CN111777630A - Rare earth terbium (III) complex and preparation method and application thereof - Google Patents
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Abstract
The rare earth terbium (III) complex has good fluorescence intensity and monochromaticity, can emit strong green fluorescence under a three-purpose ultraviolet lamp when the excitation wavelength is 254nm, shows excellent selectivity on the aspect of iron ion detection, and can emit strong green fluorescence when being used as Fe3+The concentration is 0.0-1.5 mmol.L‑1In the range of (1), the ratio of the fluorescence intensity of the above-mentioned rare earth terbium (III) complex in an aqueous solution to the fluorescence intensity thereof in an iron ion solution to Fe3+The concentration presents extremely strong linear relation, so the rare earth terbium (III) complex can be used as a fluorescent probe to identify Fe3+The method has wide application range and high detection accuracy.
Description
Technical Field
The invention relates to the technical field of rare earth metal complexes, in particular to a rare earth terbium (III) complex and a preparation method and application thereof.
Background
The rare earth ion complex has unique photoluminescence performance, and can play a role in the photoluminescence performance of the rare earth ion complex in the fields of laser materials, optical fiber communication, fluorescent probes and the like. The fluorescence intensity of the rare earth ion complex is closely related to the selected sensitizer, and beta-diketone, aromatic carboxylic acid and the like are generally adopted as organic ligands in the prior art.
Chinese patent document CN107556486A discloses a rare earth organic framework material for iron ion fluorescence detection, which takes linear dicarboxylic acid with hydroxyl functional groups as an organic ligand, and the rare earth organic framework material can be applied to iron ion concentration detection, when the iron ion concentration is 0-53 mu mol-1In the range of the concentration on the left and right, the fluorescence intensity and the iron ion concentration are in a linear relationship, and ratio type fluorescence detection can be realized for the iron ions, but as can be seen from fig. 3 in the literature, the fitting degree of the obtained formula is not ideal, and the range of the linear relationship between the iron ion concentration and the fluorescence intensity of the rare earth organic framework material is narrow, so that the application scene is greatly limited. In addition, the rare earth organic framework material in the above document is prepared by a hydrothermal method, the temperature is continuously above 120 ℃ in the reaction process, and the energy consumption is high.
Chinese patent document CN108864158A discloses a tetranuclear rare earth terbium complex which has better fluorescence intensity and monochromaticity, and in the document, the tetranuclear rare earth terbium complex is prepared by a diffusion method, and the synthesis process is carried out at normal temperature, thereby saving energy and protecting environment. However, the above documents do not disclose the results of the selective recognition test of iron ions by the tetranuclear rare earth terbium complex, and the synthesis process of the tetranuclear rare earth terbium complex requires three weeks of rest to obtain the product, which takes a long time.
Disclosure of Invention
One of the purposes of the invention is to provide a rare earth terbium (III) complex with a brand new network structure, which can realize ratio type fluorescence detection on iron ions in a larger concentration range.
In order to achieve the above object, the present invention provides a rare earth terbium (III) coordination polymer, the crystal molecular structural formula of which is:
in the above formula, R is a water molecule.
Wherein, the crystallography data of the rare earth terbium (III) complex are as follows: the crystal belongs to monoclinic system, space group P21/n
α＝90.0°,β＝109.056(2)°,γ＝90.0°,
Z＝2,GooF＝1.105，F(000)＝1984.0，R1＝0.0709。
In addition, the invention also provides a method for preparing the rare earth terbium (III) complex, which comprises the following steps:
adding a proper amount of 2, 5-bis (4-methylbenzoyl) terephthalic acid into a reaction container, adding a 1# mixed solvent consisting of water and ethanol, adding a sodium hydroxide solution to adjust the pH value to 5-6, stirring and dissolving at normal temperature, adding a proper amount of terbium nitrate hexahydrate, stirring and dissolving at normal temperature to obtain a mixed solution, firstly adding a 2# mixed solvent consisting of water and ethanol on the liquid surface of the mixed solution, adding an ethanol solution dissolved with phenanthroline, layering the solution, covering the reaction container under the condition of ensuring air permeability, standing at room temperature for two weeks, and obtaining a colorless crystal at the middle layer of the reaction container, namely the rare earth terbium (III) complex.
Wherein, in the mixed solvent No. 1, the volume ratio of the water to the ethanol is 1: 2; in the mixed solvent No. 2, the volume ratio of the water to the ethanol is 1: 5.
further, the ratio of the 2, 5-bis (4-methylbenzoyl) terephthalic acid to the 1# mixed solvent is that every 0.31mmol of 2, 5-bis (4-methylbenzoyl) terephthalic acid corresponds to 21ml of the 1# mixed solvent;
the molar ratio of the 2, 5-di (4-methylbenzoyl) terephthalic acid, the terbium nitrate hexahydrate and the phenanthroline is as follows: 31: 20: 19;
the volume ratio of the 1# mixed solvent to the 2# mixed solvent to the phenanthroline ethanol solution is 21: 5: 5.
the rare earth terbium (III) complex can be applied as a luminescent material.
In addition, the rare earth terbium (III) complex can also be applied to an iron ion fluorescent probe.
Finally, the rare earth terbium (III) complex can also be used for the Fe in the iron ion-containing solution3+The concentration detection method specifically comprises the following steps: in Fe3+The concentration is not more than 1.5mmol.L-1Using the rare earth terbium (III) coordination polymer as an indicator to obtain Fe in the solution to be detected according to the following formula3+Concentration value:
I0/I＝1.0017+185.81[Fe3+]；
in the above formula, I0The fluorescence intensity of the rare earth terbium (III) coordination polymer in a blank aqueous solution is shown, I is the fluorescence intensity of the rare earth terbium (III) coordination polymer in an iron ion solution to be detected, [ Fe ]3+]Is Fe in the solution to be measured3+And (4) concentration.
The rare earth terbium (III) complex has good fluorescence intensity and monochromaticity, and can emit extremely strong green fluorescence when excited by ultraviolet light with the wavelength of 254nm under a three-way ultraviolet lamp. In addition, the rare earth terbium (III) complex shows excellent selectivity on detection of iron ions, when Fe3+The concentration is 0.0-1.5 mmol.L-1In the range of (1), the ratio of the fluorescence intensity of the above-mentioned rare earth terbium (III) complex in an iron ion solution to the fluorescence intensity thereof in an aqueous solution to Fe3+The concentration is in a strong linear relation, and based on the characteristics, the rare earth terbium (III) complex can be used as a fluorescent probe for recognizing Fe3+Compared with the background technology, the rare earth terbium (III) coordination polymer can realize ratio type fluorescence detection on iron ions in a larger concentration range, and has wider application scene and high detection accuracy. The above-mentioned terbium (III) organic framework is matched in comparison with the two products of the prior art (documents CN107556486A and CN108864158A)The polymer can realize ratio type fluorescence detection on iron ions in a larger concentration range, and has high detection accuracy. Different from the rare earth organic framework material in CN107556486A in the literature which adopts a hydrothermal method, the invention adopts a diffusion method to synthesize the rare earth terbium (III) complex at normal temperature, thereby being more energy-saving and environment-friendly. Meanwhile, the synthesis device used by the invention is simpler and the operation is simpler. In addition, compared with the tetranuclear rare earth terbium complex in the document CN108864158A, the time required for preparing the rare earth terbium (III) complex is greatly shortened.
Description of the drawings:
FIG. 1 is a molecular structural diagram of a rare earth terbium (III) complex prepared in the example;
FIG. 2 is a photograph of a terbium (III) coordination polymer emitting strong green fluorescence under a three-way ultraviolet lamp at an excitation wavelength of 254 nm;
FIG. 3 is a solid fluorescence emission spectrum of a rare earth terbium (III) complex at room temperature;
FIG. 4 is a graph showing the effect of different metal ions on the fluorescence emission spectrum of a rare earth terbium (III) complex;
FIG. 5 shows the coordination polymer of rare earth terbium (III) in Fe3+The concentration is 0.0-1.5 mmol.L-1Of a solution of (a) having a fluorescence intensity ratio of I0I and Fe3+A linear plot of concentration;
FIG. 6 is a graph showing the effect of different metal ions on the fluorescence emission spectrum of a tetranuclear rare earth terbium complex;
FIG. 7 shows the four-core rare earth terbium complex in Fe3+The concentration is 0.00-1.0 mmol.L-1Emission spectra in different solutions; the insert in the upper right corner of the graph is the fluorescence intensity ratio I0I and Fe3+Graph of concentration dependence.
Detailed Description
In order to facilitate the understanding of those skilled in the art, the present invention will be further described with reference to the following examples, which are not intended to limit the present invention. It should be noted that the following examples are carried out in the laboratory, and it should be understood by those skilled in the art that the amounts of the components given in the examples are merely representative of the proportioning relationship between the components, and are not specifically limited.
1. And (3) synthesizing a rare earth terbium (III) complex.
0.31mmol of 2, 5-bis (4-methylbenzoyl) terephthalic acid is added into a round-bottom flask, 21ml of a mixed solvent consisting of water and ethanol (volume ratio is 1: 2) is added, sodium hydroxide solution is added to adjust the pH value of the solution to be 5-6, the solution is stirred to be dissolved, then 0.20mmol of terbium nitrate hexahydrate is added into the mixed solution, stirring is continued, and the obtained mixed solution is transferred into a glass test tube. Adding 5ml of mixed solvent consisting of water and ethanol (volume ratio is 1: 5) on the liquid surface in the test tube, and then adding 5ml of ethanol solution dissolved with 0.19mmol of phenanthroline. Covering the test tube mouth with the small-hole preservative film, standing at room temperature, and slowly precipitating a colorless crystal product after two weeks. It should be noted that the pH of the solution, and particularly the choice of the solvent mixture, is important during the preparation process, and an inappropriate pH and solvent mixture will result in no formation of the desired product. The crystallographic data of the rare earth terbium (III) complex are as follows: the crystal belongs to monoclinic system, space group P21/n
α＝90.0°,β＝109.056(2)°,γ＝90.0°,
Z＝2,GooF＝1.105，F(000)＝1984.0，R1＝0.0709。IR(KBr，cm-1)：1665(s)，1572(vs),1422(s)，1344(s)，1261(m),843(m)，733(m)，520(w)，480(w)。
2. Crystal structure of rare earth terbium (III) complex.
The molecular structure of the rare earth terbium (III) complex is shown in figure 1, and as can be seen from the crystal structure diagram 1, in a coordination polymer molecule, 2, 5-di (4-methylbenzoyl) terephthalate is used as a bridging ligand and is simultaneously coordinated with two adjacent terbium (III) ions, so that the whole molecule forms a net structure. The central terbium (III) ion is in a coordination environment of nine atoms, of which 6 oxygen atoms come from three 2, 5-bis (4-methylbenzoyl) terephthalate radicals, 2 nitrogen atoms come from one phenanthroline molecule, and the other 1 oxygen atom comes from a water molecule. Meanwhile, the complex molecules also have water molecules which are not coordinated.
3. And (3) testing the performance of the rare earth terbium (III) coordination polymer.
3.1 As shown in figure 2, under a three-way ultraviolet lamp, when excited by ultraviolet light with the wavelength of 254nm, the rare earth terbium (III) complex emits strong green fluorescence; the fluorescence spectrum was measured using a fluorescence spectrophotometer, and as shown in FIG. 3, the rare earth terbium (III) complex had four fluorescence emission peaks at 491, 546, 586 and 622nm, corresponding to Tb, respectively, when the excitation wavelength was 336nm3+Is/are as follows5D4→7F6、5D4→7F5、5D4→7F4And, and5D4→7F3wherein the emission peak at 546nm is strongest.
3.2 adding the fully ground rare earth terbium (III) complex and barium sulfate powder into a high polymer material adhesive, uniformly dispersing by ultrasonic, and uniformly fixing the mixture on a glass slide.
The glass slides were each added at a concentration of 0.01mol.L-1Different metal ion (Ag)+、Al3+、Ba2+、Ca2+、Ca2+、Cd2+、Co2+、Cr3+、Cu2+、Fe2+、Hg2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+、Fe3+) In the solution, the fluorescence emission spectrum of the rare earth terbium (III) complex is detected, as shown in FIG. 4. As can be seen from FIG. 4, the fluorescence emission spectra of the terbium (III) rare earth complexes in the respective solutions have approximately the same peak shape, but slightly different intensities. Comparison of Tb in the above-mentioned rare earth Terbium (III) Complex3+At 545nm (5D4→7F5) Change in fluorescence emission intensity: in Ag+、Al3+、Ba2+、Ca2+、Ca2+、Cd2+、Co2+、Cr3+、Cu2+、Fe2+、Hg2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+And Zn2+When the rare earth terbium (III) complex is in the solution, the fluorescence emission intensity of the rare earth terbium (III) complex is rarely changed; and in Fe3+In solution, the fluorescence intensity of the rare earth terbium (III) complex is significantly reduced, which may be Fe3+The addition of (a) inhibits the transfer of energy from the ligand to the rare earth ion.
To further detect Fe3+Effect on fluorescence emission intensity of Terbium (III) rare earth coordination Polymer, the glass slides were added to different concentrations of Fe3+In solution, under the same detection conditions, with Fe3+Increase in concentration, Tb3+The fluorescence intensity at 545nm gradually decreased. Setting the fluorescence intensity of the rare earth terbium (III) coordination polymer in a blank aqueous solution as I0In Fe3 +The fluorescence intensity in the solution is I, the ratio thereof (I)0I) and Fe3+The solution is 0.0-1.5 mmol.L-1The range shows an extremely strong linear relationship, as shown in fig. 5, the linear equation is:
I0/I＝1.0017+185.81[Fe3+]r2 ═ 0.9867 where [ Fe ═ is3+]Is Fe in the solution to be measured3+And (4) concentration.
4. Tetranuclear rare earth terbium complex pair Fe3+Selective identification test of (2).
The tetranuclear rare earth terbium complex is prepared according to the method in the document CN108864158A, and the molecular structure of the tetranuclear rare earth terbium complex is shown in figure 1 in the document CN 108864158A. And adding the fully ground four-core rare earth terbium complex and barium sulfate powder into a high polymer material adhesive, uniformly dispersing by ultrasonic, and uniformly fixing on a glass slide.
4.1 Add the slide to 0.01mol.L-1Different metal ion (Ag)+、Al3+、Ba2+、Ca2+、Ca2+、Cd2+、Co2+、Cr3+、Cu2+、Fe2+、Hg2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+、Fe3+) In the solution, the fluorescence emission spectrum of the tetranuclear rare earth terbium complex is detected, and the detection result is shown in figure 6. As can be seen from FIG. 6, the fluorescence intensity of the tetranuclear rare earth terbium complex is in Fe3+Almost quenched in the solution, and the fluorescence intensity change is not obvious in other metal ion solutions, which shows that the tetranuclear rare earth terbium complex can also act on Fe3+Identified, has high selectivity and can be used as Fe3+The fluorescent probe of (1).
4.2 to further study Fe3+The influence on the fluorescence emission intensity of the tetranuclear rare earth terbium complex is realized by adding the glass slide into Fe with different concentrations3+In solution, under the same detection conditions, the presence of Fe is recorded3+Fluorescence emission spectrum of tetranuclear rare earth terbium complex in solution (see FIG. 7), as shown in FIG. 7, tetranuclear rare earth terbium complex for Fe3+Has high fluorescence sensitivity with Fe3+Increase in concentration, Tb3+The fluorescence intensity at 545nm gradually decreased. Setting the fluorescence intensity of the tetranuclear rare earth terbium complex in a blank aqueous solution as I0In Fe3+The fluorescence intensity in the solution is I, the ratio thereof (I)0I) and Fe3+The concentration is 0.0-1.0 mmol.L-1The linear relation is presented in the range (see the inset in the upper right corner of fig. 7), and the linear equation is I0/I＝1.0+712.82[Fe3+]，R2＝0.9974。
From the above test results, it can be seen that the rare earth terbium (III) complex provided by the present invention can realize ratio-type fluorescence detection of iron ions in a larger concentration range than the tetranuclear rare earth terbium complex in document CN 108864158A.
From the test results of the above-mentioned rare earth terbium (III) complex and the preparation process thereof, it was determined that: the rare earth terbium (III) complex has good fluorescence intensity and monochromaticity, and can emit extremely strong green fluorescence when excited by ultraviolet light with the wavelength of 254nm under a three-way ultraviolet lamp. In addition, the rare earth terbium (III) complex shows excellent selectivity on detection of iron ions, when Fe3+At a concentration of 0.0～1.5mmol.L-1In the range of (1), the ratio of the fluorescence intensity of the above-mentioned rare earth terbium (III) complex in an iron ion solution to the fluorescence intensity thereof in an aqueous solution to Fe3+The concentration is in a strong linear relation, and based on the characteristics, the rare earth terbium (III) complex can be used as a fluorescent probe for recognizing Fe3+Compared with the rare earth organic framework material disclosed in the document CN107556486A and the tetranuclear rare earth terbium complex disclosed in the document CN108864158A, the rare earth terbium (III) complex prepared in the embodiment can realize ratio type fluorescence detection on iron ions in a larger concentration range, and has wider application scenes. Different from the hydrothermal method adopted by the rare earth organic framework material in CN107556486A in the literature, the rare earth terbium (III) complex is synthesized by adopting the diffusion method at normal temperature in the embodiment, so that the method is more energy-saving and environment-friendly, and meanwhile, the used synthesis device is simpler and the operation is simpler. In addition, compared with the tetranuclear rare earth terbium complex in the document CN108864158A, the time required for preparing the rare earth terbium (III) complex in the above examples is less than that of the tetranuclear rare earth terbium complex in the document CN108864158A by one week, and the synthesis time is greatly shortened.
The above embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Finally, it should be emphasized that some of the descriptions of the present invention have been simplified to facilitate the understanding of the improvements of the present invention over the prior art by those of ordinary skill in the art, and that other elements have been omitted from this document for the sake of clarity, and those skilled in the art will recognize that these omitted elements may also constitute the content of the present invention.
Claims (8)
1. The rare earth terbium (III) complex is characterized in that the crystal molecular structural formula of the rare earth terbium (III) complex is as follows:
in the above formula, R is a water molecule.
2. The terbium (III) complex according to claim 1, wherein the crystallography data of the terbium (III) complex polymer are: the crystal belongs to monoclinic system, space group P21/n
α＝90.0°,β＝109.056(2)°,γ＝90.0°,
Z＝2,GooF＝1.105，F(000)＝1984.0，R1＝0.0709。
3. The method for preparing a rare earth terbium (III) complex according to claim 1 or 2, comprising the steps of:
adding a proper amount of 2, 5-bis (4-methylbenzoyl) terephthalic acid into a reaction container, adding a 1# mixed solvent consisting of water and ethanol, adding a sodium hydroxide solution to adjust the pH value to 5-6, stirring and dissolving at normal temperature, adding a proper amount of terbium nitrate hexahydrate, stirring and dissolving at normal temperature to obtain a mixed solution, firstly adding a 2# mixed solvent consisting of water and ethanol on the liquid surface of the mixed solution, adding an ethanol solution dissolved with phenanthroline, layering the solution, covering the reaction container under the condition of ensuring air permeability, standing at room temperature for two weeks, and obtaining a colorless crystal at the middle layer of the reaction container, namely the rare earth terbium (III) complex.
4. The production method according to claim 3, characterized in that:
in the mixed solvent No. 1, the volume ratio of the water to the ethanol is 1: 2; in the mixed solvent No. 2, the volume ratio of the water to the ethanol is 1: 5.
5. the method of claim 4, wherein:
the ratio of the 2, 5-bis (4-methylbenzoyl) terephthalic acid to the 1# mixed solvent is that every 0.31mmol of 2, 5-bis (4-methylbenzoyl) terephthalic acid corresponds to 21ml of the 1# mixed solvent;
the molar ratio of the 2, 5-di (4-methylbenzoyl) terephthalic acid, the terbium nitrate hexahydrate and the phenanthroline is as follows: 31: 20: 19;
the volume ratio of the 1# mixed solvent to the 2# mixed solvent to the phenanthroline ethanol solution is 21: 5: 5.
6. use of a rare earth terbium (III) complex as defined in claim 1 or 2 as a luminescent material.
7. Use of the terbium (III) rare earth complex according to claim 1 or 2 in an iron ion fluorescent probe.
8. The terbium (III) rare earth complex of claim 1 or 2 in a solution containing iron ions in the presence of Fe3+The application of concentration detection is characterized in that: in Fe3+The concentration is not more than 1.5mmol.L-1Using the rare earth terbium (III) coordination polymer as an indicator to obtain Fe in the solution to be detected according to the following formula3+Concentration value:
I0/I＝1.0017+185.81[Fe3+]；
in the above formula, I0The fluorescence intensity of the rare earth terbium (III) complex in a blank aqueous solution is shown, I is the fluorescence intensity of the rare earth terbium (III) complex in an iron ion solution to be detected, [ Fe ]3+]Is Fe in the solution to be measured3+And (4) concentration.
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| CN108864158A (en) * | 2018-06-20 | 2018-11-23 | 衡阳师范学院 | A kind of four core rare-earth terbium complex and preparation method thereof and application as luminescent material |
| CN110240707A (en) * | 2019-06-10 | 2019-09-17 | 江苏师范大学 | Rear modified metal-organic framework material and the preparation method and application thereof of one kind detection iron ion |
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