CN105566363A - Rare earth coordination polymer based on tripod flexible ligand, preparation method and applications thereof - Google Patents
Rare earth coordination polymer based on tripod flexible ligand, preparation method and applications thereof Download PDFInfo
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- CN105566363A CN105566363A CN201610004171.0A CN201610004171A CN105566363A CN 105566363 A CN105566363 A CN 105566363A CN 201610004171 A CN201610004171 A CN 201610004171A CN 105566363 A CN105566363 A CN 105566363A
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- rare earth
- coordination polymer
- polymer based
- trivet
- flexible part
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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 System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
- 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
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
The invention relates to a rare earth coordination polymer based on a tripod flexible ligand, a preparation method and applications thereof. According to the preparation method, Eu(NO3)3.6H2O, an organic ligand (H3tci), and solvents (N,N-dimethyl formamide and water) are added into a container and stirred at a room temperature, then the container is sealed and placed in a baking oven with a temperature of 378 K for three days; the container is slowly cooled to the room temperature, colorless transparent block-liked crystals are obtained; and then the crystals are washed by N,N-dimethyl formamide, filtered and dried to obtain the target product. The provided rare earth coordination polymer based on a tripod flexible ligand has a strong fluorescence performance and a specific Fe<3+> recognition function and can be used as a fluorescence probe therefore.
Description
Technical field
The present invention relates to a kind of preparation method and application of the rare earth coordination polymer based on the flexible part of trivet, specifically, relate to a kind of to Fe
3+there is specific recognition function, can be used as the rare earth coordination polymer based on the flexible part of trivet of fluorescent probe.
Background technology
The multi-function metal ligand polymer with character such as luminescence, magnetic, highly porouies due to have charming Diversity structure with in gas adsorption, be separated, photoluminescence, magnetic, catalysis, especially as the application of the aspects such as chemical sensor, in recent years, increasing concern is received.Based on the analysis of synthesis strategy, the structure of metal organic coordination polymer can realize by selecting suitable organic ligand and metal center and suitable reaction conditions (as temperature, solvent, pH and reactive chemistry metrology etc.).And wherein the most important thing is, select the geometric configuration of suitable organic ligand, rigidity/handiness and coordinating group are a kind of methods of effective control and the stuctures and properties coordinating polymkeric substance.Therefore passing through design, select organic linker and metal unit to build the metallic organic framework with special construction and function, is the direction of constantly research.
Summary of the invention
The object of the invention is to utilize Eu
iIIas metal node, utilize three (2-hydroxyethyl) chlorinated isocyanurates (H
3tci) as organic ligand, at a certain temperature, the method for solvent thermal is utilized to synthesize a kind of rare earth coordination polymer based on the flexible part of trivet.
The technical solution used in the present invention is: a kind of rare earth coordination polymer based on the flexible part of trivet, and preparation method comprises the following steps:
1) by Eu (NO
3)
36H
2o, organic ligand H
3tci (three (2-hydroxyethyl) chlorinated isocyanurates), DMF, water adds in container, under normal temperature, stirs;
2) put into baking oven by after container sealing, under 373-383K, keep 70-75h; Preferably, temperature rise rate is 5Kmin
-1;
3) progressively cool to room temperature, at least leave standstill after 1 day, obtain water white transparency bulk crystals; Preferably, the rate of temperature fall progressively cooling to room temperature is 5Kh
-1, and at room temperature at least leave standstill 24 hours;
4) with DMF washing, filter, dry, obtain target product.
The invention has the beneficial effects as follows: the present invention selects H
3tci as organic ligand, H
3tci has the arm of high flexible, can promote the formation of novel network topology and coordinate the construction of polymkeric substance.A kind of rare earth coordination polymer based on the flexible part of trivet prepared by the present invention can be used as multifunctional material and is applied to fluorescent molecular probe field.The synthetic method of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention is simple, has great application prospect.
Accompanying drawing explanation
Fig. 1 is the synthesis schematic diagram of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention.
Fig. 2 is the XRD figure of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention.
Fig. 3 is the coordination environment schematic diagram of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention.
Fig. 4 is the coordination mode schematic diagram of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention.
Fig. 5 is the three-dimensional packed structures schematic diagram of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention.
Fig. 6 is the fluorescence spectrum figure of the fluorescence intensity of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention.
Fig. 7 is methyl alcohol suspension liquid fluorescence intensity figure under different metal of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention.
Embodiment
Embodiment 1 one kinds of rare earth coordination polymers based on the flexible part of trivet
Preparation method is as follows:
By the Eu (NO of 0.075mmol
3)
36H
2three (2-hydroxyethyl) chlorinated isocyanurates (H of O, 0.005mmol
3tci), the DMF (DMF) of 1.5ml, the water of 1.5ml adds in vial, under normal temperature, stirs 30 minutes.Vial good seal is put into baking oven.Heating makes the temperature of baking oven reach 378K from room temperature, and temperature rise rate is 5Kmin
-1, and be incubated 72 hours under maintaining the temperature at this condition.With 5Kh
-1rate of temperature fall progressively cool to room temperature, obtain water white transparency bulk crystals; With N, N '-dimethyl methane amide (DMF) solution washing, filtration are also dry in atmosphere, and be a kind of rare earth coordination polymer based on the flexible part of trivet of target product, productive rate is 35%.
As shown in Figure 2, in figure, i is the crystal powder diffractogram of simulation to the XRD of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention's synthesis, and ii is the powder diagram that composite crystals is surveyed.
As shown in Figure 3-Figure 5, this crystalline structure belongs to triclinic(crystalline)system to the structure of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention's synthesis, and spacer is P-1.Molecular formula is: [Eu (tci) (H
2o)] DMF2H
2o.This compound is by H
3a kind of interesting three-dimensional structure of tci part bridging.Each H
3tci part and six Eu
3+ion coordination, each Eu
3+ion and eight come from H
3oxygen on tci carboxyl and an oxygen coordination from coordinated water.
Embodiment 2 one kinds is based on the luminescence of the rare earth coordination polymer of the flexible part of trivet
Method: carry out luminescent properties experiment with a kind of rare earth coordination polymer based on the flexible part of trivet prepared by embodiment 1.
1. be 396nm with excitation wavelength, record the fluorescence emission spectrogram (em396nm) based on the rare earth coordination polymer crystal of the flexible part of trivet, its emission peak is
5d
0→
7f
0(581nm),
5d
0→
7f
1(594nm),
5d
0→
7f
2(621nm),
5d
0→
7f
3(651nm) and
5d
0→
7f
4(700nm), wherein
5d
0→
7f
2(621nm) emission peak is the strongest fluorescence emission peak.Be 621nm with emission wavelength, record the fluorescent exciting spectrogram (ex621nm) based on the rare earth coordination polymer crystal of the flexible part of trivet, its excitation peak is 396nm.As shown in Figure 6, Fig. 6 is a kind of Solid fluorescene spectrum figure of the rare earth coordination polymer based on the flexible part of trivet to result.
2. the crystal getting a kind of rare earth coordination polymer based on the flexible part of trivet is dissolved in methanol solvate, and obtaining a kind of rare earth coordination polymer concentration based on the flexible part of trivet is 1 × 10
-4the mixing solutions of M.
Get mixing solutions 5ml respectively, adding 25ul concentration is respectively 1 × 10
-4the Fe of M
3+, Al
3+, Mg
2+, Pb
2+, Cu
2+, Li
+, Cd
2+, Cr
3+, Zn
2+, Na
+, Ca
2+, Hg
2+, Ag
+, Ni
2+methanol solution, does blank (blank) simultaneously.Take wavelength as 396nm light be exciting light, detect the change of the fluorescence intensity of a kind of rare earth coordination polymer based on the flexible part of trivet in mixing solutions with fluorophotometer.
As shown in Figure 7, as seen from Figure 7, a kind of crystal of the rare earth coordination polymer based on the flexible part of trivet has very strong fluorescence property to result in methanol solvate, and meets Fe
3+fluorescent quenching.This illustrates that the crystal of a kind of rare earth coordination polymer based on the flexible part of trivet of the present invention can be used as fluorescent probe and detects Fe
3+.
Claims (7)
1. based on a rare earth coordination polymer for the flexible part of trivet, it is characterized in that: preparation method comprises the steps:
1) by Eu (NO
3)
36H
2o, organic ligand H
3tci, DMF, water adds in container, under normal temperature, stirs;
2) put into baking oven by after container sealing, under 373-383K, keep 70-75h;
3) progressively cool to room temperature, at least leave standstill after 1 day, obtain water white transparency bulk crystals;
4) with DMF washing, filter, dry, obtain target product.
2. a kind of rare earth coordination polymer based on the flexible part of trivet according to claim 1, it is characterized in that: the described rare earth coordination polymer based on the flexible part of trivet, its crystal belongs to triclinic(crystalline)system, and spacer is P-1, each organic ligand H
3tci and six Eu
3+ion coordination, each Eu
3+ion and eight come from organic ligand H
3oxygen on tci carboxyl and an oxygen coordination from coordinated water.
3. a kind of rare earth coordination polymer based on the flexible part of trivet according to claim 1 and 2, is characterized in that: step 2) in, put into baking oven by after container sealing, temperature rise rate is 5Kmin
-1.
4. a kind of rare earth coordination polymer based on the flexible part of trivet according to claim 1 and 2, is characterized in that: the described rate of temperature fall progressively cooling to room temperature is 5Kh
-1.
5. the application in fluorescent probe field of a kind of rare earth coordination polymer based on the flexible part of trivet according to claim 1.
6. application according to claim 5, it is characterized in that: a kind of rare earth coordination polymer based on the flexible part of trivet according to claim 1 is mixed with methyl alcohol suspension liquid, the methanol solution of dropping metal ion take wavelength as 396nm light is exciting light, carries out fluoroscopic examination.
7. application according to claim 6, is characterized in that: described metal ion is Fe
3+.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337669A (en) * | 2017-07-03 | 2017-11-10 | 虞雯 | A kind of preparation method of tripod-type part for unimolecule magnetic |
| CN115819786A (en) * | 2022-11-08 | 2023-03-21 | 江苏科技大学 | Europium-based luminescent metal organic framework material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1811430A (en) * | 2005-01-26 | 2006-08-02 | 中国科学院大连化学物理研究所 | Singlet oxygen europium coordination compound fluorescent probe and application thereof |
-
2016
- 2016-01-04 CN CN201610004171.0A patent/CN105566363B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1811430A (en) * | 2005-01-26 | 2006-08-02 | 中国科学院大连化学物理研究所 | Singlet oxygen europium coordination compound fluorescent probe and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SONG DANG ET AL.: "A layer-structured Eu-MOF as a highly selective fluorescent probe for Fe3+ detection through a cation-exchange approach", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| 张明洋: "三脚架型羧酸配体构筑的配位聚合物的合成、结构及其性质研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337669A (en) * | 2017-07-03 | 2017-11-10 | 虞雯 | A kind of preparation method of tripod-type part for unimolecule magnetic |
| CN115819786A (en) * | 2022-11-08 | 2023-03-21 | 江苏科技大学 | Europium-based luminescent metal organic framework material and preparation method and application thereof |
| CN115819786B (en) * | 2022-11-08 | 2023-08-22 | 江苏科技大学 | Europium-based luminescent metal organic framework material and preparation method and application thereof |
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