CN117263866A - Preparation method and application of crystal material with fluorescence-phosphorescence dual emission - Google Patents
Preparation method and application of crystal material with fluorescence-phosphorescence dual emission Download PDFInfo
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- CN117263866A CN117263866A CN202310060419.5A CN202310060419A CN117263866A CN 117263866 A CN117263866 A CN 117263866A CN 202310060419 A CN202310060419 A CN 202310060419A CN 117263866 A CN117263866 A CN 117263866A
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000013078 crystal Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000009977 dual effect Effects 0.000 title claims abstract description 17
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 230000005284 excitation Effects 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 239000002178 crystalline material Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 13
- 229910052792 caesium Inorganic materials 0.000 description 12
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 cesium ions Chemical class 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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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
- C07D233/66—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/181—Metal complexes of the alkali metals and alkaline earth metals
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- Health & Medical Sciences (AREA)
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Abstract
Preparation method and application of crystal material with fluorescence-phosphorescence dual emission, which is ligand H 3 And (3) reacting the ImDC and the CsCl in a mixed solvent at the temperature of 100 ℃ for 72 hours, performing program cooling to obtain white rod-shaped crystals, and washing and drying to obtain a target product. The product has a cyan fluorescence emission at 525 nm under excitation light of 330 nm; when the excitation light of 370 nm is removed, a yellowish green afterglow is emitted at 538 nm. Therefore, the material of the invention is expected to be popularized and applied in the relevant fields of anti-counterfeiting materials and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of inorganic-organic hybrid materials, and particularly relates to a preparation method and application of a cesium-based metal-organic framework crystal material with fluorescence-phosphorescence dual-emission capability.
Background
Metal-organic frameworks (MOFs) are porous network crystalline materials composed of inorganic nodes (metal ions or clusters) and organic linkers through coordination bonds. The porous ceramic material has the characteristics of high porosity, specific surface area, diversity, adjustability and the like, and is widely applied to the fields of gas storage and separation, optics, catalysis and the like. The optical function MOFs uses the advantages of tunable porosity, structural diversity and abundant photoactive sites in metals and ligands, and has been greatly developed in the fields of sensors, illumination, anti-counterfeiting and the like. At present, the research on cesium-based metal-organic framework phosphorescent materials is not more, but the heavy atomic effect caused by the larger atomic number of Cs is beneficial to the generation of phosphorescence and the increase of the quantum yield of phosphorescence, and the synthesis and the exploration of the materials not only provide a new method for the research on fluorescent-phosphorescent double-emission materials, but also have important reference significance for the function expansion research of the metal-organic framework materials.
Disclosure of Invention
The invention aims to provide a preparation method and application of cesium-based metal-organic framework crystal material with fluorescence-phosphorescence dual-emission capability. The material has a cyan fluorescence emission at 525 nm under excitation light of 330 nm; when the excitation light of 370 nm is removed, a yellowish green afterglow is emitted at 538 nm. Therefore, the product is expected to be popularized and applied in the field of anti-counterfeiting materials.
The invention comprises a cesium-based metal-organic framework crystal material with fluorescence-phosphorescence dual emission capability, and the chemical formula is as follows: [ Cs (H) 2 ImDC)]In which H 2 ImDC - Is H 3 ImDC loses 1 hydrogen ion to obtain H 3 ImDC is 4, 5-imidazole dicarboxylic acid. The minimum asymmetric unit comprises 1 cesium ion and 1H 2 ImDC - 。
The cesium-based metal-organic framework crystal material with fluorescence-phosphorescence dual-emission capability belongs to a monoclinic system, and the space group isP2 1 /cThe unit cell parameters are:a = 3.8558 Å，b = 13.9608 Å，c = 14.2491 Å，α=γ= 90 o ，β = 96.433 o 。
the cesium-based metal-organic framework with fluorescence-phosphorescence dual emission capability has the following crystal structure: the cesium-based metal-organic framework structure has a cesium ion, each of which is in an eight-coordinate, twelve-face ligand configuration. Each cesium ion is associated with two H' s 2 ImDC - Two N atoms of the ligand and H from five ligands 2 ImDC - Is coordinately bound to six O atoms. Cesium-based metal-organic in-frame H 2 ImDC - Is represented by mu 3 -η 3 :η 0 The coordination of the form is carried out,another is mu 2 -η 2 :η 1 Wherein one N atom is attached to two cesium ions and the other N atom is not coordinated. Two cesium ions pass through two μ of the two ligands 3 -O chelation to form a dinuclear structure with a distance of 4.725A, the dinuclear structure passing through mu 3 O is connected with other binuclear, one-dimensional chain structure extends along a direction, and one-dimensional chain passes through H 2 ImDC - And extending in the directions b and c to form a three-dimensional framework structure.
The synthesis method of the cesium-based metal-organic framework crystal material with fluorescence-phosphorescence dual-emission capability comprises the following steps:
an amount of organic ligand H 3 Adding ImDC and CsCl into a certain amount of mixed solvent of N, N-diethyl formamide and deionized water, stirring, mixing uniformly, completely dissolving reactants under the action of ultrasonic waves, reacting at 100 ℃ for 72 hours, cooling to room temperature by a program to obtain white rod-shaped crystals, washing, and drying in vacuum to obtain the product.
The cesium-based metal-organic framework crystal material has excellent fluorescence-phosphorescence double-emission capability. The fluorescence and phosphorescence emission spectra can be seen in fig. 1 and 2.
The invention has the advantages that: the preparation method provided by the invention has the advantages of simple process, short preparation period and low energy consumption. The product has a cyan fluorescence emission at 525 nm under excitation light of 330 nm; when the excitation light of 370 nm is removed, a yellowish green afterglow is emitted at 538 nm. The product provides a feasible material for fluorescence-phosphorescence dual emission, and has good popularization and application prospects in the related fields of luminescent materials and anti-counterfeiting materials.
Description of the drawings:
FIG. 1 is a fluorescence emission spectrum of a fluorescent-phosphorescent dual-emission crystalline material according to the present invention
FIG. 2 shows the phosphorescence emission spectrum of the fluorescent-phosphorescent dual-emission crystalline material of the present invention
FIG. 3 is a diagram showing the minimum coordination unit structure of the fluorescent-phosphorescent dual-emission crystalline material according to the present invention
FIG. 4 shows a one-dimensional chain structure of a fluorescent-phosphorescent dual-emission crystalline material according to the invention
FIG. 5 is a three-dimensional framework of a fluorescent-phosphorescent dual-emission crystalline material according to the present invention
Description of the embodiments
2 mL of N, N-diethyl formamide and 4-mL deionized water are added into a reaction kettle of 25 mL, and the mixture is stirred uniformly to obtain a mixed solvent. 0.0468 g (0.3 mmol) of the organic ligand H was weighed out separately 3 ImDC and 0.0337 g (0.2 mmol) CsCl, the two reactants were added to the above-described reactor and the solid reactants were completely dissolved under the action of ultrasound. And (3) sealing the reaction kettle, putting the reaction kettle into an oven, gradually heating the reaction kettle to 100 ℃, reacting for 72 hours at the temperature, and after the reaction is finished, reducing the temperature by a program for 24 hours to 25 ℃ to obtain the white rod-shaped crystal material with fluorescence-phosphorescence dual emission. The mixed solvent of N, N-diethylformamide and water was recovered by suction filtration, washed three times with N, N-dimethylformamide, each time with 4. 4 mL, and then three times with 95% ethanol, each time with 4. 4 mL. Vacuum drying gives a white rod-like crystalline product, 0.0438, g, in a yield of about 76% calculated as CsCl charge. The product was characterized using the following instrument and method:
crystals of moderate size were selected for single crystal structure analysis, single crystal diffraction data were collected on a Bruker Smart 1000 CCD diffractometer, and mokα rays (λ= 0.71073 a) monochromatized with a graphite monochromator, with θ being 1.75 ° or more and 27.96 ° or less. The obtained compound belongs to monoclinic system, and the space group isP2 1 /cThe unit cell parameters are:a = 3.8558 Å，b = 13.9608 Å，c = 14.2491 Å，α=γ= 90 o ，β = 96.433 o . The crystal structure is shown in fig. 3, fig. 4 and fig. 5, and fig. 3-5 are drawn using Diamond software.
Claims (10)
1. A preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: the raw material used in the preparation process is ligand H 3 ImDC and metal salts CsCl, csCl: h 3 The mass ratio of ImDC is 1: 1.39.
2. a preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: the solvent used in the preparation process is a mixed solvent of N, N-diethyl formamide and deionized water, and the volume ratio of the solvents is N, N-diethyl formamide to deionized water=1 to 2.
3. A preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: mixed solvent 178 mL is required per gram CsCl.
4. A preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: the preparation process is carried out in a sealed reaction kettle, and the reaction kettle is placed in a baking oven at the temperature of 100 ℃ for 72 hours.
5. A preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: after the reaction is completed, the temperature is reduced by the program for 24 hours to 25 ℃.
6. A preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: the minimum asymmetric unit composition of the crystalline material is [ Cs (H) 2 ImDC)]In which H 2 ImDC - Is H 3 ImDC loses 1 hydrogen ion to obtain H 3 ImDC is 4, 5-imidazole dicarboxylic acid.
7. A preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: the crystal material belongs to monoclinic system, and the space group isP2 1 /cThe unit cell parameters are:a = 3.8558 Å，b = 13.9608 Å，c = 14.2491 Å，α = γ = 90 o ，β = 96.433 o 。
8. a preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: the fluorescence of this crystalline material has an emission wavelength of 525 nm at an excitation wavelength of 330 nm.
9. A preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: the phosphorescence of the crystalline material has an emission wavelength of 538 nm at an excitation wavelength of 370 nm.
10. A preparation method and application of a crystal material with fluorescence-phosphorescence dual emission are characterized in that: the crystal material is applied to the related fields of anti-counterfeiting materials and the like.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310060419.5A CN117263866A (en) | 2023-01-17 | 2023-01-17 | Preparation method and application of crystal material with fluorescence-phosphorescence dual emission |
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| CN202310060419.5A CN117263866A (en) | 2023-01-17 | 2023-01-17 | Preparation method and application of crystal material with fluorescence-phosphorescence dual emission |
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| CN202310060419.5A Pending CN117263866A (en) | 2023-01-17 | 2023-01-17 | Preparation method and application of crystal material with fluorescence-phosphorescence dual emission |
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- 2023-01-17 CN CN202310060419.5A patent/CN117263866A/en active Pending
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