CN111484625A - Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivative with conjugated structure and synthetic method thereof - Google Patents

Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivative with conjugated structure and synthetic method thereof Download PDF

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CN111484625A
CN111484625A CN202010318122.0A CN202010318122A CN111484625A CN 111484625 A CN111484625 A CN 111484625A CN 202010318122 A CN202010318122 A CN 202010318122A CN 111484625 A CN111484625 A CN 111484625A
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冯勋
陈楠
方海鹏
张慧娟
于晶晶
赵鑫
张振涛
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Luoyang Normal University
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Abstract

The invention relates to a Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivatives with conjugated structures, which is characterized in that: the chemical formula of the coordination polymer is: [ Tb (tcptpy) ((H))2O)2·2H2O]n, wherein n is greater than 1, ligand H3tcptpy is 4- (2,4, 6-tricarboxyphenyl) -4, 2': 6', 4' -bipyridine, the coordination polymer crystal basic unit belongs to monoclinic system, space group is P21/c, and the chemical formula is as follows: C24H16N3O8Tb with unit cell parameters of
Figure DDA0002460324610000013
Figure DDA0002460324610000011
α=90°,β=95.143(3)°,γ=90°,
Figure DDA0002460324610000012
The luminescent material can be excited by near ultraviolet light and emits bright green fluorescence. The material has low cost of raw materials, simple preparation process equipment and excellent comprehensive performance, is suitable for industrial production, and can meet the requirements of the electronic industry, display and illumination in public places and the application field of environmental ion detection.

Description

Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivative with conjugated structure and synthetic method thereof
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivatives with conjugated structures and a synthesis method thereof.
Background
Iron is one of elements commonly existing in our living environment, Fe3+Ions are present in a wide range of environments and biological systems, and play an important role not only in the living body but also in the transport of oxygen, the synthesis of DNA and RNA. And, Fe3+The lack of ions destroys the homeostasis and metabolism of cells, thereby causing various serious diseases such as hepatitis, hereditary hemochromatosis, parkinson's disease. The presence of too much excess iron is also toxic and can cause vomiting, diarrhea and intestinal damage. When a person ingests an excessive amount of iron or contacts Fe for a long time3+Or repeated blood transfusion, or chronic alcoholism, iron may accumulate in the body. Conventionally, Fe is measured by conventional chemical analysis and atomic absorption spectrometry3+Including AAS (atomic absorption spectrophotometry), ICP-AES (inductively coupled plasma atomic emission spectrometry) and electrochemical protocols. However, these available methods are very limited and only in certain cases, especially complex and expensive, are Fe detected under field conditions3+It is not realistic that L n (III) metal organic frameworks which have been rapidly developed in recent years can be used as excellent fluorescent probes of materials, and also have caused academia due to their advanced characteristics such as high stability, sensitivity and selectivity, and reproducibility and fast response timeThere is a wide concern.
The lanthanide frameworks (L n-MOFs) have superior optical properties compared to transition metals, including high color purity, strong sharp emission, large Stokes shift, high quantum yield, long luminescence lifetime, and high photochemical stability, low toxicity, and narrow absorption and emission bands, especially L n-MOFs of Tb (III) and Eu (III) conjugated ligand derivatives have been widely used in recent years in ion detection.
Disclosure of Invention
The invention aims to solve the defects of the technical problems and provides a Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivatives with conjugated structures and a synthetic method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that: a Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivatives with conjugated structures is disclosed, wherein the chemical formula of the coordination polymer is as follows: [ Tb (tcptpy) ((H))2O)2·2H2O]n, wherein n is greater than 1, ligand H3tcptpy is 4- (2,4, 6-tricarboxyphenyl) -4, 2': 6', 4' -bipyridine, the coordination polymer crystal basic unit belongs to monoclinic system, space group is P21/c, and the chemical formula is as follows: C24H16N3O8Tb with unit cell parameters of
Figure BDA0002460324590000021
α=90°,β=95.143(3)°,γ=90°,
Figure BDA0002460324590000022
The luminescent material can be excited by near ultraviolet light and emits bright green fluorescence.
The synthesis method of the coordination polymer green luminescent material comprises the following steps:
first, preparing precursor liquid
a. Taking organic ligand H3tcptpy is dissolved in a mixed solution of water and an organic solvent to obtain a solution A;
b. adding a Tb source into the solution A, and uniformly stirring to obtain a solution B;
c. stirring the solution B at normal temperature and normal pressure, and then adding acid to adjust the pH value to 2-4 to obtain a precursor solution C for later use;
secondly, preparing luminescent material
d. And transferring the precursor solution C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding a mixed solution of water and DMF, sealing the reaction kettle, then putting the reaction kettle into an oven, reacting at the temperature of 130 ℃ and 170 ℃ for 60-90h, controlling the reaction kettle to cool to room temperature at the cooling rate of 5 ℃/h after the reaction is finished, collecting colorless crystals in the reaction kettle, and washing and drying the crystals to obtain the white powdery luminescent material.
As a further optimization of the synthesis method of the coordination polymer green luminescent material: the organic solvent in the mixed solution in the step a is methanol, ethanol or propanol, and the volume ratio of water to the organic solvent is 0.1:1-3: 1.
As a further optimization of the synthesis method of the coordination polymer green luminescent material: the adding amount ratio of the organic ligand to the mixed solution in the step a is that 0.1-0.5mmol of organic ligand H is added into every 30ml of the mixed solution3tcptpy。
As a further optimization of the synthesis method of the coordination polymer green luminescent material: the Tb source in the step b is Tb4O7Or Tb (NO)3)3·H2O。
As a further optimization of the synthesis method of the coordination polymer green luminescent material: the ratio of the Tb source to the addition amount of the solution A in the step b is as follows: 10-50ml of solution A is added with 0.01-0.1mmol of Tb4O7Or Tb (NO)3)3·H2O。
As a further optimization of the synthesis method of the coordination polymer green luminescent material: in the step c, dissolvingStirring liquid B with magnetic stirrer, adding diluted HNO3The pH value is adjusted.
As a further optimization of the synthesis method of the coordination polymer green luminescent material: and d, washing the crystals for 2-3 times by using a mixed solution of ethanol and water, and drying the crystals in a vacuum drying oven at 50-80 ℃.
Advantageous effects
The synthesized coordination polymer green luminescent material has the advantages of good crystal crystallinity, good light transmittance, no toxicity, no pollution, high thermal stability, low raw material cost, simple preparation process equipment and excellent comprehensive performance, can be excited by near ultraviolet light to emit green fluorescence, is suitable for industrial production, and can meet the requirements of the application fields of electronic industry, display in public places, information, illumination and ion detection;
secondly, the coordination polymer green luminescent material of the invention uses H3the semi-rigid ligand of tcptpy (Chinese name 2,4, 6-tricarboxyphenyl) -4,2 ': 6', 4 "-terpyridine was used to construct L N-MOF for the design of sensing materials, which in one aspect has multiple N and O donor sites that facilitate interaction with L N-MOF3+Coordination of ions; on the other hand, it serves chromophores with large conjugated pi systems to sensitize the luminescence of lanthanide ions; and, it has lewis base sites that interact with the target analyte to enhance detection selectivity and sensitivity.
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FIG. 1 is a graph comparing an X-ray diffraction (XRD) pattern of a product prepared according to example 1 of the present invention with simulated PXRD of single crystal diffraction data;
FIG. 2 is an infrared spectrum of the product produced in example 1 of the present invention;
FIG. 3 is a structural view of the essential elements of the product produced in example 1 of the present invention;
FIG. 4 is a thermogravimetric differential thermal analysis spectrum of a product prepared in example 1 of the present invention;
FIG. 5 is a fluorescence emission spectrum of the product prepared in example 1 of the present invention;
FIG. 6 is a graph showing the variation of the emitted fluorescence intensity with the concentration of Fe3+ for the product prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments.
Example 1
A Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivatives with conjugated structures is disclosed, wherein the chemical formula of the coordination polymer is as follows: [ Tb (tcptpy) ((H))2O)2·2H2O]n, wherein n is greater than 1, ligand H3tcptpy is 4- (2,4, 6-tricarboxyphenyl) -4, 2': 6', 4' -bipyridine, the coordination polymer crystal basic unit belongs to monoclinic system, space group is P21/c, and the chemical formula is as follows: C24H16N3O8Tb with unit cell parameters of
Figure BDA0002460324590000031
α=90°,β=95.143(3)°,γ=90°,
Figure BDA0002460324590000032
The luminescent material can be excited by near ultraviolet light and emits bright green fluorescence.
The preparation method of the coordination polymer green luminescent material comprises the following steps:
raw materials: tb (terbium) oxide4O7,Tb(NO3)36H2O, glacial acetic acid, dilute hydrochloric acid, ethanol, N-Dimethylformamide (DMF) concentrated hydrochloric acid, and NaOH, all of analytical purity, were supplied by shanghai national medicine, luoyang chemical reagents, beijing fengts chemical materials, inc.
An intelligent magnetic heating and stirring electric heating jacket of Zhengzhou Dufu instrument factory; a flat electronic analytical balance at sea; a Fourier transform infrared spectrometer, Avater370, Nicolet corporation, USA; the device comprises a numerical control ultrasonic cleaner, a circulating water type vacuum pump, a melting point tester and a rotary evaporation instrument, wherein an X-ray single crystal diffractometer is CCD2000 of Bruker Smart company in Germany, an X-ray powder diffractometer, Bruker D8Advance in Germany, an element analyzer Perkin-Elmer2400, the fluorescence characteristics are tested on a HitachiF-7000 fluorescence spectrometer, and a thermogravimetric analyzer NETZSCH 51-A449C.
Preparing a precursor solution:
a. 0.3mmol of organic ligand H is taken3tcptpy dissolved in 30ml of water mixed with organic solvent
Mixing the solution to obtain a solution A;
b. 0.05mmol of Tb was taken4O7Adding the mixture into the solution A, and uniformly stirring to obtain a solution B;
c. b, stirring the solution B prepared in the step B for 20min at normal temperature and normal pressure by using a magnetic stirrer, and then adding diluted HNO3And adjusting the pH value to 2.0 to obtain a precursor solution C for later use.
(II) preparing a luminescent material:
d. and C, transferring the precursor solution C prepared in the step C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding a mixed solution of water and DMF, sealing the reaction kettle, putting the reaction kettle into an oven, selecting a temperature control mode for reaction, controlling the temperature to be about 150 ℃, controlling the reaction kettle to cool to room temperature at a cooling rate of 5 ℃/h after reacting for about 2 days, collecting colorless crystals appearing at the bottom in the reaction kettle, washing the collected crystals for multiple times by using distilled water, and drying in a vacuum drying oven at 60 ℃ to obtain a white powdery luminescent material.
The chemical formula of H3tcptpy in step a is as follows:
Figure BDA0002460324590000041
and c, mixing the water and the organic solvent in the step c, wherein the organic solvent is methanol, ethanol or propanol, and the volume ratio of the water to the organic solvent is 0.5: 1.
The obtained product { [ Tb (H) ]3tcptpy)2·2H2O]N was analyzed with a Bruker SMARTAPEXII model single crystal X-ray diffractometer, Germany, as shown in FIG. 1: the XRD pattern of the product is identical with the PXRD pattern simulated by single crystal diffraction data, and strong characteristic diffraction peaks appear at positions with 2 theta of 7.8,11.4,16.8,18.1,19.6, 26.2 and the like. Simultaneously, the single crystal structure of the obtained product is analyzed, and the crystal structure data is shown in the following table:
Figure BDA0002460324590000051
R=∑||F0|-|Fc||\∑|F0|,wR={∑[w(F0 2-Fc 2)2]/∑(F0 2)2}1/2
the obtained product was subjected to elemental analysis using an elemental analyzer, Perkin-Elmer-2000, available from America, and analysis showed that the material consisted of the following components: the compound is C24H16N3O8Tb, and the content percentage of elements calculated theoretically is as follows: c45.51, H2.55, N6.64, actual assay: c45.40, H2.67, N4.66. The resulting product [ Tb (tcptpy) ((H))2O)2·2H2O]n is analyzed by Nicolet6700 Fourier Infrared Spectroscopy, and the IR spectrum is shown in FIG. 2 at 3420cm-1The broad and weak peak is the water molecule hydroxyl vibration at 1516cm-1,1390cm-1, 1320cm-1Corresponding to the symmetrical and asymmetrical vibration peaks of the ligand carboxyl, the wave number difference is less than 200nm, which shows that the carboxyl of the ligand adopts a monodentate coordination mode and a chelation mode to link metal ions. The crystal structure of the product was obtained by simulating crystal software with Diamond3D, and as shown in FIG. 3, the compound belongs to monoclinic crystal system and space group is P21/c. In the basic unit there is a crystallographically independent Tb3+Ion, a fully deprotonated tcptpy3-A ligand and two coordinated water molecules. Central Tb3+The ion shows an octadentate [ TbO7N1 ]]Coordination environment body, showing coordination geometry of a double-crown triangular pyramid in which five oxygen atoms come from tcptpy3-The ligand, the other two oxygen atoms from water molecules, and one nitrogen atom from the pyridine atom, complete coordination with the metal center. Thermogravimetric analysis found an initial mass loss of 10.31% from room temperature to 215 ℃, probably due to the loss of two lattices H2The O molecule and two coordinated water molecules (calculated: 10.70%). Decomposition from 215 ℃ to 505 ℃, the overall framework of the compound is heated, resulting in tcptpy3-Ligand elimination, as shown in FIG. 4. The measured fluorescence spectrum is shown in fig. 5, when the product is excited under 342nm near ultraviolet light, the emission fluorescence peak appears in a visible region of 485nm, 653nm and the like, and particularly, the most powerful emission spectrum appears in a yellow-green light region of 545 nm. By monitoring the emission spectrum intensity of 5D4 → 7F5 at 545nm, it was found that the spectrum intensity of the inventive compound has little change in the pre-fluorescence of various metal cations in aqueous solution. Interestingly, only Fe was found3+To further understand the fluorescent response of the compounds to Fe3+ ions, 1 × 10-3mol/LFe3+Added dropwise to a solution containing [ Tb (tcptpy) (H) by a microsyringe2O)2·2H2O]The fluorescence spectra were collected when the n compound was suspended in water and it was found that the luminescence intensity dropped to 40.7% in a 1x10-4 mol/L Fe3+ aqueous solution, in particular, the luminescence was completely quenched when the concentration of Fe3+ in an aqueous solution was 4.03 × 10-4 mol/L, and as a result, as shown in fig. 6, the compound of the present invention was found to exhibit a high examination sensitivity KSV of 3.54 × 104M-1 and a linear correlation R2 of 0.99209, according to the Stern-Volmer equation.
Example 2
A Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivatives with conjugated structures is disclosed, wherein the chemical formula of the coordination polymer is as follows: [ Tb (tcptpy) ((H))2O)2·2H2O]n, wherein n is greater than 1, ligand H3tcptpy is 4- (2,4, 6-tricarboxyphenyl) -4, 2': 6', 4' -bipyridine, the coordination polymer crystal basic unit belongs to monoclinic system, space group is P21/c, and the chemical formula is as follows: C24H16N3O8Tb with unit cell parameters of
Figure BDA0002460324590000061
α=90°,β=95.143(3)°,γ=90°,
Figure BDA0002460324590000062
The luminescent material can be excited by near ultraviolet light and emits bright green fluorescence.
The preparation method of the coordination polymer green luminescent material comprises the following steps:
preparing a precursor solution:
a. 0.3mmol of organic ligand H is taken3tcptpy dissolved in 30ml of water mixed with organic solvent
Mixing the solution to obtain a solution A;
b. 0.02mmol of Tb (NO) was taken3)3·H2Adding O into 10ml of the solution A, and uniformly stirring to obtain a solution B;
c. b, stirring the solution B prepared in the step B for 30min at normal temperature and normal pressure by using a magnetic stirrer, and then adding diluted HNO3And adjusting the pH value to 4.0 to obtain a precursor solution C for later use.
(II) preparing a luminescent material:
d. and C, transferring the precursor solution C prepared in the step C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding a mixed solution of water and DMF, sealing the reaction kettle, putting the reaction kettle into an oven, selecting a temperature control mode for reaction, controlling the temperature to be about 130 ℃, controlling the reaction kettle to cool to room temperature at a cooling rate of 5 ℃/h after reacting for 60 hours, collecting colorless crystals appearing at the bottom in the reaction kettle, washing the collected crystals for multiple times by using distilled water, and drying in a vacuum drying oven at 50 ℃ to obtain a white powdery luminescent material.
Example 3
A Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivatives with conjugated structures is disclosed, wherein the chemical formula of the coordination polymer is as follows: [ Tb (tcptpy) ((H))2O)2·2H2O]n, wherein n is greater than 1, ligand H3tcptpy is 4- (2,4, 6-tricarboxyphenyl) -4, 2': 6', 4' -bipyridine, the coordination polymer crystal basic unit belongs to monoclinic system, space group is P21/c, and the chemical formula is as follows: C24H16N3O8Tb with unit cell parameters of
Figure BDA0002460324590000071
α=90°,β=95.143(3)°,γ=90°,
Figure BDA0002460324590000072
The luminescent material can be excited by near ultraviolet light and emits bright green fluorescence.
The preparation method of the coordination polymer green luminescent material comprises the following steps:
preparing a precursor solution:
a. 0.4mmol of organic ligand H is taken3tcptpy dissolved in 50ml of water mixed with organic solvent
Mixing the solution to obtain a solution A;
b. 0.08mmol of Tb (NO)3)3·H2Adding O into 40ml of the solution A, and uniformly stirring to obtain a solution B;
c. b, stirring the solution B prepared in the step B for 30min at normal temperature and normal pressure by using a magnetic stirrer, and then adding diluted HNO3And adjusting the pH value to 3.0 to obtain a precursor solution C for later use.
(II) preparing a luminescent material:
d. and C, transferring the precursor solution C prepared in the step C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding a mixed solution of water and DMF, sealing the reaction kettle, putting the reaction kettle into an oven, selecting a temperature control mode for reaction, controlling the temperature to be about 170 ℃, controlling the reaction kettle to cool to room temperature at a cooling rate of 5 ℃/h after reacting for 80 hours, collecting colorless crystals appearing at the bottom in the reaction kettle, washing the collected crystals for multiple times by using distilled water, and drying in a vacuum drying oven at 80 ℃ to obtain a white powdery luminescent material.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (8)

1. A Tb coordination polymer green luminescent material containing pyridine carboxylic acid derivatives with conjugated structures is characterized in that: the chemical formula of the coordination polymer is: [ Tb (tcptpy) ((H))2O)2·2H2O]n, wherein n is greater than 1, ligand H3tcptpy is 4- (2,4, 6-tricarboxyphenyl) -4, 2': 6', 4' -bipyridine, coordination polymer crystal basic unit belongs to monoclinic system and space groupIs P21/c, and has the chemical formula: C24H16N3O8Tb with unit cell parameters of
Figure FDA0002460324580000011
Figure FDA0002460324580000012
α=90°,β=95.143(3)°,γ=90°,
Figure FDA0002460324580000013
The luminescent material can be excited by near ultraviolet light and emits bright green fluorescence.
2. The method for synthesizing coordination polymer green luminescent material according to claim 1, wherein: the method comprises the following steps:
first, preparing precursor liquid
a. Taking organic ligand H3tcptpy is dissolved in a mixed solution of water and an organic solvent to obtain a solution A;
b. adding a Tb source into the solution A, and uniformly stirring to obtain a solution B;
c. stirring the solution B at normal temperature and normal pressure, and then adding acid to adjust the pH value to 2-4 to obtain a precursor solution C for later use;
secondly, preparing luminescent material
d. And transferring the precursor solution C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding a mixed solution of water and DMF, sealing the reaction kettle, then putting the reaction kettle into an oven, reacting at the temperature of 130 ℃ and 170 ℃ for 60-90h, controlling the reaction kettle to cool to room temperature at the cooling rate of 5 ℃/h after the reaction is finished, collecting colorless crystals in the reaction kettle, and washing and drying the crystals to obtain the white powdery luminescent material.
3. The method for synthesizing coordination polymer green luminescent material according to claim 2, wherein: the organic solvent in the mixed solution in the step a is methanol, ethanol or propanol, and the volume ratio of water to the organic solvent is 0.1:1-3: 1.
4. The method for synthesizing coordination polymer green luminescent material according to claim 3, wherein: the adding amount ratio of the organic ligand to the mixed solution in the step a is that 0.1-0.5mmol of organic ligand H is added into every 30ml of the mixed solution3tcptpy。
5. The method for synthesizing coordination polymer green luminescent material according to claim 2, wherein: the Tb source in the step b is Tb4O7Or Tb (NO)3)3·H2O。
6. The method for synthesizing coordination polymer green luminescent material according to claim 5, wherein: the ratio of the Tb source to the addition amount of the solution A in the step b is as follows: 10-50ml of solution A is added with 0.01-0.1mmol of Tb4O7Or Tb (NO)3)3·H2O。
7. The method for synthesizing coordination polymer green luminescent material according to claim 2, wherein: in the step c, the solution B is stirred by a magnetic stirrer, and diluted HNO is added after stirring3The pH value is adjusted.
8. The method for synthesizing coordination polymer green luminescent material according to claim 2, wherein: and d, washing the crystals for 2-3 times by using a mixed solution of ethanol and water, and drying the crystals in a vacuum drying oven at 50-80 ℃.
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CN114672038B (en) * 2022-04-22 2023-03-10 山西大学 Two-dimensional binuclear terbium coordination polymer and preparation method and application thereof
CN114716688A (en) * 2022-05-17 2022-07-08 山西大学 Terbium complex and preparation method and application thereof
CN114716688B (en) * 2022-05-17 2022-12-30 山西大学 Terbium complex and preparation method and application thereof

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