CN105541883A - Metal organic complex containing thiophene functional group and preparing method and application of metal organic complex - Google Patents
Metal organic complex containing thiophene functional group and preparing method and application of metal organic complex Download PDFInfo
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- CN105541883A CN105541883A CN201610004999.6A CN201610004999A CN105541883A CN 105541883 A CN105541883 A CN 105541883A CN 201610004999 A CN201610004999 A CN 201610004999A CN 105541883 A CN105541883 A CN 105541883A
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 title abstract description 10
- 239000002184 metal Substances 0.000 title abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- 230000005284 excitation Effects 0.000 claims description 6
- 150000001457 metallic cations Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- 238000002050 diffraction method Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000007850 fluorescent dye Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 20
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 230000006870 function Effects 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HIHKYDVSWLFRAY-UHFFFAOYSA-N thiophene-2,3-dicarboxylic acid Chemical group OC(=O)C=1C=CSC=1C(O)=O HIHKYDVSWLFRAY-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000008673 vomiting 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
- 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
-
- 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
-
- 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)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
Abstract
The invention relates to a metal organic complex containing a thiophene functional group and a preparing method and application of the metal organic complex. According to the technical scheme, Cd(NO3)2.6H2O, a ligand 2,2'-bithiophene-5,5'-dicarboxylic acid(H2btdc), a solvent N,N-dimethyl formamide and ethyl alcohol are added into a high-temperature-resistant spiral opening glass bottle, and stirring is carried out at the room temperature; the container is sealed and then put into an oven, and heating is carried out for 1-2 days at the temperature of 75 DEG C; the container is slowly cooled to the room temperature, and yellow transparent bulk crystals are obtained; the mixture is washed with N,N-dimethyl formamide, filtered and dried, and the target product is obtained. The prepared metal organic complex containing the thiophene functional group shows a good fluorescence characteristic and can be used for efficiently and selectively recognizing heavy metal zinc ions.
Description
Technical field
The present invention relates to a kind of porous metal organic coordination compound containing thiophene functional site and its preparation method and application, specifically, relate to a kind of preparation and the application thereof with a metal-organic complex of the porous of zine ion Selective recognition function.
Background technology
In recent years, functional metal organic framework materials has obtained as a field developed rapidly and has paid close attention to quite widely, and a bit very important reason is because they have huge potentiality in practical application area.In photochemical reaction, the absorption of luminous energy and release are by being achieved to the transfer of driving electronic center by reactive center catching energy in optical compounds.For making the efficiency in energy transfer process reach maximization, it is vital for catching the relative orientation of component in optical compounds.In order to simulated light building-up process, the synthesis of molecule depends on effective control of relative orientation between component equally, and we utilize covalently bound realization usually.And metal organic frameworks (MOFs), by the relative position of linking group different in fixed crystal or connexon and coordinating metal, provide a unique chance for realizing energy and electronics in effective control of different linking group or the transfer between connexon and coordinating metal.Poly and oligothiophene have the concern that good photoelectric property obtains more investigators.
Zinc is one of trace element of needed by human, play an important role in the important physiological processs such as growth in humans's growth, reproduction heredity, immunity, internal secretion, but zinc intake too much can cause poisoning, too much can cause acute zinc poisoning as eaten zinc, having the gastrointestinal symptom such as vomiting, diarrhoea; Zincalism can have the symptoms such as anaemia; Experimentation on animals can cause Liver and kidney function and immunizing power is impaired.So in environment, in food, the detection of zinc element has just embodied its importance.
Summary of the invention
The object of the invention is to utilize three core cadmiums bunch secondary building unit as metal node, utilize 2,2 '-two bithiophene-5,5 '-dicarboxylic acid (H containing thienyl group
2btdc) as organic ligand, at a certain temperature, the method for solvent thermal is utilized to synthesize a kind of a metal-organic complex containing thiophene functional group.
The technical solution used in the present invention is: a kind of a metal-organic complex containing thiophene functional group, preparation method comprises the steps:
1) by 2,2 '-two bithiophene-5,5 '-dicarboxylic acid H
2btdc, Cd (NO
3)
26H
2o and DMF join in container, stir lower dissolving;
2) add ethanol, stir, put into baking oven by after container sealing, at 70-80 DEG C, heat 1-2 days;
3) progressively cool to room temperature, have yellow bulk crystals to generate;
4) with DMF washing, filter, dry, obtain target product.
The above-mentioned a metal-organic complex containing thiophene functional group, in molar ratio, 2,2 '-two bithiophene-5,5 '-dicarboxylic acid H
2btdc:Cd (NO
3)
26H
2o=1:2.5.
The above-mentioned a metal-organic complex containing thiophene functional group, step 2) in, put into baking oven by after container sealing, temperature rise rate is 5 DEG C of min
-1.
The above-mentioned a metal-organic complex containing thiophene functional group, the described rate of temperature fall progressively cooling to room temperature is 5 DEG C of h
-1.
A metal-organic complex containing thiophene functional group of the present invention can be used as fluorescent probe and applies.Method is as follows: in the methyl alcohol suspension liquid of a metal-organic complex containing thiophene functional group, add the methanol solution containing metallic cation, under excitation wavelength 300nm, detect fluorescent emission intensity.
The invention has the beneficial effects as follows: a metal-organic complex containing thiophene functional group prepared by the present invention all shows very strong fluorescent emission in the solid state with in methyl alcohol.In complex structure, introduce functional site by constructing a metal-organic complex with the part containing thienyl group, its fluorescence radiation is shown Zn
2+selective recognition, along with Zn
2+the fluorescence intensity adding title complex obviously strengthen, but add other metal ions, fluorescence intensity does not have considerable change, or weakens even cancellation.This photoluminescent property of title complex of the present invention can be applied as Zn
2+fluorescent probe.Synthetic method is simple, has application prospect.
Accompanying drawing explanation
Fig. 1 a is organic ligand 2,2 '-two bithiophene-5,5 '-dicarboxylic acid H of the present invention
2the structural formula of btdc.
Fig. 1 b is H in a metal-organic complex structure of the present invention
2a kind of coordination mode of btdc part.
Fig. 1 c is H in a metal-organic complex structure of the present invention
2the another kind of coordination mode of btdc part.
Fig. 2 a is three core cadmiums bunch secondary building unit in a metal-organic complex structure of the present invention.
Fig. 2 b is the coordination environment of Cd (II) ion in a metal-organic complex structure of the present invention.
Fig. 3 a is the two-dimensional mesh compartment schematic diagram of a metal-organic complex of the present invention.
Fig. 3 b is the topological net that the 4-of a metal-organic complex of the present invention connects.
Fig. 3 c is the one dimension rhombus duct schematic diagram in [101] direction in a metal-organic complex structure of the present invention.
Fig. 3 d is the accumulation graph of one-dimensional channels in a metal-organic complex structure of the present invention.
Fig. 4 is that the solid fluorescence of a metal-organic complex of the present invention excites (468nm) and launching curve (275nm).
Fig. 5 is the Zn adding 0-5equiv in methyl alcohol suspension liquid of the present invention
2+fluorescence emission curves (300nm excites).
Fig. 6 is the impact of each metal ion on fluorescent emission (300nm) intensity of a metal-organic complex of the present invention.
Fig. 7 is that the methyl alcohol suspension liquid of a metal-organic complex of the present invention is doped into Zn simultaneously
2+and Cd
2+, Hg
2+, Na
+fluorescence intensity change.
Embodiment
The a metal-organic complex of embodiment 1 containing thiophene functional group
By H
2btdc (0.005g, 0.02mmol) and Cd (NO
3)
26H
2o (0.015g, 0.05mmol) joins in the high temperature resistant spiral mouth vial that volume is 5mL, and add 0.75mLDMF, magnetic stirrer is dissolved, then adds 0.75mlC
2h
5oH, stirs 15 minutes until metal-salt all dissolves mixes with part, puts into 75 DEG C of baking ovens, heat 2 days at such a temperature, with 5 DEG C of h after being sealed by vial
-1rate of temperature fall progressively cool to room temperature, have yellow bulk crystals to generate, with DMF washing, filter, dry, obtain target product, a metal-organic complex namely containing thiophene functional group, productive rate is 58%.
Ultimate analysis calculated value (%): C30.64, H1.97; Observed value (%): C30.70, H2.01.
Infrared spectra (KBr, cm
– 1): 3437m, 2928m, 1650s, 1563s, 1518s, 1425s, 1384s, 818m, 770m..
The present invention synthesis a metal-organic complex be one by thiophene dicarboxylic acid's part H
2the porous metal organic frame of btdc and the three core Cd bunch two-dimensional layer that secondary building unit is built into.Two crystallography independently Cd (II) ion is comprised, one and half H in a unsymmetrical structure unit
2btdc part (Fig. 1 a), the ethanol molecule of a coordinated water molecule and a coordination.As shown in Figure 2 a, two crystallography independently Cd (II) ion has two kinds of different coordination modes, and Cd1 (II) ion connects the pentagonal bipyramid coordination geometric configuration that seven Sauerstoffatoms form distortion.Wherein five Sauerstoffatoms (O1, O2, O4, O5, O6) come from the carboxyl of three independently btdc parts respectively, another Sauerstoffatom (O7), from the water molecules of a coordination, also has a Sauerstoffatom (O8) to come from the hydroxyl of the ethanol molecule of coordination.And for Cd2 (II) ion, it forms with six oxygen atom ligands coming from three independently btdc parts respectively the octahedral coordination geometry reversed.Two Cd1 (II) are passed through μ by three carboxyls from different btdc part respectively from a Cd2 (II)
2o; κ
2o, O ' and μ
2-carboxylato-κ
1o: κ
1the coordination mode of O ' is connected, and forms three core cadmium bunch [Cd
3(COO)
6] secondary structure unit (Fig. 2 b).In the structure of this title complex, part H
2btdc shows two kinds of different coordination modes (Fig. 1 b and Fig. 1 c).First two adjacent three core cadmium bunch secondary structure units pass through H
2the carboxyl of btdc part is with μ
2-carboxy-lato-κ
1o: κ
1o ', μ
2o; κ
2o, O ' coordination mode be connected to form one-dimensional chain structure, chain and interchain are connected by btdc part further, by the structure of title complex expand become two-dimensional layered structure (Fig. 3 a and Fig. 3 b).Two-dimensional layered structure is by further piling up, and define one dimension rhombus duct in [101] direction, pore size is
(Fig. 3 c and Fig. 3 d).
A metal-organic complex containing thiophene functional group of the present invention, containing thiophene functional site in structure, its crystal belongs to oblique system, and spacer is C2/c.
The photoluminescent property of a metal-organic complex of embodiment 2 one kinds containing thiophene functional group and Selective recognition metal ion function
Method: as fluorescent optical sensor, Selective recognition is carried out to metal ion using a kind of a metal-organic complex containing thiophene functional group prepared by embodiment 1.
1) a metal-organic complex containing thiophene functional group of the present invention is carried out to the fluorescence radiation test of solid under room temperature and liquid.
The configuration of liquid sample: get a certain amount of Function for Organometallic Complex Crystals containing thiophene functional group, be ground to uniform powder, be then dissolved in methanol solution, being configured to concentration is 1 × 10
-4the methyl alcohol suspension liquid of M.
It is under the exciting of 275nm at wavelength that solid fluorescence analytical results shows this metal-organic complex containing thiophene functional group, displays very strong emission band (Fig. 4) at about 468nm.The fluorescent liquid measurement result display of the methyl alcohol suspension liquid of a metal-organic complex of thiophene functional group should be contained, be under the exciting of 300nm in excitation wavelength, show obvious fluorescent emission at about 404nm.
2) different metal ion pair should contain the impact of the fluorescent characteristic of a metal-organic complex of thiophene functional group
The configuration of the methanol solution containing metallic cation: the nitrate (Na getting a certain amount of metallic cation
+, Ca
2+, Ba
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Pd
2+, Hg
2+, Mn
2+and Cd
2+), be dissolved in methyl alcohol and be configured to certain density solution.
The configuration of a metal-organic complex methyl alcohol suspension liquid containing thiophene functional group: get a certain amount of Function for Organometallic Complex Crystals containing thiophene functional group, be ground to uniform powder, be then dissolved in methanol solution, being configured to concentration is 1 × 10
-4the methyl alcohol suspension liquid of M.
Getting concentration is respectively 1 × 10
-4some parts of a metal-organic complex methyl alcohol suspension liquid 5mL containing thiophene functional group of M, respectively to mix in every increment product 3equiv containing the methanol solution of metallic cation, testing in excitation wavelength is the change of a metal-organic complex fluorescent emission intensity under 300nm excites.Result as shown in Figure 6, when the metal ion added is Ba
2+, Fe
2+, Ca
2+, Cu
2+, Mn
2+, Pd
2+, Co
2+and Ni
2+time, the fluorescence intensity of a metal-organic complex of the present invention is weakened to be even quenched, and remaining metal ion Na
+, Hg
2+and Cd
2+then that its fluorescence intensity is not significantly affected.And the fluorescent emission of a metal-organic complex of the present invention is to Zn
2+illustrate selectivity sensing.
3) zinc ion concentration contains the impact of the fluorescent characteristic of a metal-organic complex of thiophene functional group on the present invention
Getting concentration is 1 × 10
-4m containing a metal-organic complex methyl alcohol suspension liquid 5mL of thiophene functional group, progressively mix the methanol solution of the metallic zinc ion of 0-5equiv, testing in excitation wavelength is the change of a metal-organic complex fluorescent emission intensity under 300nm excites.Result as shown in Figure 5 (in Fig. 5, be followed successively by from bottom to top 0,1,2,3,4 and 5equiv), result shows, along with Zn
2+add, the emissive porwer of a metal-organic complex of the present invention is obviously strengthened.Even more noteworthy, along with Zn
2+the increase of concentration, the fluorescence intensity of a metal-organic complex of the present invention shows thereupon and constantly obviously strengthens---and the emissive porwer of title complex is along with the Zn of 1-5equiv
2+add and had corresponding enhancing.When adding the Zn of 3equiv
2+time, the fluorescence intensity of this metal-organic complex reaches about 800, enhances about 2 times.Work as Zn
2+when continuing to be added to 5equiv, the fluorescent emission of title complex shows by force the trend continuing to strengthen, but growth degree but reduces to some extent.So the fluorescent emission of this metal-organic complex is to Zn
2+illustrate selectivity sensing.
4) whether the function of a metal-organic complex Selective recognition zine ion of the present invention is subject to the research of other ion interference
Getting concentration is respectively 1 × 10
-4the a metal-organic complex methyl alcohol suspension liquid 5mL containing thiophene functional group of M, then adds 3equivZn respectively
2+, 3equivCd
2+, 3equivHg
2+, 3equivNa
+, 3equivCd
2+and 3equivZn
2+, 3equivHg
2+and 3equivZn
2+, 3equivNa
+and 3equivZn
2+, testing in excitation wavelength is the change of a metal-organic complex fluorescent emission intensity under 300nm excites.Cd
2+, Hg
2+and Na
+a metal-organic complex fluorescence intensity of the present invention is had no significant effect.As shown in Figure 7, the methyl alcohol suspension liquid of a metal-organic complex of the present invention is having Cd to experimental result
2+, Hg
2+and Na
+when ion exists, along with Zn
2+add, the emissive porwer of a metal-organic complex of the present invention still there occurs obvious enhancing.Show the metal ion (Cd that a metal-organic complex of the present invention is had no significant effect
2+, Hg
2+and Na
+) to a metal-organic complex of the present invention to Zn
2+selective recognition function do not disturb.
Claims (9)
1. a metal-organic complex containing thiophene functional group, is characterized in that: preparation method comprises the steps:
1) by 2,2 '-two bithiophene-5,5 '-dicarboxylic acid H
2btdc, Cd (NO
3)
26H
2o and DMF join in container, stir lower dissolving;
2) add ethanol, stir, put into baking oven by after container sealing, at 70-80 DEG C, heat 1-2 days;
3) progressively cool to room temperature, have yellow bulk crystals to generate;
4) with DMF washing, filter, dry, obtain target product.
2. a metal-organic complex containing thiophene functional group according to claim 1, it is characterized in that: the described a metal-organic complex containing thiophene functional group, containing thiophene functional site in structure, its crystal belongs to oblique system, and spacer is C2/c.
3. a metal-organic complex containing thiophene functional group according to claim 2, it is characterized in that: the described a metal-organic complex containing thiophene functional group, two crystallography independently Cd (II) ion is comprised in structure, two crystallography independently Cd (II) ion has two kinds of different coordination modes, the first coordination mode, Cd1 (II) ion connects the pentagonal bipyramid coordination geometric configuration that seven Sauerstoffatoms form distortion; The second coordination mode, Cd2 (II) ion with come from three independently H respectively
2six oxygen atom ligands of btdc part form the octahedral coordination geometric configuration reversed.
4. a metal-organic complex containing thiophene functional group according to claim 1, is characterized in that: in molar ratio, 2,2 '-two bithiophene-5,5 '-dicarboxylic acid H
2btdc:Cd (NO
3)
26H
2o=1:2.5.
5., according to the arbitrary described a metal-organic complex containing thiophene functional group of claim 1-4, it is characterized in that: step 2) in, put into baking oven by after container sealing, temperature rise rate is 5 DEG C of min
-1.
6., according to the arbitrary described a metal-organic complex containing thiophene functional group of claim 1-4, it is characterized in that: the described rate of temperature fall progressively cooling to room temperature is 5 DEG C of h
-1.
7. a metal-organic complex containing thiophene functional group according to claim 1 is as the application of fluorescent probe.
8. application according to claim 7, is characterized in that, method is as follows: in the methyl alcohol suspension liquid of a metal-organic complex containing thiophene functional group, add the methanol solution containing metallic cation, under excitation wavelength 300nm, detect fluorescent emission intensity.
9. application according to claim 8, is characterized in that: described metallic cation is zine ion.
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| CN107674213A (en) * | 2017-10-01 | 2018-02-09 | 桂林理工大学 | A kind of La MOF materials and preparation method with double parts |
| CN110143943A (en) * | 2019-05-15 | 2019-08-20 | 中国石油大学(华东) | A kind of barium base complex and preparation method thereof and the application in fluorescence identifying field |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732785A (en) * | 2017-01-23 | 2017-05-31 | 辽宁大学 | A kind of application of porous metal-organic framework compound based on rare earth in silicon cyanation |
| CN106732785B (en) * | 2017-01-23 | 2019-07-02 | 辽宁大学 | A kind of application of the porous metal-organic framework compound in silicon cyanation based on rare earth |
| CN107674213A (en) * | 2017-10-01 | 2018-02-09 | 桂林理工大学 | A kind of La MOF materials and preparation method with double parts |
| CN110143943A (en) * | 2019-05-15 | 2019-08-20 | 中国石油大学(华东) | A kind of barium base complex and preparation method thereof and the application in fluorescence identifying field |
| CN110143943B (en) * | 2019-05-15 | 2022-02-08 | 中国石油大学(华东) | Barium-based complex, preparation method thereof and application thereof in field of fluorescence recognition |
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