CN104804027A - Rare earth metal-organic frame material as well as preparation method and application thereof - Google Patents
Rare earth metal-organic frame material as well as preparation method and application thereof Download PDFInfo
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- CN104804027A CN104804027A CN201510198517.0A CN201510198517A CN104804027A CN 104804027 A CN104804027 A CN 104804027A CN 201510198517 A CN201510198517 A CN 201510198517A CN 104804027 A CN104804027 A CN 104804027A
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 238000002050 diffraction method Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 3
- 239000010931 gold Substances 0.000 claims 3
- 229910052737 gold Inorganic materials 0.000 claims 3
- 239000002689 soil Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 1
- -1 phenyl aldehyde Chemical class 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 10
- 235000019445 benzyl alcohol Nutrition 0.000 description 10
- 229960004217 benzyl alcohol Drugs 0.000 description 10
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 description 8
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910021644 lanthanide ion Inorganic materials 0.000 description 3
- 239000013384 organic framework Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100000652 hormesis Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- UNFWWIHTNXNPBV-WXKVUWSESA-N spectinomycin Chemical compound O([C@@H]1[C@@H](NC)[C@@H](O)[C@H]([C@@H]([C@H]1O1)O)NC)[C@]2(O)[C@H]1O[C@H](C)CC2=O UNFWWIHTNXNPBV-WXKVUWSESA-N 0.000 description 1
- 229960000887 spectinomycin hydrochloride Drugs 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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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
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a rare earth metal-organic frame with a fluorescent recognition function. The chemical formula is {[Tb2(TATAB)2)].4H2O.6DMF}n, wherein the TATAB in the formula is 4,4',4''-s-triazine-1,3,5-tri-para aminobenzoic acid; each metal framework structure elementary unit comprises two crystallographically independent Tb<3+> ions and two TATAB ligands, and the two Tb<3+> ions are connected into a dual-core elementary unit [Tb2(CO2)4] through six oxygen atoms on the two TATAB ligands; the dual-core units are connected into a one-dimensional Tb-carboxyl chain through the ligands, and extend towards four directions respectively through rigid benzene ring carboxyl on TATAB to form a three-dimensional porous network frame. The rare earth metal-organic frame has the advantages that the material synthesis process is simple, the crystal purity is high, the structure is novel, the stability in organic solvent is high, and formaldehyde and benzaldehyde can be recognized at the same time.
Description
[technical field]
The present invention relates to a kind of preparation method of Xi Tu Jin Shu – organic framework materials and the application in fluorescence sense thereof.
[background technology]
In recent years, various fluorescent sensing material causes the great interest of people, wherein Lanthanide-metal organic backbone (Ln-MOFs) gets most of the attention, and this is mainly because it is perfectly combined togather the porous of the fluorescence feature of lanthanide ion and MOFs.Lanthanide ion is as the metal center of Ln-MOFs, and for which providing good photoluminescent property, mainly because the fluorescence of lanthanide ion has stokes (Stokes) displacement greatly, glow color purity is high, fluorescence lifetime length and red (Eu
3+), green (Tb
3+), blue (Eu
2+) feature that three primary colours are various.For a lot of Ln-MOFs, the realization of their fluorescence detection functions also will be fixed against guest molecule (comprising negatively charged ion, metallic cation and organic molecule) and enter duct in skeleton.Thus, the first step of constructing Ln-MOFs fluorescent probe is exactly enable guest molecule enter duct by the size of crystal engineering adjustment aperture.By object interactional with specific guest molecule can be played to the adjustment of duct shape and inner surfaces of pores environment.In addition, functional groups on skeleton, such as organic ligand has the site of Lewis acid or alkalescence or exposed metallic site, can and analyte between form hydrogen bond, coordination or π-π and interact, and then improve the sensitivity to object identification.In a word, guest molecule enters inside, duct and organic wall or the metal center intimate contact of main body frame, enhances Zhu – object and interacts.Guest molecule enter the physicochemical property that can affect or change main body frame, comprise the absorption and transmitting etc. of light.
A series of Ln-MOFs fluorescent sensing material is in the news, and their sensing range comprises inorganic metal ion, negatively charged ion, organic molecule pollutent and explosive substance.But PARA FORMALDEHYDE PRILLS(91,95) and phenyl aldehyde have the few of the Ln-MOFs fluorescent probe report of measuring ability, and the fluorescence Ln-MOFs that can detect these two kinds of organic molecules is more rare simultaneously.As everyone knows, formaldehyde is widely used in art work, is a kind of indoor pollutant extremely harmful to human body.Phenyl aldehyde is a kind of important solvent and chemical raw material, has hormesis to eyes and respiratory system.Phenylcarbinol has analgesic effect as the solvent of spectinomycin hydrochloride, but its exposure is easily oxidized to phenyl aldehyde in atmosphere." Chinese Pharmacopoeia " specifies, in phenylcarbinol, the content of phenyl aldehyde must not more than 0.2%, and the limitation of " European Pharmacopoeia " and " American Pharmacopeia " is lower, is 0.05%.For these reasons, the selectivity fluorescence identifying realizing PARA FORMALDEHYDE PRILLS(91,95) and phenyl aldehyde gets a good eye value.
[summary of the invention]
The object of the invention is for the above-mentioned state of the art, a kind of Xi Tu Jin Shu – organic framework materials and its preparation method and application is provided, this compound PARA FORMALDEHYDE PRILLS(91,95) and phenyl aldehyde have the function of fluorescence identifying, and can detect the existence of micro-benzene formaldehyde in phenylcarbinol injection liquid, can be applicable to suitability for industrialized production.
Technical scheme of the present invention:
Have a Xi Tu Jin Shu – organic frame for fluorescence identifying function, chemical formula is { [Tb
2(TATAB)
2] 4H
2o6DMF}
n(Tb-MOF), in formula, TATAB is 4,4 ', 4 "-s-triazine-1,3,5-tri--para-amino benzoic acid, n be 1 be metal-organic framework to just infinite natural number, MOF; Described metal-organic framework elementary cell comprises two crystallography independently Tb
3+ion and two TATAB parts.Two TATAB parts take similar coordination mode, just make their extension degree slightly different because the atom N on amino is different from the angle that adjacent triazine ring C atom and phenyl ring C atom are formed; Three carboxyls on TATAB part take two kinds of different coordination modes: the first is chelating/bridging three tooth, and another kind is the bidentate of symmetrical bridging, and whole part is as μ
6-bridge is connected to six Tb
3+ion center; Tb1 and Tb2 all comes from eight oxygen atom ligands of six TATAB parts, and solvent molecule does not participate in coordination; Bond distance's scope of Tb-O key is
consistent with Tb-O bond distance's scope of other compound; Tb1 and Tb2 connects into double-core elementary cell [Tb by six Sauerstoffatoms on three TATAB parts
2(CO
2)
4], double-core unit connects into the Tb-carboxyl chain of one dimension by part, these one-dimensional chains extend formation three-dimensional network framework by the rigidity phenyl ring carboxyl on TATAB respectively to four direction, this three-dimensional framework presents the rhomboid duct A of class of one dimension on crystallography c-axis, around surrounded by 4 olivary duct B, opening cross-sectional area is
calculate programanalysis by the porosity in para figure software (PLATON/SOLV), the solvent occupation rate in framework is about 60.0%; Described metal-organic framework belongs to oblique system, P2
1/ c spacer, unit cell parameters is:
β=76.36 (3) °.
A preparation method for described multifunctional rare-earth Jin Shu – organic frame, with Tb (NO
3)
36H
2o is metal-salt, with H
3tATAB is part, with DMF and H
2o is solvent, and synthesis step is as follows:
1) by the Tb (NO of 43.5mg
3)
36H
2the H of O and 47mg
3the polytetrafluoroethylliner liner that TATAB puts into hydrothermal reaction kettle mixes, then adds 3mL DMF and 2mL H
2in the mixed solvent of O, stirring at normal temperature 30min, obtains mixed solution;
2) above-mentioned mixed solution is smoked 72h at 80 DEG C, after taking out product, solid is separated;
3) with DMF by above-mentioned solids wash 3-5 time, obtain colourless needles hybrid material crystal.
An application for described multifunctional rare-earth Jin Shu – organic frame, for the fluorescence identifying of organic molecule.
Advantage of the present invention is:
This preparation method's technique is simple, and can obtain single crystal form, highly purified crystalline material; This product structure is novel, has higher stability in organic solvent; This product PARA FORMALDEHYDE PRILLS(91,95) and phenyl aldehyde have the function of fluorescence identifying, may be used for the existence detecting micro-benzene formaldehyde in phenylcarbinol injection liquid, and compared with traditional vapor-phase chromatography, the method has the qualitative advantage such as quick, economic, easy.
[accompanying drawing explanation]
Fig. 1 is { [Tb
2(TATAB)
2] 4H
2o6DMF}
nsingle crystal diffraction structure iron.
Fig. 2 is { [Tb
2(TATAB)
2] 4H
2o6DMF}
nthe X-ray powder diffraction pattern after three days is soaked in formaldehyde and phenyl aldehyde.
Fig. 3 (a) is { [Tb
2(TATAB)
2] 4H
2o6DMF}
nfluorescence intensity figure in selected organic molecule, Fig. 3 (b) are that material is in selected organic molecule
5d
4→
7f
5fluorescent emission intensity variation diagram.
Fig. 4 (a) is the fluorescence intensity change figure of the phenyl aldehyde adding different amount in the strongest ethanol of fluorescence intensity, Fig. 4 (b) is when adding the phenyl aldehyde of different amount to ethanol
5d
4→
7f
5fluorescent emission intensity variation diagram.
Fig. 5 (a) is the fluorescence intensity change figure adding different amount phenyl aldehyde in phenylcarbinol, when Fig. 5 (b) is the phenyl aldehyde adding different amount in phenylcarbinol
5d
4→
7f
5fluorescent emission intensity variation diagram.
[embodiment]
Embodiment:
Have a Xi Tu Jin Shu – organic frame for fluorescence identifying function, as shown in Figure 1, chemical formula is { [Tb
2(TATAB)
2] 4H
2o6DMF}
n(Tb-MOF), in formula, TATAB is 4,4 ', 4 "-s-triazine-1,3,5-tri--para-amino benzoic acid, n be 1 be metal-organic framework to just infinite natural number, MOF; Described metal framework structure elementary cell comprises two crystallography independently Tb
3+ion and two TATAB parts.Two TATAB parts take similar coordination mode, just make their extension degree slightly different because the atom N on amino is different from the angle that adjacent triazine ring C atom and phenyl ring C atom are formed; Three carboxyls on TATAB part take two kinds of different coordination modes: the first is chelating/bridging three tooth, and another kind is the bidentate of symmetrical bridging, and whole part is as μ
6-bridge is connected to six Tb
3+ion center; Tb1 and Tb2 all comes from eight oxygen atom ligands of six TATAB parts, and solvent molecule does not participate in coordination; Bond distance's scope of Tb-O key is
consistent with Tb-O bond distance's scope of other compound; Tb1 and Tb2 connects into double-core elementary cell [Tb by six Sauerstoffatoms on three TATAB parts
2(CO
2)
4], double-core unit connects into the Tb-carboxyl chain of one dimension by part, these one-dimensional chains extend formation three-dimensional network framework by the rigidity phenyl ring carboxyl on TATAB respectively to four direction, this three-dimensional framework presents the rhomboid duct A of class of one dimension on crystallography c-axis, around surrounded by 4 olivary duct B, opening cross-sectional area is
calculate programanalysis by the porosity in para figure software (PLATON/SOLV), the solvent occupation rate in framework is about 60.0%; Described metal-organic framework belongs to oblique system, P2
1/ c spacer, unit cell parameters is:
β=76.36 (3) °.
A preparation method for described multifunctional rare-earth Jin Shu – organic frame, with Tb (NO
3)
36H
2o is metal-salt, with H
3tATAB is part, with DMF and H
2o is solvent, and synthesis step is as follows:
1) by the Tb (NO of 43.5mg
3)
36H
2the H of O and 47mg
3the polytetrafluoroethylliner liner that TATAB puts into hydrothermal reaction kettle mixes, then adds 3mL DMF and 2mL H
2in the mixed solvent of O, stirring at normal temperature 30min, obtains mixed solution;
2) above-mentioned mixed solution is smoked 72h at 80 DEG C, after taking out product, solid is separated;
3) with DMF by above-mentioned solids wash 3 times, obtain colourless needles hybrid material crystal.The productive rate calculated based on metal Tb is 75%.
The Xi Tu Jin Shu – metal-organic framework hybrid material of preparation is used for the fluorescence identifying of organic molecule, method the material of preparation is got respectively 3mg to be immersed in 2mL formaldehyde, ethanol, methyl alcohol, phenylcarbinol, m-xylene, p-Xylol, o-Xylol, N-Methyl pyrrolidone, toluene, tetrahydrofuran (THF), cyanobenzene, 1, in 4-dioxane, benzene, methylene dichloride, chloroform, phenyl aldehyde, ultrasonic oscillation to suspension liquid, with its characteristic emission peak intensity of fluorescent spectrophotometer assay.
This multi-function metal You – machine frame material structure and property representation:
1) structure determination of this Jin Shu You – machine frame material
Crystal structure determination adopts Supernova type X-ray single crystal diffraction instrument, uses through graphite monochromatised Mo-K
αray
for incident radiation source, with
scan mode collects point diffraction, obtains unit cell parameters, utilize SHELXL-97 direct method to solve crystalline structure from difference Fourier electron density map through least-squares refinement, and through Lorentz and polarizing effect correction.All H atom are synthesized by difference Fourier and are determined by ideal position calculating.Solvent molecule accurately quantity is determined by thermogravimetric and ultimate analysis test, and detailed axonometry data are in table 1, and structure is shown in Fig. 1.
Table 1: the crystallographic data of title complex
Fig. 1 is { [Tb
2(TATAB)
2] 4H
2o6DMF}
nsingle crystal diffraction structure iron, show that this material is polymkeric substance.
2) stability test
20mg sample is immersed in respectively 40% formalin and phenyl aldehyde in keep three days, filter, dry in solid washing with alcohol air, carry out powdery diffractometry test.
Fig. 2 is { [Tb
2(TATAB)
2] 4H
2o6DMF}
npowder diagram after immersion, shows in figure: the structure of material can well be kept, and illustrates that this material has higher stability in organic solvent.
3) photoluminescent property of this skeleton construction characterizes:
Described skeleton construction is tested as shown in Fig. 3, Fig. 4 and Fig. 5 the fluorescence identifying effect of different organic molecule and sensitive detection.
As can be seen from Figure 3, in selected solvent, the fluorescence intensity of material shows the dependency to organic molecule, and wherein PARA FORMALDEHYDE PRILLS(91,95) shows maximum Fluorescence Increasing, shows fluorescent quenching effect completely to phenyl aldehyde.As can be seen here, the phenomenon of this Fluorescence Increasing of this material and cancellation is suitable for detecting formaldehyde and phenyl aldehyde.As far as we know, this is the Ln-MOF that the first PARA FORMALDEHYDE PRILLS(91,95) and phenyl aldehyde have fluorescence identifying function simultaneously.
In order to the sensitivity of research material identification phenyl aldehyde, phenyl aldehyde is added dropwise in the alcohol suspending liquid of this material gradually, and have recorded the change (why selecting ethanol to be that this material has the strongest fluorescence in ethanol because in all solvents that can dissolve each other with phenyl aldehyde) of fluorescence intensity.As shown in Figure 4, the fluorescence intensity of material adds along with phenyl aldehyde the downtrending still presented in various degree.When the volume content of phenyl aldehyde is 0.01% to 0.1% time, fluorescence intensity presents linear changing relation, when the volume content of phenyl aldehyde is 2.5% time, the fluorescence of material is just substantially by complete cancellation, and this result shows that this material has very high sensitivity in the process detecting phenyl aldehyde.
There is based on the detection of this material to phenyl aldehyde the susceptibility of height, can be used for detecting the existence of micro-benzene formaldehyde in phenylcarbinol injection liquid.As shown in Figure 5, along with the increase of phenyl aldehyde volume content in phenylcarbinol, the fluorescence intensity of described material presents downward trend gradually.When phenyl aldehyde volume content is 2%, the fluorescence of material, just almost by complete cancellation, has the sensitivity of the MOFs of recognition reaction high a lot of to phenyl aldehyde than other reports.With the increase of phenyl aldehyde content, there is decline in various degree in fluorescence intensity, and when phenyl aldehyde content is 0.01% to 0.15% time, linear decline appears in fluorescence intensity, illustrate can be quantitative within the scope of this detection phenylcarbinol in the content of phenyl aldehyde.
Claims (3)
1. rare soil gold with fluorescence identifying function belongs to a – organic frame, it is characterized in that: chemical formula is { [Tb
2(TATAB)
2] 4H
2o6DMF}
n(Tb-MOF), in formula, TATAB is 4,4 ', 4 "-s-triazine-1,3,5-tri--para-amino benzoic acid, n be 1 be metal-organic framework to just infinite natural number, MOF; Described metal-organic framework elementary cell comprises two crystallography independently Tb
3+ion and two TATAB parts.Two TATAB parts take similar coordination mode, just make their extension degree slightly different because the atom N on amino is different from the angle that adjacent triazine ring C atom and phenyl ring C atom are formed; Three carboxyls on TATAB part take two kinds of different coordination modes: the first is chelating/bridging three tooth, and another kind is the bidentate of symmetrical bridging, and whole part is as μ
6-bridge is connected to six Tb
3+ion center; Tb1 and Tb2 all comes from eight oxygen atom ligands of six TATAB parts, and solvent molecule does not participate in coordination; Bond distance's scope of Tb-O key is
consistent with Tb-O bond distance's scope of other compound; Tb1 and Tb2 connects into double-core elementary cell [Tb by six Sauerstoffatoms on three TATAB parts
2(CO
2)
4], double-core unit connects into the Tb-carboxyl chain of one dimension by part, these one-dimensional chains extend formation three-dimensional network framework by the rigidity phenyl ring carboxyl on TATAB respectively to four direction, this three-dimensional framework presents the rhomboid duct A of class of one dimension on crystallography c-axis, around surrounded by 4 olivary duct B, opening cross-sectional area is
calculate programanalysis by the porosity in para figure software (PLATON/SOLV), the solvent occupation rate in framework is about 60.0%; Described metal-organic framework belongs to oblique system, P2
1/ c spacer, unit cell parameters is:
β=76.36 (3) °.
2. multifunctional rare-earth gold belongs to a preparation method for – organic frame as claimed in claim 1, it is characterized in that: with Tb (NO
3)
36H
2o is metal-salt, with H
3tATAB is part, with DMF and H
2o is solvent, and synthesis step is as follows:
1) by the Tb (NO of 43.5mg
3)
36H
2the H of O and 47mg
3the polytetrafluoroethylliner liner that TATAB puts into hydrothermal reaction kettle mixes, then adds 3mL DMF and 2mL H
2in the mixed solvent of O, stirring at normal temperature 30min, obtains mixed solution;
2) above-mentioned mixed solution is smoked 72h at 80 DEG C, after taking out product, solid is separated;
3) with DMF by above-mentioned solids wash 3-5 time, obtain colourless needles hybrid material crystal.
3. multifunctional rare-earth gold belongs to an application for – organic frame as claimed in claim 1, it is characterized in that: for the fluorescence identifying of organic molecule.
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| CN105753891A (en) * | 2016-03-23 | 2016-07-13 | 浙江大学 | Rare earth organic framework material for fluorescence detection of trace water and preparation method of rare earth organic framework material |
| CN105885057A (en) * | 2016-04-20 | 2016-08-24 | 郑州轻工业学院 | Metal-organic framework coordination polymer composite material and preparation method and application thereof |
| CN106916317A (en) * | 2017-02-27 | 2017-07-04 | 三峡大学 | A kind of Rare Earth Europium base organic crystalline material, prepares and the application on fluorescence identifying antibiotic |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090050014A1 (en) * | 2007-08-23 | 2009-02-26 | Sensient Colors Inc. | Self-dispersed pigments and methods for making and using the same |
| CN102125790A (en) * | 2011-01-20 | 2011-07-20 | 中国科学院化学研究所 | Application of metal organic framework material in adsorption of indoor polluted air |
-
2015
- 2015-04-24 CN CN201510198517.0A patent/CN104804027B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090050014A1 (en) * | 2007-08-23 | 2009-02-26 | Sensient Colors Inc. | Self-dispersed pigments and methods for making and using the same |
| CN102125790A (en) * | 2011-01-20 | 2011-07-20 | 中国科学院化学研究所 | Application of metal organic framework material in adsorption of indoor polluted air |
Non-Patent Citations (4)
| Title |
|---|
| JU-HSIOU LIAO等: "Synthesis, Characterization and Photoluminescence of Lanthanide Metal-organic Frameworks, Constructed from Triangular 4,4",4""-s-triazine-1,3,5-triyl-p-aminobenzoate Ligands", 《J.CHIN.CHEM.SOC.》 * |
| MIAO DU等: "Versatile Mesoporous DyIII Coordination Framework for Highly efficient Trapping of Diverse Pollutants", 《INORGANIC CHEMISTRY》 * |
| TAHEREH MORADPOUR等: "A nanoporous 3D zinc(II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
| 杨井花: "铕（III）/铽（III）及镝（III）金属有机荧光配位聚合物的合成及其在醛类分子识别中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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