CN110790943A - Metal-organic framework polymer with fluorescent light-emitting characteristic, and synthesis method and application thereof - Google Patents
Metal-organic framework polymer with fluorescent light-emitting characteristic, and synthesis method and application thereof Download PDFInfo
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Abstract
The invention discloses a metal-organic framework polymer with fluorescent light-emitting characteristic, a synthesis method and application, belonging to the field of metal-organic framework compounds, wherein the metal-organic framework polymer is prepared by synthesizing ligand 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine, ligand terephthalic acid and zinc nitrate or cadmium nitrate by a hydrothermal method, and the chemical formula of the metal-organic framework polymer is C24H14F2N2O4M, M are Zn2+Ions or Cd2+The synthetic method of the ion is simple in steps, green and environment-friendly, and high in implementation feasibility; the metal-organic framework polymer has strong fluorescence luminescence characteristics (the emission peak is positioned at about 400 nm), can be used as a fluorescence luminescent material, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of metal-organic framework compounds, and particularly relates to a metal-organic framework polymer with a fluorescent light-emitting characteristic, a synthesis method and application.
Background
The metal-organic framework compound (MOF) is a mixture with a special framework and a nano-pore structure in coordination polymers, and refers to a crystalline porous material which is formed by mutually connecting an inorganic metal center and an organic functional group through a coordination bond or an ion-covalent bond and has a regular pore or cavity structure. This is an emerging class of materials emerging from the 20 th century, in the field of intersection of materials science and inorganic coordination chemistry. Since its birth, MOF material is highly valued by experts and scholars in many international fields (it relates to chemistry, physics, materials science, etc.), and rapidly develops into one of the research hotspots across disciplines. The material not only has a crystal structure similar to that of zeolite molecular sieve, but also has a designable and tailorable structure, and can obtain pore channels or cavities with different sizes and structures by the directional design of topological structure and the selection of organic matters. The special structural characteristics enable the metal-organic framework compound (MOF) to have wide application prospects in the research fields of catalytic reaction processes, separation materials, adsorption materials with special properties, sensing materials, energy storage materials and the like. The invention aims to provide a metal-organic framework compound (MOF) with a novel structure, which has remarkable fluorescence luminescence characteristics and potential application value.
Disclosure of Invention
The invention aims to provide a metal-organic framework polymer with fluorescence emission characteristics, a synthesis method and application thereof, wherein the metal-organic framework polymer has excellent fluorescence emission characteristics (an emission peak is positioned at about 400 nm), can be used as a fluorescence emission material, and has the advantages of simple synthesis method and high implementation feasibility.
In order to achieve the purpose, the technical scheme of the invention is to design a metal-organic framework polymer with fluorescent light-emitting characteristic, wherein the metal-organic framework polymer is synthesized by ligand 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine, ligand terephthalic acid and metal M ion salt under certain conditions, and the chemical formula of the metal-organic framework polymer is C24H14F2N2O4M, the structural formula of the 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine is as follows:
the preferable technical scheme is that the metal M ion salt is Zn2+Ionic salts or Cd2+An ionic salt.
Further preferably, the metal M ion salt is zinc nitrate or cadmium nitrate.
In order to facilitate the smooth preparation of the metal-organic framework polymer with the fluorescent light-emitting characteristic, a synthesis method of the metal-organic framework polymer with the fluorescent light-emitting characteristic is proposed: the method comprises the following steps:
s1: synthesizing ligand 4', 4- (2, 5-difluoro-1, 4-phenylene) bipyridine, namely adding 1, 4-dibromo-2, 5-difluorobenzene, 4-pyridine boric acid and potassium carbonate into a reaction vessel according to a certain molar ratio, quickly adding a certain amount of catalyst under the protection of inert gas, then adding a proper amount of solvent into the reaction vessel, stirring and heating to 90 ℃, and reacting for 72 hours to obtain a reaction product mixed solution; cooling the reaction product mixed solution to room temperature, performing rotary evaporation to remove the solvent, and sequentially performing extraction, drying, evaporation concentration and column chromatography on the reaction product concentrated solution to obtain 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine;
s2: metal-organic with fluorescent light emitting characteristicsSynthesis of framework Polymer 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine obtained in step S1, terephthalic acid and Zn (NO)3)2∙6H2O or Cd (NO)3)2∙2H2Weighing O according to the molar ratio of 1: 1, and dissolving the O in sufficient solvent to obtain a raw material mixed solution; placing the raw material mixed solution in a stainless steel reaction kettle, heating to 95 ℃, standing for 3 days, and slowly cooling to room temperature to obtain colorless blocky crystals.
Preferably, in the step S1, the catalyst is tetrakis (triphenylphosphine) palladium, wherein the molar ratio of 1, 4-dibromo-2, 5-difluorobenzene, 4-pyridineboronic acid, potassium carbonate and tetrakis (triphenylphosphine) palladium is 1: 2.3-3: 4-5: 0.3-0.5, the solvent is a mixed solution of water and 1, 4-dioxane, and the volume ratio of water and 1, 4-dioxane is 1: 2.
In a further preferred embodiment, the solvent in step S2 is a mixture of water and DMF, and the volume ratio of water to DMF is 1: 6.
The metal-organic framework polymer having fluorescent light emitting characteristics can be used as a fluorescent light emitting material.
The invention has the advantages and beneficial effects that:
1. the metal-organic framework polymer with the fluorescent light-emitting characteristic has stronger fluorescent property (the emission peak is positioned at about 400 nm), can be used as a fluorescent light-emitting material, and has wide application prospect.
2. The synthesis method of the metal-organic framework polymer with the fluorescent light-emitting characteristic has the advantages of simple steps, environmental protection and high implementation feasibility.
Drawings
FIG. 1 (a) shows C in example 124H14F2N2O4Crystal unit structure of Zn polymer, the polymer using Zn2+Is a central ion, of which 1 Zn2+Ions are coordinated with 4O atoms and 1N atom respectively; FIG. 1 (b) is C in example 124H14F2N2O4A crystal stacking diagram of a Zn polymer having a three-dimensional stereo structure;
FIG. 2 (a) shows C in example 224H14F2N2O4Structure of crystal unit of Cd polymer, the polymer is represented by Cd2+Is a central ion, of which 1 Cd2+Ions are respectively coordinated with 4O atoms and 2N atoms; FIG. 2 (b) is C in example 224H14F2N2O4A crystal stacking diagram of the Cd polymer, wherein the Cd polymer has a three-dimensional structure and is inserted in a double way;
FIG. 3 (a) shows C in example 124H14F2N2O4Polycrystalline powder X-ray diffraction pattern of Zn polymer, showing C24H14F2N2O4The test data and the simulation data of the Zn polymer are basically consistent; FIG. 3 (b) is C in example 224H14F2N2O4Polycrystalline powder X-ray diffraction pattern of Cd polymer, showing C24H14F2N2O4The test data of the Cd polymer is basically consistent with the simulation data; FIG. 3 (C) shows C in example 124H14F2N2O4TGA profile of Zn polymer showing collapse of the crystal structure of the polymer at 352 ℃; FIG. 3 (d) is C in example 224H14F2N2O4A TGA profile of the Cd polymer showing the polymer's crystal structure collapse at 328 ℃;
FIG. 4 shows a graph of C in example 124H14F2N2O4The fluorescence emission spectra of the Zn polymer and the ligand 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine are greatly enhanced in fluorescence intensity compared with the ligand;
FIG. 5 is a nuclear magnetic spectrum of ligand 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine with peak chemical shifts substantially matching the ligand structure.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
Synthesis of ligand 4', 4- (2, 5-difluoro-1, 4-phenylene) bipyridine (dfdp):
1, 4-dibromo-2, 5-difluorobenzene (1.0g,3.7mmol), 4-pyridineboronic acid (1.35g,11 mmol) and potassium carbonate (2.54g,18mmol) were added to a reaction flask, respectively, under N2Rapid addition of Pd (PPh) under protection3)4(0.50g,0.433mmol), adding a mixed solution of water and 1, 4-dioxane (10 mL of water and 20mL of 1, 4-dioxane), stirring and heating to 90 ℃, and reacting for 72 hours to obtain a reaction product mixed solution; cooling the reaction mixture to room temperature, and removing 1, 4-dioxane by rotary evaporation; the reaction product concentrate was extracted with ethyl acetate three times (20 mL each) over anhydrous MgSO4Drying the organic layer, and performing rotary evaporation to obtain a crude product; the crude product was separated by silica gel column chromatography (eluent was a mixture of petroleum ether and ethyl acetate at a volume ratio of 2: 1) to obtain 1.4g (yield 35.14%) of 4 '4- (2, 5-difluoro-1, 4-phenylene) bipyridine as a white solid, and the nuclear magnetic spectrum of 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine is shown in FIG. 5.
Example 2
C24H14F2N2O4Method for synthesizing Zn Polymer (Compound 1):
the ligand 4', 4- (2, 5-difluoro-1, 4-phenylene) bipyridine (dfdp)27.3mg (0.1mmol), terephthalic acid 16.6mg (0.1mmol) and Zn (NO)3)2∙6H2Dissolving O29.7 mg (0.1mmol) in a mixed solution of 7mL of water and DMF (the volume ratio of the two is 1: 6) to obtain a raw material mixed solution; placing the raw material mixture in a stainless steel reaction kettle, heating to 95 deg.C, standing for 3 days, and slowly cooling to room temperature to obtain colorless blocky crystal (C)24H14F2N2O4Zn Polymer, Compound 1)13.7mg, yield 27.3%. Wherein C is24H14F2N2O4The crystallographic data of the Zn polymer are shown in Table 1, the structure diagram of the crystal unit is shown in (a) of figure 1, the crystal stacking diagram is shown in (b) of figure 1, and the polycrystalline powder X-ray diffraction pattern of the Zn polymer is shown in figure 3(a) TGA spectrum is shown in (c) of FIG. 3, and fluorescence emission spectrum of the polymer and ligand 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine is shown in FIG. 4.
Example 3
C24H14F2N2O4Synthesis method of Cd Polymer (Compound 2):
27.3mg (0.1mmol) of 4', 4- (2, 5-difluoro-1, 4-phenylene) bipyridine (dfdp), 16.6mg (0.1mmol) of terephthalic acid and Cd (NO)3)2∙2H2Dissolving O27.2 mg (0.1mmol) in 7mL of mixed solution of water and DMF (the volume ratio of the two is 1: 6) to obtain raw material mixed solution; placing the raw material mixture in a stainless steel reaction kettle, heating to 95 deg.C, standing for 3 days, and slowly cooling to room temperature to obtain colorless blocky crystal (C)24H14F2N2O4Cd Polymer, Compound 2)11.7mg, yield 21.5%. Wherein C is24H14F2N2O4The crystallographic data of the Cd polymer are shown in Table 1, the structure diagram of crystal units is shown in (a) of figure 2, the crystal stacking diagram is shown in (b) of figure 2, and the polycrystalline powder X-ray diffraction pattern of the Cd polymer is shown in (b) of figure 3, and the TGA pattern is shown in (d) of figure 3.
TABLE 1C24H14F2N2O4Zn polymer and C24H14F2N2O4Crystallographic data of Cd polymers
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A metal-organic framework polymer with fluorescent light-emitting characteristic is characterized in that the metal-organic framework polymer is synthesized by ligand 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine, ligand terephthalic acid and metal M ion salt under certain conditions, and the chemical formula of the metal-organic framework polymer is C24H14F2N2O4M, the structural formula of the 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine is as follows:
2. the metal-organic framework polymer having fluorescent light emitting characteristics of claim 1, wherein the metal M ion salt is Zn2+Ionic salts or Cd2+An ionic salt.
3. The metal-organic framework polymer having fluorescent light emitting characteristics of claim 2, wherein the metal M ion salt is zinc nitrate or cadmium nitrate.
4. A method for synthesizing a metal-organic framework polymer having fluorescent light-emitting characteristics according to claim 1, comprising the steps of:
s1: synthesizing ligand 4', 4- (2, 5-difluoro-1, 4-phenylene) bipyridine, namely adding 1, 4-dibromo-2, 5-difluorobenzene, 4-pyridine boric acid and potassium carbonate into a reaction vessel according to a certain molar ratio, quickly adding a certain amount of catalyst under the protection of inert gas, then adding a proper amount of solvent into the reaction vessel, stirring and heating to 90 ℃, and reacting for 72 hours to obtain a reaction product mixed solution; cooling the reaction product mixed solution to room temperature, performing rotary evaporation to remove the solvent, and sequentially performing extraction, drying, evaporation concentration and column chromatography on the reaction product concentrated solution to obtain 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine;
s2: metal-organic framework polymerization with fluorescent light-emitting characteristicsSynthesizing 4' 4- (2, 5-difluoro-1, 4-phenylene) bipyridine prepared in the step S1, terephthalic acid and Zn (NO)3)2∙6H2O or Cd (NO)3)2∙2H2Weighing O according to the molar ratio of 1: 1, and dissolving the O in sufficient solvent to obtain a raw material mixed solution; placing the raw material mixed solution in a stainless steel reaction kettle, heating to 95 ℃, standing for 3 days, and slowly cooling to room temperature to obtain colorless blocky crystals.
5. The method for synthesizing a metal-organic framework polymer having fluorescent light-emitting characteristics according to claim 4, wherein the catalyst in step S1 is tetrakis (triphenylphosphine) palladium, wherein the molar ratio of 1, 4-dibromo-2, 5-difluorobenzene, 4-pyridineboronic acid, potassium carbonate, and tetrakis (triphenylphosphine) palladium is 1: 2.3 to 3: 4 to 5: 0.3 to 0.5, the solvent is a mixture of water and 1, 4-dioxane, and the volume ratio of water and 1, 4-dioxane is 1: 2.
6. The method for synthesizing a metal-organic framework polymer having fluorescent light-emitting characteristics as claimed in claim 5, wherein the solvent in step S2 is a mixture of water and DMF, and the volume ratio of water to DMF is 1: 6.
7. Use of the metal-organic framework polymer having fluorescent light-emitting property according to claim 1, wherein the metal-organic framework polymer having fluorescent light-emitting property is used as a fluorescent light-emitting material.
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| CN114957696A (en) * | 2022-06-16 | 2022-08-30 | 陕西科技大学 | Amino-functionalized metal organic framework MOFs long afterglow coordination compound SUST-WZ-1, preparation and application thereof |
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| CN108314646A (en) * | 2018-04-11 | 2018-07-24 | 胡鹏 | A kind of method of high dispersive bimetal nano material preparation urogenital system pharmaceutical intermediate |
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| JEFFREY T. CULP等: "Screening Hofmann Compounds as CO2 Sorbents: Nontraditional Synthetic Route to Over 40 Different Pore-Functionalized and Flexible Pillared Cyanonickelates", 《INORGANIC CHEMISTRY》 * |
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| CN114957696A (en) * | 2022-06-16 | 2022-08-30 | 陕西科技大学 | Amino-functionalized metal organic framework MOFs long afterglow coordination compound SUST-WZ-1, preparation and application thereof |
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