CN106432295A - Construction of shining metal organic frame for Eu<3+> sensitization - Google Patents
Construction of shining metal organic frame for Eu<3+> sensitization Download PDFInfo
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- CN106432295A CN106432295A CN201610841597.1A CN201610841597A CN106432295A CN 106432295 A CN106432295 A CN 106432295A CN 201610841597 A CN201610841597 A CN 201610841597A CN 106432295 A CN106432295 A CN 106432295A
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- metal organic
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- rare earth
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 206010070834 Sensitisation Diseases 0.000 title claims abstract description 33
- 230000008313 sensitization Effects 0.000 title claims abstract description 33
- 238000010276 construction Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 8
- 238000002189 fluorescence spectrum Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- GDLZGLLSIVMLOL-UHFFFAOYSA-N C(=O)N.C(=O)N.S1C=CC=C1 Chemical compound C(=O)N.C(=O)N.S1C=CC=C1 GDLZGLLSIVMLOL-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 150000001661 cadmium Chemical class 0.000 claims 1
- 239000012153 distilled water Substances 0.000 claims 1
- 238000010998 test method Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- -1 rare earth ion Chemical class 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 208000011580 syndromic disease Diseases 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 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
- 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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention relates to synthesis of a shining metal organic frame and an application of the shining metal organic frame to Eu<3+> protection and sensitization. The synthesized shining metal organic frame can be used for protection and sensitization of the Eu<3+> in a water solution. The fluorescence intensity of the shining metal organic frame is gradually changed along with increasing of the concentration and the sensitization time of the Eu<3+>. Therefore, the shining metal organic frame has the potential application in Eu<3+> protection and sensitization.
Description
Technical field
The present invention relates to a kind of luminescent metal organic frame is in Eu3+Application in sensitization.
Technical background
Luminescent metal organic framework materials are that a class porosity is high, specific surface area is big, pore structure is controlled, stable chemical nature
The simply novel porous crystalline, luminescent material with preparation process.Recent research indicate that, such material is protected and quick in rare earth ion
Change aspect has potential using value, becomes adjustable luminescent material of new generation.Luminescent metal organic framework materials conduct
Scalable luminescent material of new generation mainly has following two reasons 1) luminescent metal organic frame has porosity characteristic and Gao Bibiao
Area, can absorb a large amount of rare earth ions, thus improving detection sensitivity；2) metal organic frame having difference in functionality group can
To produce the support of a protectiveness, it is to avoid be quenched in the hydration of host-guest system Rare Earth Ion.There is machine frame with metal on document
Frame come to protect and be sensitized rare earth ion report also little.We select centered on thiphene ring, and introduce the carboxylic of many coordination sites
Base group and polar amide groups, make part can not only bond together to form porous with multiple flexible coordination modes and metal ion
Luminescent metal organic framework materials, and metal can be caused by using the interaction between amide group and guest molecule
The characteristic of organic framework materials luminescent behavior change, realizes the selective protection to rare earth ion and sensitization.Analyzed based on above
We have probed into 2,5- bis--(3,5- dicarboxyphenyi) thiophene diformamide as lighting that organic ligand and cadmium ion are constructed
Application in rare earth ion protection and sensitization for the metal organic frame.
Content of the invention
It is an object of the invention to probing into a kind of luminescent metal organic framework materials in rare earth ion protection and sensitization
Application, thus provide experiment basis for rare earth ion protection in aqueous.
For achieving the above object, the present invention adopts following technical proposals：
The present invention is prepared for 2,5- bis--(3,5- dicarboxyphenyi) thiophene diformamide (H using solvent-thermal method4L) and
CdCl2·5/2H2The luminescent metal organic frame that O is formed, its concrete preparation process is：By CdCl2·5/2H2O、H4L part,
The mixture of DMF and water is placed in polytetrafluoroethylliner liner, isothermal reaction 3 days at 85 DEG C, naturally cools to room temperature, filters,
Products therefrom is washed with DMF, drying at room temperature, obtains bulk crystals.
As shown in figure 1, belonging to anorthic system, space group is P ī to the structure of metal organic frame disclosed by the invention, structure cell
Parameter isα=82.19 (3) °, β=76.50 (3) ° and γ=
70.14(3)°.Z=2.Independent cadmium ion in two crystallography is comprised in the asymmetric cell of coordination compound, four
Individual L part, hydrone, five free hydrones and two free DMF molecules of four coordinations.Cd1 is seven coordinations, four
Individual oxygen atom comes from two different L parts WithThree oxygen atoms come from three hydrones Therefore Cd1 is the pentagonal bipyramid body of distortion.With
Unlike Cd1, Cd2 is hexa-coordinate, and four oxygen atoms come from two different L parts Two oxygen are former
Son comes from two hydrones Therefore Cd2 is the octahedron of distortion.
In coordination compound, the carboxyl half in all of L part is deprotonation, and second half is non-deprotonation.
And, in coordination compound, each L ligand molecular takes monodentate ligand and the coordination mode of bidentate chelating respectively, connects Cd ion
Define the layer structure of two dimension.These two-dimentional layer structures further pass through hydrogen bond and pi-pi accumulation connects formation 3D and surpasses
Molecular network, is shown in Fig. 2.From in figure it will be seen that coordination compound has larger hole, in hole, it is filled with solvent
DMF and hydrone, are calculated by platon, and after removing solvent molecule, the porosity of coordination compound is 22.9%.
The rare earth ion that the present invention is sensitized is Eu3+, Tb3+And La3+.
The present invention protects and the method for sensitization rare earth ion is, with Eu3+Sensitization as a example：
Preparing substance withdrawl syndrome is 10-1M, 10-2M, 10-3M, 10-4M and 10-5The Eu of M3+Aqueous solution standby, claim respectively
The metal organic frame taking 5mg synthesis adds the above-mentioned Eu of 3mL3+Aqueous solution standing.Interval same time measures its fluorescence respectively
Emission spectrum simultaneously draws different sensitization times and the fluorescence emission spectrum of different sensitization concentration.Have not yet to see document or specially
Profit is using the protection of this coordination compound and sensitization Eu3+Report.
In the same manner to Tb3+And La3+Sensitization effect see accompanying drawing.
This has absolutely proved that fluorescent sensing material provided by the present invention can be used for Eu3+Protection and sensitization.
Luminescent metal organic frame application provided by the present invention has following features：
1. the luminescent metal organic frame of synthesis is by Eu3+, Tb3+And La3+Sensitization test discovery can be used as aqueous solution
Middle Eu3+Encapsulation.
2. the luminescent metal organic framework materials of synthesis are in Eu3+Protection and sensitization aspect have quick, easy, sensitive etc.
Advantage.
In sum, the invention provides a kind of luminescent metal organic frame is protected and sensitization Eu3+A kind of method, dilute
Native ion protection and sensitization aspect have potential using value.
Brief description
Fig. 1 is the structure chart of synthesized luminescent metal organic frame；
Fig. 2 is the supramolecular structured composition of 3D of synthesized luminescent metal organic frame；
Fig. 3 is the sensitization design sketch to different rare earth ions for the synthesized luminescent metal organic frame；
Fig. 4 is synthesized luminescent metal organic frame to variable concentrations Eu3+Sensitization design sketch；
Fig. 5 is synthesized luminescent metal organic frame is 10 to concentration-2M Eu3+The sensitization design sketch of different time；
Specific embodiment
The synthesis of embodiment 1 coordination compound：
By H4L (17.4mg, 0.035mmol), CdCl2·5/2H2O (22.8mg, 0.1mmol), 3mL DMF (N, N- diformazan
Base Methanamide) and 2mL H2O mixture is placed in polytetrafluoroethylliner liner, and at 85 DEG C, isothermal reaction 3 days, naturally cool to room
Temperature, filters, and products therefrom is washed with DMF, and drying at room temperature obtains bulk crystals [Cd2(H2L)2(H2O)5]·5H2O·2DMF.
Embodiment 2 (selection of sensitization rare earth ion), process is as follows：
Preparing substance withdrawl syndrome is 10-2The Eu of M3+, Tb3+And La3+Aqueous solution is standby, weighs the metal of 5mg synthesis respectively
Organic frame adds the aqueous solution standing of the above-mentioned different rare earth ions of 3mL.Measure its fluorescence emission spectrum two days later and draw glimmering
Optical emission spectroscopy is shown in Fig. 3.
Embodiment 3 (variable concentrations Eu3+Sensitization), process is as follows：
Preparing substance withdrawl syndrome is 10-1M, 10-2M, 10-3M, 10-4M and 10-5The Eu of M3+Aqueous solution standby, claim respectively
The metal organic frame taking 5mg synthesis adds the above-mentioned Eu of 3mL3+Aqueous solution standing.Measure its fluorescence emission spectrum respectively and paint
The fluorescence emission spectrum of system different sensitization concentration is shown in Fig. 4.
Embodiment 4 (10-2MEu3+Different sensitization times), process is as follows：
Preparing substance withdrawl syndrome is 10-2The Eu of M3+Aqueous solution standby, weigh respectively 5mg synthesis metal have machine frame
Frame adds the above-mentioned Eu of 3mL3+Aqueous solution standing.Interval same time measures its fluorescence emission spectrum respectively and draws different sensitizations
The fluorescence emission spectrum of time is shown in Fig. 5.
Claims (7)
1. one kind can be used for Eu3+The preparation method of the luminescent metal organic frame of sensitization, prepares cadmium salt and 2 using solvent-thermal method,
5- bis--(3,5- dicarboxyphenyi) thiophene diformamide (H4L) the luminescent metal organic frame that part is formed, it was specifically prepared
Cheng Wei：H4L part and CdCl2·5/2H23.5: 10 addition DMF 3mL and distilled water 2mL mixing are placed in polytetrafluoro to O in molar ratio
In ethylene inner bag, isothermal reaction 3 days at 85 DEG C, then naturally cool to room temperature, filter, products therefrom is washed with DMF, room temperature
It is dried, obtain bulk crystals [Cd2(H2L)2(H2O)5]·5H2O·2DMF.
2. luminescent metal organic frame according to claim 1 is it is characterised in that the structure of described coordination compound is：Crystal belongs to
In anorthic system, space group isCell parameter isα
=82.19 (3) °, β=76.50 (3) ° and γ=70.14 (3) °.
3. the luminescent metal organic frame described in claim 1 is in Eu3+Application in encapsulation.
4. the application described in claim 3, the rare earth ion of selection is Eu3+, Tb3+And La3+.
5. the application described in claim 3 or 4, method of testing is：(1) weigh appropriate metal organic frame to sequentially add mole
Concentration is 10-1M, 10-2M, 10-3M, 10-4M and 10-5In the aqueous solution of the rare earth ion of M, test different sensitization times respectively
Fluorescence emission spectrum (2) draws different sensitization times and the fluorescence emission spectrum of different sensitization concentration.
6., shown in claim 4, rare earth ion and metal organic frame can produce interaction, thus leading to the glimmering of coordination compound
Light changes.
7. the method described in claim 5 is it is characterised in that described solvent is aqueous solution, luminescent metal organic backbone and solvent
Proportioning is 5mg: 3mL.
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| CN201610841597.1A CN106432295A (en) | 2016-09-21 | 2016-09-21 | Construction of shining metal organic frame for Eu<3+> sensitization |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108593610A (en) * | 2018-04-17 | 2018-09-28 | 武汉大学 | A kind of preparation method of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV-MOF |
| CN109575296A (en) * | 2017-09-28 | 2019-04-05 | 天津工业大学 | A kind of transition metal Zn complex and Fe3+The photocatalysis performance of modified composite material |
-
2016
- 2016-09-21 CN CN201610841597.1A patent/CN106432295A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575296A (en) * | 2017-09-28 | 2019-04-05 | 天津工业大学 | A kind of transition metal Zn complex and Fe3+The photocatalysis performance of modified composite material |
| CN108593610A (en) * | 2018-04-17 | 2018-09-28 | 武汉大学 | A kind of preparation method of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV-MOF |
| CN108593610B (en) * | 2018-04-17 | 2020-01-24 | 武汉大学 | Preparation method of fluorescence-enhanced test paper based on nanometer MV-MOF |
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