with ω -2 θ
The mode of retouching collects point diffraction, and cell parameter is obtained by least square refinement, utilizes soft from difference Fourier electron-density map
Part solves the crystallographic data of single crystal data table complex.
Detailed axonometry data are shown in Table 1, and important bond distance and bond angle data is shown in Table 2, and crystal structure is shown in Fig. 1, Fig. 2 and
Fig. 3.
The predominant crystal data of the complex of table 1
R1=∑ (| | Fo|-|Fc||)/∑|Fo| wR2=[∑ w (Fo 2-|Fc 2)2/∑w(Fo)2]1/2
The important bond distance of table 2With bond angle (°)
#1-x+1,-y,-z；#2-x+1,-y+1,-z；
(2) the phase purity of complex is characterized
The powder X-ray RD of complex, which is characterized, shows that it has reliable phase purity, is provided for it as the application of fluorescent material
Ensure, see Fig. 4 (INSTRUMENT MODELs：Bruker/8Advance).
(3) heat endurance of complex is characterized
The thermogravimetric analysis of complex, which is characterized, shows that its skeleton still keeps stable until 370 DEG C or so, steady with preferable heat
It is qualitative, it is it as application material and further develops there is provided heat endurance guarantee, sees Fig. 5.(INSTRUMENT MODEL：SDT Q600)
(4) gas absorption performance research
Low temperature 273K can be used to illustrate the adsorption property of poromerics from adsorption experiment.About 0.25g synthetic sample is weighed,
Constant temperature 3 hours in about 80 DEG C of baking ovens are placed on after grinding, the water for allowing it to lose crystal performance absorption is subsequently transferred to physics suction
In attached instrument sample cell, sample quality is accurately measured for 0.2547g, sample cell work station is transferred to, by determining a series of two
Carbon oxide gas can draw out carbon dioxide adsorption isothermal curve than sample adsorption amount of carbon dioxide under pressure P/Po, be carried with instrument
Software data processing, it is 57.8342cm to the maximum storage value of carbon dioxide to record sample3/g。
(5) the solid fluorescence performance study of complex
Fluorescence experiments：It is put in after solid sample is ground into film-making in sepectrophotofluorometer sample cell, by light source atmosphere arc lamp
The light sent makes it become interrupted light by chopper, as fluorescent material after becoming monochromatic light through exciting light monochromator after
Exciting light, when mapping fluorescence emission time spectrum, the grating of exciting light monochromator is fixed at a length of 240nm of excitation light wave,
Emission spectrum is recorded, it can be seen that fluorescence intensity is maximum at 390nm wavelength, this is the optimal transmitting of sample
Wavelength.When mapping fluorescent exciting time spectrum, the grating of emission monochromator is fixed at 390nm wavelength, excitation spectrum is recorded,
The maximum intensity of excitation spectrum is at 240nm wavelength.The optimal launch wavelength and excitation wavelength of so sample can be very
Good is mapped, and further illustrating synthetic sample has photoluminescent property.See Fig. 6.(INSTRUMENT MODEL：HITACHI/F-
4600)。
Embodiment 2
By 4- (2-methylimidazole) benzoic acid (40.4mg, 0.2mmol), potassium hydroxide (11.2mg, 0.2mmol) and nitric acid
Zinc (35.2mg, 0.15mmol) is dissolved in 10mL DMF solutions, and it is the anti-of polytetrafluoroethylene (PTFE) that above-mentioned mixed solution is loaded into liner
Answer in kettle, 120 DEG C are heated to 6 DEG C per hour of speed, maintain this temperature 3 days, be then naturally cooling to room temperature, you can obtain
Colourless bulk crystals, spend DMF and rinse crystal, obtain target crystal product by being filtered under diminished pressure, target product is positioned over into 80
DEG C baking oven in 3 hours of constant temperature.Finally, target product yield about 75% is obtained.
Embodiment 3
By 4- (2-methylimidazole) benzoic acid (20.2mg, 0.1mmol), sodium hydroxide (11.2mg, 0.2mmol) and nitric acid
Zinc (35.2mg, 0.15mmol) is dissolved in 10mL DMF solutions, and it is the anti-of polytetrafluoroethylene (PTFE) that above-mentioned mixed solution is loaded into liner
Answer in kettle, 130 DEG C are heated to 10 DEG C per hour of speed, maintain this temperature 3 days, be then naturally cooling to room temperature, you can
To colourless bulk crystals, crystal is rinsed with DMF, target crystal product is obtained by being filtered under diminished pressure, target product is placed and 80
DEG C baking oven in 3 hours of constant temperature.Finally, target product yield about 67% is obtained.
Embodiment 4
By 4- (2-methylimidazole) benzoic acid (20.2mg, 0.1mmol), sodium hydroxide (5.6mg, 0.1mmol) and chlorination
Zinc (22.8mg, 0.1mmol) is dissolved in 10mL DMF, and above-mentioned mixed solution is loaded into the reactor that liner is polytetrafluoroethylene (PTFE)
In, 120 DEG C are heated to 10 DEG C per hour of speed, this temperature is maintained 3 days, room temperature is then naturally cooling to, you can obtain nothing
Color bulk crystals, the crystal is separated, and is sequentially passed through DMF washings, vacuum drying treatment, is obtained target product yield about
58%.
Claims (7)
1. the Zn complex that one kind is constructed based on 4- (2-methylimidazole) benzoic acid, it is characterised in that：
Complex is that chemical expression is [Zn (MIBA) with the three-dimensional quadruple of single node interspersed diamond topological structure2]n, its
In, HMIBA is negative one valency anion ligand 4- (2-methylimidazole) benzoic acid with structure shown in formula 1；
2. the Zn complex constructed based on 4- (2-methylimidazole) benzoic acid as described in claim 1, it is characterised in that：It is described
Complex belongs to rhombic system, and space group is P4nc, cell parameter is a=14.1883 (6), b=14.1868 (6), c=
13.5156 (8), α=β=γ=90.00,
3. a kind of preparation method of the Zn complex constructed based on 4- (2-methylimidazole) benzoic acid described in claim 1, its
It is characterised by：Using solvent-thermal method, by divalent zinc salt, 4- (2-methylimidazole) benzoic acid, inorganic base and DMF at 100~130 DEG C
Lower reaction 3~5 days, is cooled to room temperature after reaction, produce chemical expression for [Zn (MIBA)2]nComplex.
4. the preparation method of the Zn complex constructed based on 4- (2-methylimidazole) benzoic acid as described in claim 3, it is special
Levy and be：By 4- (2-methylimidazole) benzoic acid (HMIBA), inorganic base and divalent zinc salt 0.0001-0.0004 in molar ratio:
0.0001-0.0002:0.0001-0.0003 ratio mixing, is dissolved in excessive DMF after mixing and obtains mixed solution, described
Mixed liquor is carried out under 100~130 DEG C of temperature environment after the completion of solvent thermal reaction, solvent thermal reaction, and natural cooling separates out brilliant
Body, washs after drying through deionized water, produces complex.
5. the preparation method of the complex constructed based on 4- (2-methylimidazole) benzoic acid as described in claim 4, its feature
It is：The mixed solution is increased to 100-130 DEG C in sealed autoclave with 6-10 DEG C per hour of heating rate
Temperature environment under carry out solvent thermal reaction 72-96h.
6. the preparation method of the Zn complex constructed based on 4- (2-methylimidazole) benzoic acid as described in claim 3 or 4, its
It is characterised by：The inorganic base is one or more in potassium hydroxide, sodium hydroxide, lithium hydroxide；Divalent zinc salt be zinc chloride,
Zinc acetate or zinc nitrate hexahydrate.
7. a kind of application of the Zn complex constructed based on 4- (2-methylimidazole) benzoic acid described in claim 1, its feature
It is：Application of the complex in gas absorption or fluorescent material.
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| CN110157003A (en) * | 2019-05-27 | 2019-08-23 | 阜阳师范学院 | A kind of 4- (1- (carboxylic methylene) -1H- imidazol-4 yl) zinc benzoate crystalline material, preparation method and application |
| CN112090403A (en) * | 2020-09-07 | 2020-12-18 | 汕头大学 | MAF-stu-13 material with ultramicropore dia-a network topological structure and synthesis and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558742A (en) * | 2018-05-17 | 2018-09-21 | 商丘师范学院 | One kind being based on zinc (II) fluorescent material and preparation method thereof of 4,4 '-bipyridyls-itaconic acid derived ligand |
| CN108558742B (en) * | 2018-05-17 | 2021-05-04 | 商丘师范学院 | Zinc (II) fluorescent material based on 4, 4' -bipyridyl-itaconic acid derivative ligand and preparation method thereof |
| CN110157003A (en) * | 2019-05-27 | 2019-08-23 | 阜阳师范学院 | A kind of 4- (1- (carboxylic methylene) -1H- imidazol-4 yl) zinc benzoate crystalline material, preparation method and application |
| CN112090403A (en) * | 2020-09-07 | 2020-12-18 | 汕头大学 | MAF-stu-13 material with ultramicropore dia-a network topological structure and synthesis and application thereof |
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