CN107540644B - Dicarboxylic acid organic ligand and preparation method and application thereof - Google Patents
Dicarboxylic acid organic ligand and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dicarboxylic acid organic ligand, a preparation method and application thereof, wherein the dicarboxylic acid organic ligand is di- (3-formic acid-benzene) furan-2, 5-diamide, and the molecular formula is as follows: c20H14N2O7. A zinc complex with the molecular formula { [ Zn (C) { [20H12N2O7)(H2O)3]·3H2O·DMF}nWherein, C20H12N2O7For the dicarboxylic acid organic ligand, DMF is N, N-dimethylformamide, N represents an integer greater than 1. The zinc complex can be used for identifying Fe3+Or nitrobenzene, and also methylene blue. The invention can be used for identifying Fe with high sensitivity and high selectivity3+Or nitrobenzene, and has simple preparation process, easily controlled chemical components, good repeatability and high yield.
Description
Technical Field
The invention relates to the field of fluorescent probes, in particular to a dicarboxylic acid organic ligand and a preparation method and application thereof.
Background
Fluorescent probes are a class of fluorescent molecules that fluoresce characteristically in the ultraviolet-visible-near infrared region, and whose fluorescent properties (e.g., excitation and emission wavelengths, intensity, lifetime, polarization, etc.) can change sensitively as a function of the properties of the environment in which they are located (e.g., polarity, refractive index, viscosity, etc.). Fluorescent probes have wide applications in both environmental detection and biochemistry, for example: in the aspect of environmental detection, compared with the traditional environmental detection method, the fluorescence method utilizing the fluorescent probe has the advantages of better selectivity, higher sensitivity, simple instrument, simple and convenient operation and the like, and becomes a rapid, sensitive and efficient environmental detection analysis technology. In the prior art, the preparation of fluorescent probe materials for identifying metal ions or small molecules with high sensitivity and high selectivity is an important research topic in the field of current fluorescent probes.
Disclosure of Invention
Aim at the presentThe invention provides a dicarboxylic acid organic ligand, a preparation method and an application thereof, which have the defects in the prior art, and can be used for identifying Fe with high sensitivity and high selectivity3+Or nitrobenzene, and has simple preparation process, easily controlled chemical components, good repeatability and high yield.
The purpose of the invention is realized by the following technical scheme:
a dicarboxylic acid organic ligand is di- (3-formic acid-benzene) furan-2, 5-diamide, and the molecular formula is as follows: c20H14N2O7The structural formula is as follows:
a method for preparing a dicarboxylic acid organic ligand, comprising: putting 2, 5-furandicarboxylic acid and thionyl chloride into a reaction container, heating and refluxing for 72 hours, completely evaporating liquid in the reaction container, and adding anhydrous dimethylacetamide into the reaction container to prepare a brown yellow solution; dissolving 3-aminobenzoic acid and 4- (methylamino) pyridine in anhydrous dimethylacetamide, adding the brown yellow solution, stirring for reacting for 36 hours, and adding dilute hydrochloric acid with the mass fraction of 5% to prepare white precipitate; washing and drying the white precipitate to obtain the dicarboxylic acid organic ligand in the technical scheme;
wherein the proportion relation of the raw materials is as follows:
a zinc complex with the molecular formula { [ Zn (C) { [20H12N2O7)(H2O)3]·3H2O·DMF}nWherein, C20H12N2O7The dicarboxylic acid organic ligand in the technical scheme, DMF is N, N-dimethylformamide, N represents an integer more than 1, and the crystal thereofThe structural data is shown in the following table one:
TABLE 1 { [ Zn (C)20H12N2O7)(H2O)3]·3H2O·DMF}nCrystallographic parameters of
Preferably, the preparation method of the zinc complex comprises the following steps: mixing zinc chloride with the dicarboxylic acid organic ligand in the technical scheme, adding the mixture into an aqueous solution of N, N-dimethylformamide, stirring for 10 minutes, standing in an oven at 120 ℃ for 48 hours, and cooling to obtain the zinc complex; the zinc complex is a colorless massive crystal;
wherein the proportion relation of the raw materials is as follows:
0.27 to 2.7g of zinc chloride,
0.39 to 3.9g of the dicarboxylic acid organic ligand,
50-500 ml of N, N-dimethylformamide.
Preferably, the structure of the zinc complex is determined by a single crystal diffractometer, and the zinc complex emits blue fluorescence under the excitation of incident light with the wavelength of 372 nm.
The zinc complex in the technical scheme is used for identifying Fe3+The fluorescent probe of (1).
The zinc complex in the technical scheme is used as a fluorescent probe for identifying nitrobenzene.
The zinc complex in the technical scheme is used for adsorbing methylene blue.
According to the technical scheme provided by the invention, the dicarboxylic acid organic ligand provided by the invention can be prepared into a zinc complex, and the zinc complex can be used for reacting Fe in various metal ions3+Can be identified by quenching effect, and can be used in various organic solventsThe zinc complex has good identification effect on nitrobenzene and can also have good adsorption effect on cationic dye methylene blue, so that the zinc complex can be used as a good fluorescent probe. Therefore, the invention can be used for identifying Fe with high sensitivity and high selectivity3+Or nitrobenzene, and has simple preparation process, easily controlled chemical components, good repeatability and high yield.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic diagram of an asymmetric unit of a zinc complex prepared in example 2 of the present invention.
FIG. 2 is a diagram showing a fluorescence spectrum of a zinc complex prepared in example 3 of the present invention.
FIG. 3 is a schematic diagram of fluorescence property detection of zinc complexes in different metal ion aqueous solutions in example 3 of the present invention.
FIG. 4 is a schematic diagram of fluorescence property detection of the zinc complex in different small solvent molecules in example 3 of the present invention.
FIG. 5 is a graph showing methylene blue adsorption of the zinc complex prepared in example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The dicarboxylic acid organic ligand provided by the present invention, and the preparation method and application thereof are described in detail below.
Example 1
A dicarboxylic acid organic ligand, the preparation method comprises: 10mmol of 2, 5-furandicarboxylic acid and 256mmol of thionyl chloride were placed in the same 100ml round-bottom flask and heated under reflux for 72 hours, then the liquid in the round-bottom flask was slowly and completely evaporated, and 20ml of anhydrous dimethylacetamide was added to the round-bottom flask to prepare a brown-yellow solution, which was transferred to a 50ml constant pressure dropping funnel. Dissolving 21mmol of 3-aminobenzoic acid and 2.1mmol of 4- (methylamino) pyridine in 50ml of anhydrous dimethylacetamide, slowly dripping the brown yellow solution in a 50ml constant-pressure dropping funnel into the anhydrous dimethylacetamide, stirring at normal temperature for reacting for 36 hours, and adding 60ml of dilute hydrochloric acid with the mass fraction of 5% to prepare white precipitate; and (3) carrying out solid-liquid separation, washing the white precipitate by using 15ml of deionized water, 15ml of ethanol and 30ml of dilute hydrochloric acid with the mass fraction of 5% in sequence, and drying the white precipitate for 24 hours at 60 ℃ in a vacuum oven to obtain the dicarboxylic acid organic ligand, wherein the yield is about 72%. The dicarboxylic acid organic ligand was subjected to elemental analysis, and the results obtained were as follows: theoretical value (%): c, 60.30; h, 3.52; n, 7.04; experimental values (%): c, 59.57; h, 3.39; and N, 6.91.
Example 2
A zinc complex, the preparation method comprising: mixing 0.27g of zinc chloride and 0.39g of dicarboxylic acid organic ligand prepared in the embodiment 1 of the invention, adding the mixture into 50ml of N, N-dimethylformamide aqueous solution, stirring for 10 minutes, standing the mixture in an oven at 120 ℃ for 48 hours, and cooling to obtain a zinc complex; the zinc complex is a colorless bulk crystal.
Specifically, the dimensions are selected to be 0.22X 0.20X 0.18mm3The zinc complex prepared in the embodiment 2 of the invention is subjected to single crystal structure analysis, single crystal diffraction data is collected by adopting a Bruker-AXS SMART APEX2CCD diffractometer, and Mok alpha rays are monochromatized by a graphite monochromator
2.70 DEG-theta-23.20 DEG to obtain the following result: the zinc complex prepared in the embodiment 2 of the invention belongs to an orthorhombic system,the space groups are all Ccca, and the cell parameters are about Ccca
α is 90 °, β is 90 °, and γ is 90 °. The crystal structure of the zinc complex was plotted using Diamond software to give a schematic diagram of the minimum asymmetric unit as shown in figure 1.
Example 3
A zinc complex, the preparation method comprising: mixing 0.54g of zinc chloride and 0.78g of dicarboxylic acid organic ligand prepared in the embodiment 1 of the invention, adding the mixture into 100ml of aqueous solution of N, N-dimethylformamide, stirring for 10 minutes, standing the mixture in an oven at 120 ℃ for 48 hours, and cooling the mixture to obtain a zinc complex; the zinc complex is a colorless bulk crystal.
Specifically, the following performance tests were performed on the zinc complex prepared in example 3 of the present invention:
(1) a single crystal diffractometer is adopted to perform fluorescence test on the zinc complex prepared in the embodiment 3 of the invention, and the wavelength of incident light is 372nm, so that a fluorescence spectrum curve shown in figure 2 can be obtained; in FIG. 2, the abscissa is wavenumber (i.e., wavelength in nm) and the ordinate is intensity (i.e., intensity). As can be seen from fig. 2: the zinc complex prepared in the embodiment 3 of the invention emits blue fluorescence under the excitation of incident light with the wavelength of 372 nm.
(2) Preparing MCl of twelve metal ions with the concentration of 1mmol/L respectivelyx(M＝K+、Co2+、Cd2+、Cu2+、Ba2 +、Mg2+、Mn2+、Ni2+、Pb2+、Fe3+、Al3+) The aqueous solution is used as a liquid to be detected, and the metal chloride is used to eliminate the interference caused by different anions. Taking 3ml of each of the twelve solutions to be tested, adding the solution into twelve 10ml reaction bottles, adding 3mg of the zinc complex prepared in the embodiment 3 into the twelve reaction bottles, performing ultrasonic treatment for 3-4 minutes to uniformly disperse the zinc complex in the solution to be tested, and adopting lambda ex consistent with a solid fluorescence test as an excitation wavelength and a slit width of 1.5nm as the excitation wavelength, wherein the lambda ex is 372nmTesting the fluorescence behavior of the zinc complex in the twelve reaction bottles so as to obtain a fluorescence property detection schematic diagram of different metal ion aqueous solutions shown in FIG. 3; wherein the abscissa of fig. 3 represents the wavelength and the ordinate of fig. 3 represents the relative intensity. As can be seen from fig. 3: only contain Fe3+The fluorescence quenching of the zinc complex in the reaction bottle of the solution to be detected is very obvious (the quenching is over 95 percent), the change of the fluorescence intensity can be observed by naked eyes, and the zinc complex prepared in the embodiment 3 of the invention can be used as a fluorescent probe to identify Fe3+The ability of the cell to perform.
(3) Ten liquid small molecules (respectively: water, tetrahydrofuran, chloroform, N-dimethylformamide, acetone, cyclohexanone, methanol, nitrobenzene, toluene and ethyl acetate) are prepared respectively as a liquid to be detected. Taking 3ml of each of the ten liquid micromolecules, respectively adding into ten 10ml reaction bottles, respectively adding 3mg of the zinc complex prepared in the embodiment 3 into the ten reaction bottles, carrying out ultrasonic treatment for 3-4 minutes to uniformly disperse the zinc complex into the liquid to be detected, and then testing the fluorescence behaviors of the zinc complex in the ten reaction bottles by using lambda ex which is consistent with the solid fluorescence test as an excitation wavelength and the slit width of 1.5nm, thereby obtaining the fluorescence performance detection schematic diagram in different solvent micromolecules as shown in fig. 4; wherein the abscissa of fig. 4 represents the wavelength and the ordinate of fig. 4 represents the relative intensity. As can be seen from fig. 4: only the fluorescence quenching of the zinc complex in the reaction bottle containing nitrobenzene is obvious, and the zinc complex prepared in the embodiment 3 can be used as a fluorescence probe for specifically identifying nitrobenzene.
(4) Weighing 10mg of the zinc complex prepared in the embodiment 3 of the invention, soaking the zinc complex into 5ml of methylene blue ethanol solution with the concentration of 20mg/L, centrifuging the methylene blue ethanol solution at regular intervals, and testing the change of absorbance of the centrifuged supernatant by using an ultraviolet-visible spectrophotometer to obtain a curve graph of the zinc complex adsorbing methylene blue as shown in figure 5; in fig. 5, the abscissa represents the wavelength, and the ordinate represents the degree of absorption. As can be seen from fig. 5: the zinc complex prepared in the embodiment 3 of the invention has a remarkable absorption effect on methylene blue, and nearly 100% of methylene blue is absorbed after standing for 24 hours.
In conclusion, the embodiment of the invention can be used for identifying Fe with high sensitivity and high selectivity3+Or nitrobenzene, and has simple preparation process, easily controlled chemical components, good repeatability and high yield.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A zinc complex with the molecular formula { [ Zn (C) { [20H12N2O7)(H2O)3]·3H2O·DMF}nWherein, C20H12N2O7Is dicarboxylic acid organic ligand, DMF is N, N-dimethylformamide, and N represents an integer more than 1;
the dicarboxylic acid organic ligand is di- (3-formic acid-benzene) furan-2, 5-diamide, and the molecular formula is as follows: c20H14N2O7The structural formula is as follows:
2. the zinc complex of claim 1 having crystal structure data as set forth in table one below:
TABLE 1 { [ Zn (C)20H12N2O7)(H2O)3]·3H2O·DMF}nCrystallographic parameters of
3. The zinc complex according to claim 1 or 2, characterized in that it is prepared by a process comprising: mixing zinc chloride with the dicarboxylic acid organic ligand, adding the mixture into an aqueous solution of N, N-dimethylformamide, stirring for 10 minutes, standing in an oven at 120 ℃ for 48 hours, and cooling to obtain the zinc complex;
wherein the proportion relation of the raw materials is as follows:
0.27 to 2.7g of zinc chloride,
0.39 to 3.9g of the dicarboxylic acid organic ligand,
50-500 ml of N, N-dimethylformamide.
4. The zinc complex according to claim 1 or 2, wherein the zinc complex is a colorless bulk crystal.
5. The zinc complex according to claim 1 or 2, wherein the structure of the zinc complex is determined using a single crystal diffractometer, and the zinc complex emits blue fluorescence when excited by incident light having a wavelength of 372 nm.
6. Use of a zinc complex according to any one of the preceding claims 1 to 5 for the recognition of Fe3+The fluorescent probe of (1).
7. The zinc complex of any one of claims 1 to 5 for use as a fluorescent probe for the recognition of nitrobenzene.
8. Use of a zinc complex according to any one of the preceding claims 1 to 5 as an adsorption for methylene blue.
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| CN108610281B (en) * | 2018-05-03 | 2021-06-15 | 天津师范大学 | Zinc complex with three-dimensional porous structure and synthesis method and application thereof |
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| A luminescent 2D zinc(II) metal–organic framework for selective sensing of Fe(III) ions and adsorption of organic dyes;Tao-Guang Qu等;《Polyhedron》;20180923;第156卷;第208-217页 * |
| Evaluation of Metal-Organic Frameworks and Porous Polymer Networks for CO2-Capture Applications;Wolfgang M. Verdegaal等;《ChemSusChem》;20160203;第9卷;第636-643页 * |
| Formation of a Metal–Organic Framework with High Surface Area and Gas Uptake by Breaking Edges Off Truncated Cuboctahedral Cages;Ruirui Yun等;《Angew. Chem. Int. Ed.》;20130911;第52卷;第11282页左栏第2段，SI第2页II. * |
| Improving the Stability and Gas Adsorption Performance of Acylamide Group Functionalized Zinc Metal-Organic Frameworks through Coordination Group Optimization;Yan-Yuan Jia等;《Cryst. Growth Des.》;20170407;第17卷;第2585页左栏第2段、图1 * |
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