CN114874151A - Rare earth europium-based molecular crystalline red light material and preparation method thereof - Google Patents
Rare earth europium-based molecular crystalline red light material and preparation method thereof Download PDFInfo
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- CN114874151A CN114874151A CN202210701137.4A CN202210701137A CN114874151A CN 114874151 A CN114874151 A CN 114874151A CN 202210701137 A CN202210701137 A CN 202210701137A CN 114874151 A CN114874151 A CN 114874151A
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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Abstract
A rare earth europium-based molecular crystalline red light material and a preparation method thereof have the chemical formula: [ Eu ] Eu 2 (TATAB) 2 ·solvents]} n Wherein TATAB is 2,4, 6-tris [ (p-carboxyphenyl) amino group]-1,3, 5-triazine anionic ligand, solvants being solvent molecules. The material is prepared by a solvothermal method, can emit 530-720 nm red light under the excitation of 330nm ultraviolet light, has red light CIE coordinates (0.6102, 0.3867) which are close to saturated red light CIE coordinates, can be used as a red light material, can realize temperature fluorescence sensing, has a wider temperature detection range (303-373K), and is expected to be practically applied to the temperature sensing aspect. The attached drawing in the abstract is a coordination environment diagram of the rare earth europium-based molecular crystalline red light material.
Description
Technical Field
The invention relates to a rare earth europium-based molecular crystalline red light material and a preparation method thereof, belonging to the technical field of molecular crystal materials.
Background
Temperature is an important physical parameter in the fields of human life and natural science, and therefore its accurate measurement is of great significance in scientific and human development. Conventional contact thermometers such as glass thermometers, thermocouples based on the seebeck effect, and thermal resistance thermometers must be used for contact measurement, and the applications in many extreme environments such as strong electromagnetic field environments, the state of a measured object in rapid movement, microfluidic systems, and in living bodies (tissues and even cells) are greatly limited. Compared with conventional contact thermometers, luminescence-based thermometer technology has unique characteristics including non-invasiveness, accuracy, applicability under fast motion and strong electromagnetic fields. Therefore, there is a need to develop and develop luminescence-based thermometer technology.
As a novel luminescence-based thermometer, the europium-based molecular crystalline fluorescent sensing material has the characteristics of both molecular crystalline materials and rare earth europium ions, has designability and abundant luminescence sites, and becomes an excellent choice for preparing the fluorescence thermometer. The material has the unique advantages of larger Stokes shift, high brightness, high color purity (red), longer fluorescence life, no external interference on luminescent color and the like. Due to the emission characteristic of rare earth europium metal, the emission peak position hardly moves along with the temperature change, so that the temperature measurement parameters are limited to fluorescence intensity. Therefore, the temperature can be detected simply through the change of the fluorescence intensity along with the change of the temperature, and the method has the characteristics of high precision, high sensitivity, tiny size, short response time, good adaptability and the like.
Disclosure of Invention
The invention aims to provide a europium-based molecular crystalline red light material and a preparation method thereof, which are used for detecting temperature by applying the red light material to the change of fluorescence intensity along with temperature.
The technical scheme for realizing the invention is as follows, the rare earth europium-based molecular crystalline red light material has the following chemical formula: [ Eu ] as a source of electric potential 2 (TATAB) 2 ·solvents]} n ，
Wherein TATAB is 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine anion ligand, solvents is solvent molecule, n is natural number from 1 to positive infinity, and the structural formula of TATAB is as follows:
the rare earth europium-based molecular crystalline red light material belongs to a monoclinic system and has a space group ofP2 1 /cThe unit cell parameters are: a =27.2917(7) A, b = 23.8793(5) A, c = 14.8177(5) A,α= 90°，ß= 105.75 °，γ= 90 °；
the infrared absorption peak of the rare earth europium-based molecular crystalline red light material is as follows: 3396m, 3270m, 1656s, 1577s, 1479m, 1387m, 1231s, 1174s, 780 s.
2 kinds of europium ions with different coordination and 2 pieces of 2,4, 6-tri [ (p-carboxyl phenyl) amino ] -1,3, 5-triazine anion ligands exist in the basic unit of the rare earth europium-based molecular crystalline red light material; the europium ion and the oxygen atom in the 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine anion ligand coordinate to form a one-dimensional europium chain in space, and a three-dimensional structure is further formed between the europium chains through the 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine in space.
A preparation method of a europium-based molecular crystalline red light material comprises the following steps:
the europium salt and the 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine ligand are fully mixed in a solvent according to the mass ratio of 1: 1-1: 5, and then are cured for 24-72 hours at the temperature of 60-150 ℃ to obtain colorless bulk crystals, namely the rare earth europium-based molecular red light crystalline material.
The europium salt comprises europium chloride hexahydrate; the solvent comprises a mixed solvent of water and N, N-dimethylformamide.
The dosage ratio of the mixture of europium salt and 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine ligand to the solvent is 100mg:500 mg-100 mg:2500 mg.
The application of the rare earth europium-based molecular crystalline red light material comprises the following steps:
the rare earth europium-based molecular crystalline red light material can emit 530-720 nm red light under the excitation of 330nm ultraviolet light, has red light CIE coordinates (0.6102, 0.3867) which are close to saturated red light CIE coordinates, and can be used as a red light material.
The rare earth europium-based molecular crystalline red light material can detect temperature through the change of a fluorescence signal, has a wider temperature detection range of 303K-373K, and can be applied to the field of temperature fluorescence sensing.
The invention has the following beneficial effects: the rare earth europium-based molecular crystalline red light material can be used for fluorescence temperature sensing, and the breadth of rare earth materials and molecular crystalline materials is expanded; the rare earth europium-based molecular crystalline red light material provided by the invention has the advantages of simple preparation process, mild reaction conditions and easiness in mass preparation; the rare earth europium-based molecular crystalline red light material provided by the invention can emit 530-720 nm red light, can realize temperature fluorescence sensing, and has a wider temperature detection range (303-373K).
Drawings
FIG. 1 is a diagram of the coordination environment of the rare earth europium-based molecular crystalline red light material of the present invention;
FIG. 2 is a three-dimensional structure diagram of the rare earth europium-based molecular crystalline red light material of the present invention;
FIG. 3 is the fluorescence spectrum of the rare earth europium-based molecular crystalline red light material of the present invention;
FIG. 4 is a CIE coordinate diagram of the rare earth europium-based molecular crystalline red-light material of the present invention;
FIG. 5 is the fluorescence spectrum of the rare earth europium-based molecular crystalline red light material of the present invention responding to temperature.
Detailed Description
The present embodiment is a rare earth europium-based molecular crystalline red light material, which has a chemical formula: [ Eu ] as a source of electric potential 2 (TATAB) 2 ·solvents]} n ，
Wherein TATAB is 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine anion ligand, solvants is solvent molecule, and the structural formula of TATAB is as follows:
the preparation method of the rare earth europium-based molecular crystalline red light material comprises the following steps:
dissolving 100mg of europium chloride hexahydrate and 200mg of 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine ligand in 2000mg of N, N-dimethylformamide, and then curing for 72 hours at the temperature of 130 ℃ to obtain colorless bulk crystals, namely the rare earth europium-based molecular crystalline red light material.
The rare earth europium-based molecular crystalline red light material prepared in the embodiment is characterized as follows:
(1) the structure determination of the rare earth europium-based molecular crystalline red light material of the embodiment:
the crystal structure is measured by using a Supernova type X-ray single crystal diffractometer, using Mo-Kalpha rays (lambda = 0.71073A) subjected to graphite monochromatization as an incident radiation source, collecting diffraction points in an omega-phi scanning mode, correcting by a least square method to obtain unit cell parameters, solving a difference Fourier electron density diagram by using a SHELXL-97 direct method to obtain a crystal structure, and correcting by Lorentz and a polarization effect. All H atoms were synthesized by difference Fourier and determined by ideal position calculation, and detailed crystallography (removal of solvent molecules) data are shown in table 1.
TABLE 1 crystallography data for rare earth europium-based molecular crystalline red-light materials
Fig. 1 is a coordination environment diagram of the rare earth europium-based molecular crystalline red light material of the embodiment, and it can be seen from the diagram that: the basic structural unit of the europium ion doped 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine anionic ligand exists.
Fig. 2 is a three-dimensional structure diagram of the rare earth europium-based molecular crystalline red light material in the embodiment, wherein n is a natural number from 1 to positive infinity in the chemical formula of the rare earth europium-based molecular crystalline red light material, which indicates that the material is a polymer.
(2) The fluorescent property of the rare earth europium-based molecular crystalline red light material is characterized in that:
FIG. 3 shows the europium-based rare earth element of this exampleSolid fluorescence spectrum of the sub-crystalline red light material, and the graph shows that: the rare earth europium-based molecular crystalline red light material has 4 emission peaks at 594nm, 617nm, 652nm and 699nm, which are respectively derived from 5 D 0 → 7 F J (J = 1, 2, 3,4)。
Fig. 4 shows CIE coordinates of the rare earth europium-based molecular crystalline red light material of the present embodiment, which are (0.6102, 0.3867), located in the red region and close to the saturated red light CIE coordinates.
FIG. 5 shows the fluorescence spectra of rare earth europium-based molecular crystalline red-light materials under different temperature conditions. As can be seen from the figure: under different temperature conditions, the fluorescence intensity of the rare earth europium-based molecular crystalline red light material changes along with the change. The fluorescence intensity of the rare earth europium-based molecular crystalline red light material shows a descending trend along with the temperature rise, and the change is obvious, and finally fluorescence quenching occurs, so that the rare earth europium-based molecular crystalline red light material has good fluorescence response to the temperature and can be used as a temperature fluorescent probe.
Claims (7)
1. The rare earth europium-based molecular crystalline red light material is characterized by having the chemical formula as follows: [ Eu ] as a source of electric potential 2 (TATAB) 2 ·solvents]} n ，
Wherein TATAB is 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine anion ligand, solvants is solvent molecule, and n is a natural number from 1 to positive infinity;
the structural formula of TATAB is as follows:
the rare earth europium-based molecular crystalline red light material belongs to a monoclinic system and has a space group ofP2 1 /cThe unit cell parameters are: a =27.2917(7) A, b = 23.8793(5) A, c = 14.8177(5) A,α= 90°，ß= 105.75 °，γ= 90 °；
the infrared absorption peak of the rare earth europium-based molecular crystalline red light material is as follows: 3396m, 3270m, 1656s, 1577s, 1479m, 1387m, 1231s, 1174s, 780 s.
2. The rare earth europium-based molecular crystalline red light material as claimed in claim 1, wherein 2 different coordination europium ions and 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine anionic ligands are present in the basic unit of the rare earth europium-based molecular crystalline red light material; the europium ion and the oxygen atom in the 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine anion ligand coordinate to form a one-dimensional europium chain in space, and a three-dimensional structure is further formed between the europium chains through the 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine in space.
3. The rare earth europium-based molecular crystalline red light material of claim 1, which is prepared by the following method,
the europium salt and the 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine ligand are fully mixed in a solvent according to the mass ratio of 1: 1-1: 5, and then are cured for 24-72 hours at the temperature of 60-150 ℃ to obtain colorless bulk crystals, namely the rare earth europium-based molecular red light crystalline material.
4. The method of preparing a rare earth europium-based molecular crystalline red light material according to claim 3, wherein said europium salt comprises europium chloride hexahydrate; the solvent comprises a mixed solvent of water and N, N-dimethylformamide.
5. The method of claim 3, wherein the ratio of the mixture of europium salt and 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine ligand to solvent is 100mg:500mg to 100mg:2500 mg.
6. The rare earth europium-based molecular crystalline red light material as claimed in claim 1, wherein the rare earth europium-based molecular crystalline red light material can emit 530-720 nm red light under the excitation of 330nm ultraviolet light, and the red light CIE coordinates of the rare earth europium-based molecular crystalline red light material are (0.6102, 0.3867), are close to saturated red light CIE coordinates, and can be used as a red light material.
7. The application of the rare earth europium-based molecular crystalline red light material as claimed in claim 1, wherein the rare earth europium-based molecular crystalline red light material can detect the temperature through the change of a fluorescence signal, the wider temperature detection range is 303K-373K, and the rare earth europium-based molecular crystalline red light material can be applied to the field of temperature fluorescence sensing.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084247A (en) * | 2016-06-08 | 2016-11-09 | 三峡大学 | A kind of Rare Earth Europium base organic crystalline material, preparation and application thereof |
| CN108998007A (en) * | 2018-08-02 | 2018-12-14 | 江西省科学院应用化学研究所 | A kind of preparation method of rare earth metal organic framework materials |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084247A (en) * | 2016-06-08 | 2016-11-09 | 三峡大学 | A kind of Rare Earth Europium base organic crystalline material, preparation and application thereof |
| CN108998007A (en) * | 2018-08-02 | 2018-12-14 | 江西省科学院应用化学研究所 | A kind of preparation method of rare earth metal organic framework materials |
Non-Patent Citations (1)
| Title |
|---|
| 姚晋: ""含氮多羧酸稀土/锌配位框架的结构及功能"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 4, pages 2 - 3 * |
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