CN108912163A - A kind of lead-MOFs complex with fluorescence property - Google Patents
A kind of lead-MOFs complex with fluorescence property Download PDFInfo
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- CN108912163A CN108912163A CN201810634697.6A CN201810634697A CN108912163A CN 108912163 A CN108912163 A CN 108912163A CN 201810634697 A CN201810634697 A CN 201810634697A CN 108912163 A CN108912163 A CN 108912163A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- -1 4- (methoxycarbonyl) phenyl Chemical group 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
- 238000009825 accumulation Methods 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000004323 axial length Effects 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
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000000034 method 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
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000010865 sewage 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 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
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating 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
- 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000002604 ultrasonography 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 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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- 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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- Physics & Mathematics (AREA)
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- General Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Polymers & Plastics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The preparation of the invention discloses a kind of lead-MOFs complex with fluorescence property, molecular formula are [Pb (L)0.5(DMA)(H2O)]·DMA·2H2O, complex structure belong to monoclinic system C2/c space group, and the basic structural unit of crystal is obtained by asymmetric cell by symmetry operation, and symmetry operation code is1-1/2+X,-1/2+Y,+Z；21/2+X,1/2+Y,+Z；31-X, 1-Y, 1-Z have the ligand of 1/2 coordination, a Pb in the asymmetric cell2+Ion, the DMA molecule of a coordination, Pb2+Pentacoordinate mode is taken, wherein four oxygen atoms are respectively from two different derivative ligands, another oxygen atom is the DMA molecule that is coordinated, the average bond length of Pb-OThe 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 lead-MOFs complex with fluorescence property.
Background technique
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 getting worse for 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 disadvantages of its sensitivity is low, at high cost
General application.
Summary of the invention
The object of the present invention is to provide a kind of lead-MOFs complex with fluorescence property, to solve institute in the prior art
The existing above problem.
A kind of lead-MOFs complex with fluorescence property, molecular formula are [Pb (L)0.5(DMA)(H2O)]·DMA·
2H2O, complex structure belong to monoclinic system C2/c space group, and the basic structural unit of crystal is passed through symmetrical by asymmetric cell
Operation obtains, and symmetry operation code is1-1/2+X,-1/2+Y,+Z；21/2+X,1/2+Y,+Z；31-X, 1-Y, 1-Z, the asymmetry
There are the ligand of 1/2 coordination, a Pb in unit2+Ion, the DMA molecule of a coordination, Pb2+Pentacoordinate mode is taken, wherein four
A oxygen atom respectively from two different derivative ligands, another oxygen atom come the DMA molecule that is coordinated, Pb-O's
Average bond length isAll carboxylic acid groups and Pb2+Ion all takes chelating coordination modes, and the SBU of monokaryon passes through ligand
Be connected in a axis direction and extend to form one-dimensional catenary structure, three-dimensional structure is formed by weak pi-pi accumulation between chain and chain,
Cell parameter is axial lengthShaft angle α=90.00 °, β=
99.0296 (13) °, γ=90.00 °, unit cell volume areZ=8, wherein ligand H4L is 4,4', 4 ",
4 " '-(- 1,3,6,8- tetraphenyl) four benzoic acid, structural formula are：
A kind of preparation method of the lead-MOFs complex with fluorescence property as the aforementioned comprising following steps：
By 0.1mmol plumbi nitras and 0.01mmol ligand H4L is put into the vial of 10mL, and the N, N- of 2mL is then added
Dimethylacetamide solution tightens bottle cap after being ultrasonically treated 10min, is put into and is warming up to 100 DEG C of speed in baking oven in 300min
Rate heating, and 4320min is kept the temperature at 100 DEG C, it is cooled to room temperature, is obtained bright orange with the rate of 0.1 DEG C/min after heat preservation
Color bulk crystals, i.e., the described lead-MOFs complex.
Preferably, the ligand H4The preparation method of L is：
By 4- (methoxycarbonyl) phenyl) boric acid, 1,3,6,8- tetrabromo, tetrakis triphenylphosphine palladium (0) and anhydrous phosphoric acid
After tripotassium mixes, in an argon atmosphere, is reacted at 130 DEG C, obtain 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, adjusting pH value is 1, is filtered, washed, recrystallized and dried, obtains ligand H4L。
A kind of application of the lead-MOFs complex 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 using the method for ultrasound, promote ligand hydrolysis, reduce ligand dosage, gained complex yield is high；
5, complex shows good fluorescence property.
Detailed description of the invention
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 lead-MOFs complex of the preparation of the embodiment of the present invention 2；
Fig. 2 is the coordination mode structure chart of lead ion in the lead-MOFs complex of the preparation of the embodiment of the present invention 2；
Fig. 3 is the three-dimensional framework figure of lead-MOFs complex prepared by the embodiment of the present invention 2；
Fig. 4 is the XRD diagram of lead-MOFs complex prepared by the embodiment of the present invention 2；
Fig. 5 is the thermal multigraph of lead-MOFs complex prepared by the embodiment of the present invention 2；
Fig. 6 is the infrared spectrum of lead-MOFs complex prepared by the embodiment of the present invention 2；
Fig. 7 is the solid state fluorescence test chart of lead-MOFs complex prepared by the embodiment of the present invention 2.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.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 scope.
Embodiment 1
The present embodiment is related to a kind of preparing 4,4', 4 ", 4 " method of '-(- 1,3,6,8- tetraphenyl) four benzoic acid, tools
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 vial and cover.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 (4- (the methoxyl group carbonyl of 1,3,6,8- tetra-
Base) phenyl) pyrene 0.58g (yield 82%).Then, to contain 1,3,6,8- tetra- (4- (methoxyl group of 0.58g (0.78mmol) solid
Carbonyl) phenyl) pyrene 250mL round-bottomed flask in be added containing 1.5g (37.5mmol) NaOH 100mL tetrahydrofuran/water (ratio
Example 1:1) mixture, and by gained suspension vigorous stirring overnight under reflux.Solvent is removed under vacuum and is added water to
It is formed in the residue of clear yellow solution.Clear yellow solution is stirred at room temperature 2 hours, and uses dense HCl by pH
Value is adjusted to 1.The yellow solid being collected by filtration, and be washed with water for several times.Crude product is recrystallized with DMF, and chloroform is used in filtering
It washs 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 of lead-MOFs complex prepared with fluorescence property, specifically include as
Lower step：
Precise Pb (NO3)2(33mg, 0.1mmol), ligand H4L (5mg, 0.01mmol) is put into the vial of 10ml
In, bottle cap is tightened, the n,N-dimethylacetamide solution of 2ml is then added, it is dry that electric heating constant temperature air blast is put into after ultrasonic 10min
In dry case, 100 DEG C are warming up to 300min, and keep 4320min, then with 0.1 DEG C of min-1Rate reaction system is delayed
Slow cool down is to room temperature.Obtain yellow bulk crystals.Elemental analysis test value (theoretical value)/%：C:46.39%；H:4.77%；N:
3.61%.Elemental analysis actual value/%：C:45.85%；H:4.61%；N:3.52%.
Under room temperature, the lead-MOFs complex to manufactured in the present embodiment with fluorescence property has carried out X-ray powder
Diffraction characterization, obtained PXRD spectrogram are as shown in Figure 4, it can be seen that the powder X-ray for the lead-MOFs complex that the present embodiment measures is penetrated
The powder diffraction peak that line diffraction maximum and single crystal data are simulated coincide relatively good, this shows that testing lead-MOFs obtained matches
It is higher to close object purity.Lead-MOFs complex belongs to monoclinic system, C2/c space group, molecular formula C34HO12N0.13Pb.It is not
There are the ligand of 1/2 coordination, a Pb in symmetrical cell2+Ion, the DMA molecule (as shown in Figure 1) of a coordination.Pb2+Take five
Coordination mode, wherein four oxygen atoms are respectively from two different derivative ligands, another oxygen atom is coordinated
DMA molecule (as shown in Figure 2), the average bond length of Pb-O isAll carboxylic acid groups and Pb2+Ion all takes chelating
The SBU of coordination mode, monokaryon extends to form one-dimensional catenary structure by being connected in a axis direction for ligand, leads between chain and chain
It crosses weak pi-pi accumulation and forms three-dimensional structure (as shown in Figure 3), cell parameter is axial length Shaft angle α=90.00 °, β=99.0296 (13) °, γ=90.00 °, unit cell volume are
Z=8, actual crystal parameter are as shown in Table 1 to Table 3.
Thermogravimetric analysis is carried out to the lead-MOFs complex manufactured in the present embodiment with fluorescence property, in N2In atmosphere
With 10 DEG C of min-1Heating rate DEG C tested from 40 DEG C to 900, it is as a result as shown in figure 5, weightless before 410 DEG C
19%, this is that solvent molecule in the lattice lost includes 2 DMA molecules and 3 hydrones, and crystalline framework is opened after 410 DEG C
Begin to collapse, until 480 DEG C of skeletons collapsing weight loss 50% completely.
Infrared spectrum analysis carried out to the lead-MOFs complex manufactured in the present embodiment with fluorescence property, data by
German 37 type infrared spectrometer of Bruker Tensor is 400~4000cm in wave number-1The collection of range, using solid sample
KBr tabletting, as a result as shown in fig. 6, the main infrared absorption peak (v/cm of lead-MOFs complex-1)For：3410 (s), 2358 (s),
1603 (s), 1411 (w), 1177 (s), 1098 (w), 1007 (w), 858 (m), 789 (w), 721 (w).Wherein 3410cm-1Width
Absorption peak belongs to the hydroxyl stretching vibration of water of coordination in 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 1603 (s), 1411 (s) two features accordingly
Peak；1177 (w) absorption peak belongs to the symmetric vibration absorption peak of carboxyl in lead-MOFs complex.
Solid state fluorescence test is carried out to the lead-MOFs complex manufactured in the present embodiment with fluorescence property, as a result such as
Shown in Fig. 7, there is a maximum absorption band (λ ex=330nm) at 529nm in the absorption spectrum of ligand, this is because π ... π *
Caused by electronics transfer.Lead-MOFs complex shows strong fluorescence at room temperature, and absorption spectrum occurs one at 468nm
A maximum absorption band (λ ex=330nm).And show blue shift (Δ=61nm).This may be attributed to ligands in metal
The heart, is effectively increased the rigidity and symmetry of ligand, to reduce the energy loss of non-radiative decay.
Table 1：Crystallographic parameter
The selective bond distance of 2 lead-MOFs complex of table
The symmetry operation code of asymmetric cell in crystal basic structural unit：
1-1/2+X,-1/2+Y,+Z；21/2+X,1/2+Y,+Z；31-X,1-Y,1-Z；41-X,+Y,3/2-Z
The selective bond angle (°) of 3 lead-MOFs complex of table
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (4)
1. a kind of preparation of the lead-MOFs complex with fluorescence property, it is characterised in that：Its molecular formula is [Pb (L)0.5
(DMA)(H2O)]·DMA·2H2O, complex structure belong to monoclinic system C2/c space group, and the basic structural unit of crystal is not by
Symmetrical cell is obtained by symmetry operation, and symmetry operation code is1-1/2+X,-1/2+Y,+Z；21/2+X,1/2+Y,+Z；31-X,1-
Y, 1-Z have the ligand of 1/2 coordination, a Pb in the asymmetric cell2+Ion, the DMA molecule of a coordination, Pb2+It takes
Pentacoordinate mode, wherein four oxygen atoms are respectively from two different derivative ligands, another oxygen atom is matched
The DMA molecule of position, the average bond length of Pb-O areAll carboxylic acid groups and Pb2+Ion all takes chelating ligands mould
The SBU of formula, monokaryon extends to form one-dimensional catenary structure by being connected in a axis direction for ligand, by weak between chain and chain
Pi-pi accumulation forms three-dimensional structure, and cell parameter is axial length
Shaft angle α=90.00 °, β=99.0296 (13) °, γ=90.00 °, unit cell volume areZ=8, wherein
Ligand H4L is 4,4', 4 ", 4 " '-(- 1,3,6,8- tetraphenyl) four benzoic acid, and structural formula is：
2. a kind of preparation method of the lead-MOFs complex with fluorescence property as described in claim 1, which is characterized in that
Include the following steps：
By 0.1mmol plumbi nitras and 0.01mmol ligand H4L is put into the vial of 10mL, and the N of 2mL, N- dimethyl is then added
Acetamide solution tightens bottle cap after being ultrasonically treated 10min, is then placed in and is warming up to 100 DEG C of rate in baking oven in 300min
Heating, and 4320min is kept the temperature at 100 DEG C, it is cooled to room temperature after heat preservation with the rate of 0.1 DEG C/min, obtains glassy yellow
Bulk crystals, i.e., the described lead-MOFs complex.
3. the preparation method of the lead-MOFs complex with fluorescence property as claimed in claim 2, which is characterized in that described
Ligand H4The preparation method of L is：
By 4- (methoxycarbonyl) phenyl) boric acid, 1,3,6,8- tetrabromo, tetrakis triphenylphosphine palladium (0) and anhydrous phosphoric acid tripotassium
It after mixing, in an argon atmosphere, 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, adjusting pH value is 1, is filtered, washed, recrystallized and dried, obtains ligand H4L。
4. a kind of application of lead-MOFs complex as described in claim 1 in heavy metal ion fluorescence identifying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456754A (en) * | 2018-12-07 | 2019-03-12 | 辽宁大学 | A kind of lead base metal-organic framework material and its preparation method and application |
| CN111662320A (en) * | 2020-06-03 | 2020-09-15 | 陕西科技大学 | Pb-MOF (Metal organic framework) integrated fluorescence sensor and preparation method thereof |
| CN112442186A (en) * | 2019-09-04 | 2021-03-05 | 中国科学院大连化学物理研究所 | Metal organic framework Mn-MOF single crystal material and nanosheet as well as preparation and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456754A (en) * | 2018-12-07 | 2019-03-12 | 辽宁大学 | A kind of lead base metal-organic framework material and its preparation method and application |
| CN112442186A (en) * | 2019-09-04 | 2021-03-05 | 中国科学院大连化学物理研究所 | Metal organic framework Mn-MOF single crystal material and nanosheet as well as preparation and application thereof |
| CN112442186B (en) * | 2019-09-04 | 2021-08-10 | 中国科学院大连化学物理研究所 | Metal organic framework Mn-MOF single crystal material and nanosheet as well as preparation and application thereof |
| CN111662320A (en) * | 2020-06-03 | 2020-09-15 | 陕西科技大学 | Pb-MOF (Metal organic framework) integrated fluorescence sensor and preparation method thereof |
| CN111662320B (en) * | 2020-06-03 | 2023-05-09 | 陕西科技大学 | Pb-MOF integrated fluorescence sensor and preparation method thereof |
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