CN108690057A - A kind of cadmium-MOFs complexs with fluorescence property - Google Patents
A kind of cadmium-MOFs complexs with fluorescence property Download PDFInfo
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- CN108690057A CN108690057A CN201810634504.7A CN201810634504A CN108690057A CN 108690057 A CN108690057 A CN 108690057A CN 201810634504 A CN201810634504 A CN 201810634504A CN 108690057 A CN108690057 A CN 108690057A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 30
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- -1 4- (methoxycarbonyl) phenyl Chemical group 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- KOSQJXUTAMHQII-UHFFFAOYSA-N methyl 4-[3,6,8-tris(4-methoxycarbonylphenyl)pyren-1-yl]benzoate Chemical class COC(=O)c1ccc(cc1)-c1cc(-c2ccc(cc2)C(=O)OC)c2ccc3c(cc(-c4ccc(cc4)C(=O)OC)c4ccc1c2c34)-c1ccc(cc1)C(=O)OC KOSQJXUTAMHQII-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- KDSSEOIBFVTMNM-UHFFFAOYSA-N [K].[K].[K].P(O)(O)(O)=O Chemical compound [K].[K].[K].P(O)(O)(O)=O KDSSEOIBFVTMNM-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical class [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- 239000004744 fabric Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- MKKWZXSLSSSUIY-UHFFFAOYSA-N (4-methoxycarbonylphenoxy)boronic acid Chemical compound COC(=O)C1=CC=C(OB(O)O)C=C1 MKKWZXSLSSSUIY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000010165 autogamy Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- 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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- 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
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Optics & Photonics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The preparation of the invention discloses a kind of cadmium-MOFs complexs with fluorescence property, molecular formula are { [Cd2(L)(H2O)]·DMA·Diox·2H2O } n, complex structure belongs to P-1 space groups, and the basic structural unit of crystal is obtained by asymmetric cell by symmetry operation, and symmetry operation code is11-X,2-Y,1-Z;21+X,+Y,1+Z;31-X,3-Y,-Z;42-X,3-Y,1-Z;5-1+X,+Y,-1+Z;62-X, 3-Y ,-Z, the ligand of a coordination, two Cd in the asymmetric cell2+Ion, the H of a coordination2O molecules, there are the Cd of two kinds of coordination modes in complex2+Ion, Cd1 take seven coordination modes, and six of which oxygen atom is respectively from four different derivative ligands, H of another oxygen atom from coordination2O molecules, Cd2 take hexa-coordinate pattern, wherein four oxygen atoms are respectively from four different derivative ligands, H of other two oxygen atom from coordination2O molecules.The advantage of the invention is that:The controllable preparation of fluorescence complex.
Description
Technical field
The invention belongs to new material technology fields, specifically disclose a kind of cadmium-MOFs complexs with fluorescence property.
Background technology
Metal-organic framework materials can modify with its advantageous advantage-porosity, aperture easy-regulating, the ratio of superelevation
Surface area etc. is studied by more and more people, all there is pole at many aspects such as fluorescence identifying, the separation of gas, electro-catalysis
Big application.
With the getting worse of environmental pollution, excessive heavy metal all becomes now urgently in the improvement of sewage and reduction sewage
Problem to be solved.And traditional detection method limits its in the industry wide due to the shortcomings of its sensitivity is low, of high cost
General application.
Invention content
The object of the present invention is to provide a kind of cadmium-MOFs complexs with fluorescence property, to solve institute in the prior art
The existing above problem.
A kind of cadmium-MOFs complexs with fluorescence property, molecular formula [Cd2(L)(H2O)]·DMA·Diox·
2H2O, complex structure belong to P-1 space groups, and the basic structural unit of crystal is obtained by asymmetric cell by symmetry operation,
Symmetry operation code is11-X,2-Y,1-Z;21+X,+Y,1+Z;31-X,3-Y,-Z;42-X,3-Y,1-Z;5-1+X,+Y,-1+Z;62-
X, 3-Y ,-Z, the ligand of a coordination, two Cd in the asymmetric cell2+Ion, the H of a coordination2O molecules, complex
It is middle that there are the Cd of two kinds of coordination modes2+Ion, Cd1 take seven coordination modes, and six of which oxygen atom is respectively from four differences
Derivative ligand, H of another oxygen atom from coordination2O molecules, Cd2 take hexa-coordinate pattern, wherein four oxygen
Atom is respectively from four different derivative ligands, H of other two oxygen atom from coordination2O molecules, Cd-O's
Average bond length isCd1-Cd2-Cd1 is staggered to form three core SBU, connects to form three-dimensional frame structure by ligand,
Two are formed in b axis directionsWithOne-dimensional diamond shape duct, cell parameter is axial lengthShaft angle α=73.919 (5) °, β=79.324 (5) °, γ=
71.817 (5) °, unit cell volume areZ=2, wherein ligand H4L is 4,4',4",4"'(- 1,3,6,
8- tetraphenyls) four benzoic acid, structural formula is:
A kind of preparation method of the cadmium-MOFs complexs with fluorescence property as the aforementioned comprising following steps:
By 0.2mmol cadmium nitrates and 0.01mmol ligands H4L is put into the vial of 10mL, and the N, N- of 2mL is then added
The mixed solution of dimethylacetylamide, Isosorbide-5-Nitrae-dioxane and water, be ultrasonically treated 10min after, tighten bottle cap, be put into baking oven with
It is warming up to 100 DEG C of rate heating in 300min, and keeps the temperature 4320min at 100 DEG C, with 0.1 DEG C/min's after heat preservation
Rate is cooled to room temperature, and obtains glassy yellow bulk crystals, i.e., the described cadmium-MOFs complexs.
Preferably, the ligand H4The preparation method of L is:
By 4- (methoxycarbonyl) phenyl) boric acid, 1,3,6,8- tetrabromos, tetrakis triphenylphosphine palladium (0) and anhydrous phosphoric acid
It after tripotassium mixing, in ar gas environment, is reacted at 130 DEG C, obtains 1,3,6,8- tetra- (4- (methoxycarbonyl) phenyl)
Pyrene;
By 1,3,6,8- tetra- (4- (methoxycarbonyl) phenyl) pyrene in the mixed solution of tetrahydrofuran, water and sodium hydroxide
After back flow reaction, it is 1 to adjust pH value, through being filtered, washed, recrystallizing and dry, obtains ligand H4L。
A kind of application of the cadmium-MOFs complexs with fluorescence property in heavy metal ion fluorescence identifying as the aforementioned.
The advantage of the invention is that:
1, reaction solvent for use be easy to get, be inexpensive, green non-pollution;
2, reaction condition is simple, reaction can be carried out quickly, is energy saving, saving the time;
3, yield is high, ligand dosage is low, saves cost;
4, by the way that acidic materials are added, promote ligand hydrolysis, reduce ligand dosage, gained complex yield is high;
5, complex shows good fluorescence property.
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the coordination mode structure chart of object derived from the cadmium-MOFs complexs of the preparation of the embodiment of the present invention 2;
Fig. 2 is that coordination is formed between cadmium ion and derivative in cadmium-MOFs complexs prepared by the embodiment of the present invention 2
One-dimensional catenary structure figure;
Fig. 3 is the three-dimensional framework figure of cadmium-MOFs complexs prepared by the embodiment of the present invention 2;
Fig. 4 is the XRD diagram of cadmium-MOFs complexs prepared by the embodiment of the present invention 2;
Fig. 5 is the thermal multigraph of cadmium-MOFs complexs prepared by the embodiment of the present invention 2;
Fig. 6 is the infrared spectrum of cadmium-MOFs complexs prepared by the embodiment of the present invention 2;
Fig. 7 is the solid state fluorescence test chart of cadmium-MOFs complexs prepared by the embodiment of the present invention 2.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
The present embodiment is related to a kind of preparing 4,4',4",4"'The method of (- 1,3,6,8- tetraphenyl) four benzoic acid, tool
Body includes the following steps:By (4- (methoxycarbonyl) phenyl) boric acid (1.040g, 5.80mmol), 1,3,6,8- tetrabromo
(0.500g, 0.97mmol), tetrakis triphenylphosphine palladium (0) (0.030g 0.026mmol) and anhydrous phosphoric acid tripotassium (1.100g,
It 5.30mmol) is fitted into and (is placed in glove box) in 20mL microwave vials and be capped.Under argon gas by the mixture at 130 DEG C
It is stirred 72 hours in oil bath.Reaction mixture is evaporated to dryness, and solid residue is washed with water to remove inorganic salts.Use chlorine
Imitative extraction insoluble matter (50mL is three times) with magnesium sulfate dry extract, and reduces solvent volume under vacuum.By residue four
2 hours are boiled in hydrogen furans and are filtered;Gained filtrate mainly contains impurity.The program obtains the (4- (first of 0.58g 1,3,6,8- tetra-
Epoxide carbonyl) phenyl) pyrene 0.58g (yield 82%).Then, to containing 1,3,6,8- tetra- (4- of 0.58g (0.78mmol) solid
(methoxycarbonyl) phenyl) 250mL round-bottomed flasks in be added containing 1.5g (37.5mmol) be added 100mL tetrahydrofurans/
Water (ratio 1:1) NaOH in mixture and by gained suspension vigorous stirring overnight under reflux.Solvent is removed under vacuum
And it adds water in the residue to form clear yellow solution.Clear yellow solution is stirred at room temperature 2 hours, and is made
PH value is adjusted to 1 with dense HCl.The yellow solid being collected by filtration, and be washed with water for several times.Crude product is recrystallized with DMF,
Filtering, with chloroform and is dried in vacuo.This obtains the pure products H of 0.49g (91%)4TBAPy, abbreviation H4L。
Embodiment 2
The present embodiment is related to a kind of preparation method preparing fluorescence cadmium-MOFs complexs, specifically comprises the following steps:
Precise Cd (NO3)2·4H2O (50mg, 0.2mmol), ligand H4L (5mg, 0.01mmol) is put into the glass of 10ml
In glass bottle, bottle cap is tightened, n,N-dimethylacetamide, the mixed solution (volume of Isosorbide-5-Nitrae-dioxane and water of 2ml is then added
Than=5:2:1) it, is put into electric heating constant-temperature blowing drying box after ultrasonic 10min, is warming up to 100 DEG C with 300min, and keep
4320min, then with 0.1 DEG C of min-1Rate reaction system is slowly cooled to room temperature.Obtain glassy yellow bulk crystals.Member
Element analysis test value (theoretical value)/%:C:54.98%;H:4.32%;N:1.23%. elemental analysis actual value/%:C:
54.77%;H:4.18%;N:1.12%.
Under room temperature, powder x-ray diffraction characterization has been carried out to cadmium-MOFs complexs manufactured in the present embodiment, obtained
PXRD spectrograms as indicated at 4, it can be seen that the powder x-ray diffraction peak and monocrystalline for the cadmium-MOFs complexs that the present embodiment measures
Powder diffraction peak that digital simulation obtains coincide relatively good, this shows to test cadmium-MOFs complex purity obtained higher.
Cadmium-MOFs complexs belong to C2/c space groups, molecular formula C50H38Cd1.5NO12.In asymmetric cell one coordination match
Body, two Cd2+Ion, the H of a coordination2O molecules, there are the Cd of two kinds of coordination modes in complex2+Ion, Cd1 take seven
Coordination mode, six of which oxygen atom carry out autogamy respectively from four different derivative ligands, another oxygen atom
The H of position2O molecules, Cd2 take hexa-coordinate pattern, wherein four oxygen atoms are respectively from four different derivative ligands,
H of other two oxygen atom from coordination2The average bond length of O molecules, Cd-O isCd1-Cd2-Cd1 is staggered to form three
Core SBU, connects to form three-dimensional frame structure by ligand, and two are formed in b axis directionsWithOne
Diamond shape duct is tieed up, cell parameter is axial lengthShaft angle α=73.919
(5) °, β=79.324 (5) °, γ=71.817 (5) °, unit cell volume isZ=2.Pass through PLATON softwares
The porosity of cadmium-MOFs complexs, about 31.33% are calculated, actual crystal parameter is as shown in Table 1 to Table 3.
Thermogravimetric analysis is carried out to cadmium-MOFs complexs manufactured in the present embodiment, in N2With 10 DEG C of min in atmosphere-1's
Heating rate DEG C is tested from 40 DEG C to 900, and the results are shown in Figure 5, and weight loss 22% is 2 moisture before 366 DEG C
The solvent of son, a DMA molecule and an Isosorbide-5-Nitrae-dioxane molecule, 366~550 DEG C of crystalline frameworks cave in and have lost 70%.
Infrared spectrum analysis is carried out to fluorescence cadmium-MOFs complexs manufactured in the present embodiment, data are by German Bruker
37 type infrared spectrometers of Tensor are 400~4000cm in wave number-1The collection of range, using solid sample KBr tablettings, as a result
As shown in fig. 6, the main infrared absorption peak (v/cm-1) of cadmium-MOFs complexs is:3431 (s), 2927 (s), 1609 (s),
1534 (w), 1401 (s), 1257 (w), 1113 (w), 1007 (s), 864 (m), 784 (w), 721 (w).Wherein 3431cm-1Width
Absorption peak belongs to the hydroxyl stretching vibration of the water of coordination of complex;In 1720~1690cm-1There is not the spy of free carboxy in place
Absorption peak is levied, illustrates that all carboxyls on ligand have all sloughed proton, produces 1609 (s), 1534 (s) two features accordingly
Peak;The absorption peak of 1257 (w) belongs to the symmetric vibration absorption peak vs (COO-) of carboxyl in complex 2.
Solid state fluorescence test is carried out to cadmium-MOFs complexs manufactured in the present embodiment, the results are shown in Figure 7, ligand
There is a maximum absorption band (λ ex=330nm) at 529nm in absorption spectrum, this is because the electronics transfer of π ... π * causes
's.Cadmium-MOFs complexs show strong fluorescence at room temperature, and a maximum absorption band occurs at 475nm in absorption spectrum
(λ ex=330nm).And show blue shift (Δ=54nm).This may be attributed to ligands in metal center, effective increase
The rigidity and symmetry of ligand, to reducing the energy loss of non-radiative decay.
Table 1:Crystallographic parameter
The selective bond distance of 2 cadmium-MOFs complexs of table
The symmetry operation code of asymmetric cell in crystal basic structural unit:
11-X,2-Y,1-Z;21+X,+Y,1+Z;31-X,3-Y,-Z;42-X,3-Y,1-Z;5-1+X,+Y,-1+Z;62-X,3-
Y,-Z;7-X,2-Y,-Z
The selective bond angle (°) of 3 cadmium-MOFs complexs 2 of table
The symmetry operation code of asymmetric cell in crystal basic structural unit:
11-X,2-Y,1-Z;21+X,+Y,1+Z;31-X,3-Y,-Z;42-X,3-Y,1-Z;5-1+X,+Y,-1+Z;62-X,3-
Y,-Z;7-X,2-Y,-Z。
Claims (5)
1. a kind of preparation of the cadmium-MOFs complexs with fluorescence property, it is characterised in that:Its molecular formula is [Cd2(L)
(H2O)]·DMA·Diox·2H2O, complex belong to three biassed fabric P-1 space groups, and the basic structural unit of crystal is by asymmetry
Unit is obtained by symmetry operation, and symmetry operation code is11-X,2-Y,1-Z;21+X,+Y,1+Z;31-X,3-Y,-Z;42-X,3-
Y,1-Z;5-1+X,+Y,-1+Z;62-X, 3-Y ,-Z, the ligand of a coordination, two Cd in the asymmetric cell2+Ion, one
The H of a coordination2O molecules, there are the Cd of two kinds of coordination modes in complex2+Ion, Cd1 take seven coordination modes, six of which
Oxygen atom is respectively from four different derivative ligands, H of another oxygen atom from coordination2O molecules, Cd2 are adopted
Hexa-coordinate pattern is taken, wherein four oxygen atoms, respectively from four different derivative ligands, other two oxygen atom comes
From the H of coordination2The average bond length of O molecules, Cd-O isCd1-Cd2-Cd1 is staggered to form three core SBU, is connected by ligand
It connects to form three-dimensional frame structure, two is formed in b axis directionsWithOne-dimensional diamond shape duct, structure cell
Parameter is axial lengthShaft angle α=73.919 (5) °, β=79.324
(5) °, γ=71.817 (5) °, unit cell volume isZ=2, wherein ligand H4L is 4,4',4",4"'-
(- 1,3,6,8- tetraphenyl) four benzoic acid, structural formula are:
2. a kind of preparation method of the cadmium-MOFs complexs as described in claim 1 with fluorescence property, which is characterized in that
Include the following steps:
By 0.2mmol cadmium nitrates and 0.01mmol ligands H4L is put into the vial of 10mL, and the N of 2mL, N- dimethyl is then added
The mixed solution of acetamide, Isosorbide-5-Nitrae-dioxane and water is tightened bottle cap, is put into baking oven with 300min after being ultrasonically treated 10min
It is inside warming up to 100 DEG C of rate heating, and keeps the temperature 4320min at 100 DEG C, it is cold with the rate of 0.1 DEG C/min after heat preservation
But to room temperature, glassy yellow bulk crystals are obtained, i.e., the described cadmium-MOFs complexs.
3. a kind of preparation method of the cadmium-MOFs complexs with fluorescence property as claimed in claim 2, which is characterized in that
In the mixed solution of the n,N-dimethylacetamide, Isosorbide-5-Nitrae-dioxane and water, n,N-dimethylacetamide, Isosorbide-5-Nitrae-dioxy six
The volume ratio of ring and water is 5:2:1.
4. a kind of preparation method of the cadmium-MOFs complexs with fluorescence property as claimed in claim 2, which is characterized in that
The ligand H4The preparation method of L is:
By 4- (methoxycarbonyl) phenyl) boric acid, 1,3,6,8- tetrabromos, tetrakis triphenylphosphine palladium (0) and anhydrous phosphoric acid tripotassium
It after mixing, in ar gas environment, is reacted at 130 DEG C, obtains 1,3,6,8- tetra- (4- (methoxycarbonyl) phenyl) pyrenes;
1,3,6,8- tetra- (4- (methoxycarbonyl) phenyl) pyrene is flowed back in the mixed solution of tetrahydrofuran, water and sodium hydroxide
After reaction, it is 1 to adjust pH value, through being filtered, washed, recrystallizing and dry, obtains ligand H4L。
5. a kind of application of cadmium-MOFs complexs as described in claim 1 in heavy metal ion fluorescence identifying.
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