CN105503912B - A kind of new Zn (II) metal organic frameworks and its synthetic method and application - Google Patents
A kind of new Zn (II) metal organic frameworks and its synthetic method and application Download PDFInfo
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- CN105503912B CN105503912B CN201610004058.2A CN201610004058A CN105503912B CN 105503912 B CN105503912 B CN 105503912B CN 201610004058 A CN201610004058 A CN 201610004058A CN 105503912 B CN105503912 B CN 105503912B
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- C07F3/06—Zinc compounds
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- 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
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- 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
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- 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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
Abstract
The present invention relates to a kind of new Zn (II) metal organic frameworks and its synthetic method and application.The technical scheme of use is：By metal zinc salt, the dicarboxylic acids of 4'- (1H tetrazoles 5) biphenyl 3,5, N, N dimethylformamides are added in container, under normal temperature, are stirred；It is put into baking oven, under temperature 348K, is kept for 1 day after container is sealed；It is slowly cooled to room temperature, obtains colourless bulk crystals；Washing, filtering are simultaneously dried, and obtain target product.The metal organic frame (MOFs) that one kind prepared by the present invention is constructed by Zn (II) and the dicarboxylic acids of 4'- (1H tetrazoles 5) biphenyl 3,5 shows very strong fluorescence property, and to Mg2+With specific recognition function.
Description
Technical field
The present invention relates to the synthesis and its application of new Zn (II) metal organic framework, specifically, it is related to one kind by Zn
(II) and the metal organic framework (MOFs) constructed of 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids show it is very strong glimmering
Optical property, and to Mg2+With specific recognition function.
Background technology
Metal organic framework (MOFs) coordination polymer is novel three materials of crystal of a class, is being catalyzed, gas absorption,
Molecular recognition, the field such as optics is by extensive concern.Multi-function metal with properties such as luminescence, magnetic, high porosities has
Machine skeleton is because can be of particular concern as chemical sensor.In recent years, it is Fluoresceinated with the continuous progress of science and technology
Learning the characteristics of sensor is because of its high sensitivity enjoys people to pay close attention to.Fluorescence chemical sensor biological active matter quality detection, ion,
The field such as the detection of molecule and explosive detection all has a wide range of applications.Most metal-organic framework materials are by transition
What metal ion cluster was built, these systems are now subjected to increasing concern, not just merely because its charming structure, and also because
It can be applied in different scientific domains for him.The unique structure of coordination polymer is by different structure modules and reaction bar
Part adjusts the coordination mode of metal and part and obtained.Therefore built and had by design, selection organic ligand and metal unit
There are special construction and the metal organic framework of function, be the problem constantly researched and developed.
The content of the invention
The purpose of the present invention is, by the use of zinc as metal node, to utilize 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids
As organic ligand, at a certain temperature, a kind of 3D coordination polymers are synthesized using the method for solvent heat.
The technical solution adopted by the present invention is：New Zn (II) metal organic framework, the compound is by Zn (II) and 4'-
(1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids is constructed, and the compound crystal structure, which belongs to, two kinds in tetragonal crystal system, compound
Different Zn Atomic coordinate patterns, wherein, the first Zn Atomic coordinate pattern is four-coordination pattern：Two oxygen atoms come from 4'-
(1H- tetrazoles -5)-biphenyl -3,5- dicarboxylates a, N matches somebody with somebody from 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids
Body, an oxygen atom is from coordination OH‐；Second of Zn Atomic coordinate pattern is hexa-coordinate pattern：Three nitrogen-atoms come from 4'-
(1H- tetrazoles -5)-biphenyl -3,5- dicarboxylates, two oxygen atoms carry out 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxyl
Sour part, an oxygen atom is from coordination OH‐。
The synthetic method of above-mentioned new Zn (II) metal organic framework, including following synthesis step：
1) by metal zinc salt, 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids, DMF, which is added, to be held
In device, under normal temperature, stir；It is preferred that, described metal zinc salt is Zn (NO3)2。
2) it is put into after container is sealed in baking oven, under 343-353, keeps 22-28h；
3) it is slowly cooled to room temperature, obtains colourless bulk crystals；It is preferred that, the described cooling being slowly cooled to room temperature is fast
Rate is 15-20 DEG C of h-1。
4) wash, filter and dry, obtain target product.
The beneficial effects of the invention are as follows：Zn (II) and 4'- (1H- tetrazoles -5)-biphenyl -3,5- two prepared by the present invention
The metal organic frame (MOFs) that carboxylic acid is constructed shows very strong fluorescence property, and to Mg2+With specific recognition function.
It is prepared by the metal organic frame (MO Fs) that the Zn (II) and 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids of the present invention is constructed
Method is simple, and the compound has very big application value in field of fluorescence.
Brief description of the drawings
Fig. 1 is the synthesis schematic diagram of new Zn (II) metal organic framework (MOFs) of the invention.
Fig. 2 is the XRD of new Zn (II) metal organic framework (MOFs) of the invention.
Fig. 3 is the coordination mode schematic diagram of new Zn (II) metal organic framework (MOFs) of the invention.
Fig. 4 is the three dimensional structure diagram figure of new Zn (II) metal organic framework (MOFs) of the invention.
Fig. 5 is the fluorescent liquid launching light spectrogram of new Zn (II) metal organic framework (MOFs) of the invention.
Fig. 6 be new Zn (II) metal organic framework (MOFs) of the invention methanol suspension under different metal fluorescence it is strong
Degree figure.
Embodiment
Embodiment 1 Zn (II) metal organic framework (MOFs)
By 0.25mmol Zn (NO3)2, 0.05mmol 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids, 1mlN,
Dinethylformamide is added in 5ml vial.Vial good seal is put into baking oven.Heating reaches the temperature of baking oven
348K, and keeping temperature is incubated 24 hours under the conditions of herein.With 15-20 DEG C of h-1Rate of temperature fall be slowly cooled to room temperature, obtain
To colourless bulk crystals；Washing, filtering are simultaneously dried, as target product Zn (II) metal organic framework (MOFs), and yield is
65%.
The XRD of Zn (II) metal organic framework that the present invention is synthesized is as shown in Fig. 2 i spreads out for the crystal powder of simulation in figure
Figure is penetrated, ii is the powder diagram that synthetic crystal is surveyed.
As shown in Figure 3 and Figure 4, the crystal structure belongs to four directions to the structure of Zn (II) metal organic framework that the present invention is synthesized
Crystallographic system.Molecular formula is：{[Zn2(L)3.5(OH)2](DMF)3(H2O)2}n(L is 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxyls
Sour part).There are two kinds of different Zn Atomic coordinate patterns in the compound.Zn1 is four-coordination pattern, and two oxygen atoms come from
4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylates a, N comes from 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxyl
Sour part, an oxygen atom is from coordination OH-；Zn2 is hexa-coordinate pattern, three nitrogen-atoms from 4'- (1H- tetrazoles -5) -
Biphenyl -3,5- dicarboxylates, two oxygen atoms come 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylates, an oxygen original
Son is from coordination OH-。
(MOFs's) of embodiment 2 Zn (II) metal organic framework is luminous
Method：(MOFs) of Zn (II) metal organic framework prepared with embodiment 1 carries out luminescent properties experiment.
1) take the crystal of (MOFs) of Zn (II) metal organic framework to be dissolved in methanol solvate, obtain Zn (II) metal organic
Skeleton (MOFs) concentration is 1 × 10-4M mixed solution, using excitation wavelength as 305nm, measures the fluorescent emission of crystal, emission peak
For 560nm.
2) take the crystal of Zn (II) metal organic framework (MOFs) to be dissolved in methanol solvate, obtain the organic bone of Zn (II) metal
Frame (MOFs) concentration is 1 × 10-4M mixed solution.
Mixed solution 5ml is taken respectively, and it is 1 × 10 to be separately added into 25ul concentration-4M Ag+, Zn2+, Al3+, Bi3+, Cd2+, Ce3 +, Co2+, Cr3+, Cu2+, Fe3+, Hg2+, In3+, Mg2+, Na+, Ni2+, Pb2+Methanol solution, while doing blank (blank).With ripple
A length of 305nm light is exciting light, and Zn (II) metal organic framework (MOFs) crystal in mixed solution is detected with fluophotometer
The change of fluorescence intensity.
As a result as shown in fig. 6, occurring in that Zn (II) metal organic framework (MOFs) is characterized hair as seen from Figure 6, in collection of illustrative plates
The emission spectrum of ejected wave length.Illustrate the gold that the Zn (II) and 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids of the present invention are constructed
Category organic frame (MOFs) has very strong fluorescence property at normal temperatures.As seen from Figure 6, Zn (II) and 4'- (1H- tetrazoles -5) -
The crystal for the metal organic frame (MOFs) that biphenyl -3,5- dicarboxylic acids is constructed is in Mg2+Fluorescence is most strong in methanol solvate.This explanation is originally
The metal organic frame (MOFs) that one kind of invention is constructed by Zn (II) and 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids
Crystal can be used as fluorescence probe detection Mg2+。
Claims (7)
1. a kind of synthetic method of Zn (II) metal organic framework, it is characterised in that including following synthesis step：
1) by metal zinc salt, 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids, DMF is added in container,
In under normal temperature, stir；
2) it is put into after container is sealed in baking oven, under 343-353K, keeps 22-28h；
3) it is slowly cooled to room temperature, obtains colourless bulk crystals；
4) wash, filter and dry, obtain target product；
Described Zn (II) metal organic framework：Molecular formula is：{[Zn2(L)3.5(OH)2](DMF)3(H2O)2}n, wherein, L is
4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylates；The compound by Zn (II) and 4'- (1H- tetrazoles -5)-biphenyl -
3,5- dicarboxylic acids are constructed, and the compound crystal structure, which belongs to, two kinds of different Zn Atomic coordinate moulds in tetragonal crystal system, compound
Formula, wherein, the first Zn Atomic coordinate pattern is four-coordination pattern：Two oxygen atoms from 4'- (1H- tetrazoles -5)-biphenyl -
3,5- dicarboxylates a, N comes from 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylates, and an oxygen atom carrys out autogamy
Position OH-；Second of Zn Atomic coordinate pattern is hexa-coordinate pattern：Three nitrogen-atoms come from 4'- (1H- tetrazoles -5)-biphenyl -3,
5- dicarboxylates, two oxygen atoms carry out 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylates, and an oxygen atom comes from
It is coordinated OH-。
2. the synthetic method of Zn (II) metal organic framework according to claim 1, it is characterised in that described metallic zinc
Salt is Zn (NO3)2。
3. the synthetic method of Zn (II) metal organic framework according to claim 2, it is characterised in that：By 0.25mmol's
Zn(NO3)2, 0.05mmol 4'- (1H- tetrazoles -5)-biphenyl -3,5- dicarboxylic acids, 1mlN, dinethylformamide, which is added, to be held
In device.
4. the synthetic method of Zn (II) metal organic framework according to claim 1,2 or 3, it is characterised in that：Described
The rate of temperature fall being slowly cooled to room temperature is 15-20 DEG C of h-1。
5. according to Zn (II) metal organic frameworks the answering in fluorescence probe field of the synthetic method synthesis described in claim 1
With.
6. application according to claim 5, it is characterised in that method is as follows：By the new Zn (II) described in claim 1
Metal organic framework is configured to methanol suspension, and the methanol solution of metal ion is added dropwise, using wavelength be 305nm light as exciting light,
Carry out fluoroscopic examination.
7. application according to claim 6, it is characterised in that：Described metal ion is Mg2+。
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| CN106749348B (en) * | 2016-11-22 | 2018-10-30 | 南开大学 | A kind of metal-organic framework material and preparation method and application |
| CN106699817B (en) * | 2016-12-29 | 2019-03-15 | 西北大学 | A kind of preparation method and applications of metal-organic framework material |
| CN106824100A (en) * | 2017-03-14 | 2017-06-13 | 山西师范大学 | A kind of zinc MOF poromerics of efficient capture iodine and preparation method and application |
| CN108314628B (en) * | 2018-01-11 | 2020-03-20 | 安徽理工大学 | Magnesium metal organic complex and preparation method thereof |
| CN108384027B (en) * | 2018-05-07 | 2021-03-26 | 江西省科学院应用化学研究所 | Zinc-organic framework with acetylacetone fluorescent response and preparation method thereof |
| CN108587607B (en) * | 2018-05-18 | 2020-10-27 | 陕西科技大学 | Luminescent metal organic framework material for detecting thiocyanate ions in water and preparation method and application thereof |
| CN110776523B (en) * | 2018-07-30 | 2022-04-29 | 天津师范大学 | Ultra-stable three-dimensional luminous zinc (II) metal organic framework material and preparation method and application thereof |
| CN108864157A (en) * | 2018-08-14 | 2018-11-23 | 江苏科技大学 | A kind of fluorescent probe molecule and the preparation method and application thereof for metal ion detection |
| CN110818907B (en) * | 2018-11-26 | 2021-10-01 | 河北民族师范学院 | Zinc coordination polymer containing polycarboxylic acid and multi-nitrogen dual ligand and preparation method thereof |
| CN110853939A (en) * | 2019-10-24 | 2020-02-28 | 李建龙 | Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8Super capacitor material and its making method |
| CN113683781B (en) * | 2020-05-18 | 2023-05-05 | 天津师范大学 | Zinc coordination polymer, synthesis method thereof and application thereof in detection of kanamycin |
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| US8034952B2 (en) * | 2007-11-15 | 2011-10-11 | University Of South Florida | Supramolecular assemblies and building blocks |
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