Two Eu3+Activated fluorescent and luminous material and its synthesis
阅读说明：本技术 一种两个Eu3+激活的新型荧光、发光材料及其合成方法 (Two Eu3+Activated fluorescent and luminous material and its synthesis ) 是由 李兵 张淑华 胡振光 曾玉梅 梅毅 于 2019-08-27 设计创作，主要内容包括：本发明提供一种两个Eu~(3+)激活的新型荧光、发光材料及其合成方法,涉及荧光材料技术领域,荧光材料{[Eu_2(H_2L)(H_2-DHBDC)_(2.5)(H_2O)]·H_2O}_n是由Eu~(3+)和H_3L、H_4-DHBDC配位而成,利用溶剂热法合成的新型荧光、发光材料。本发明具有工艺简单、成本低廉、化学组分易于控制、重复性好并产量高等优点,在荧光固体材料领域有广阔的应用前景。(The invention provides two Eu 3+ An activated novel fluorescent and luminescent material and a synthetic method thereof relate to the technical field of fluorescent materials, and the fluorescent material { [ Eu ] 2 (H 2 L)(H 2 ‑DHBDC) 2.5 (H 2 O)]·H 2 O} n Is made of Eu 3+ And H 3 L、H 4 -DHBDC, and is synthesized by a solvothermal method. The invention has the advantages of simple process, low cost, easy control of chemical components, good repeatability, high yield and the like, and has wide application prospect in the field of fluorescent solid materials.)
1. Two Eu3+A novel fluorescent light-emitting material characterized in that it is { [ Eu ]2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nThe monomer structure is as follows:
wherein H2L is H with one H atom removed3L，H3L has a structural formula ofH2-DHBDC is H with two H atoms removed4-DHBDC，H4-DHBDC has the formula
2. Two Eu according to claim 13+Novel activated fluorescent, luminescent material, characterized in that said novel fluorescent, luminescent material { [ Eu ]2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nIs composed of two Eu3+And H3L、H4-DHBDC in coordination; wherein, the first europium ion Eu1 is coordinated with eight oxygen atoms, wherein four oxygen atoms of O2E, O5, O14D and O12 are from H4In DHBDC, the other four oxygen atoms O17, O18A, O19B, O20C are derived from H3In L, a micro-deformed square antiprism configuration is formed; the second europium ion Eu2 is coordinated with nine oxygen atoms, wherein seven oxygen atoms are selected from O1E, O6, O8, O9, O11, O12 and O15DFrom H4In DHBDC, O22F is from H3In L, O7 is coordinated from the terminal water molecule to form a triangular prism with three caps.
3. Two Eu according to claim 13+Novel activated fluorescent, luminescent material, characterized in that said novel fluorescent, luminescent material { [ Eu ]2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nThe monomer has the molecular formula of C42H30Eu2NO23S, the crystal system belongs to the triclinic system, the space group is P-1, the unit cell parameter isα＝98.658(4)°，β＝99.471(4)°，γ＝91.086(4)°，
4. Two Eu according to any one of claims 1 to 33+The synthesis method of the activated novel fluorescent and luminescent material is characterized by adopting a solvothermal method for synthesis, and specifically comprises the following steps:
(1) h is to be3L、H4Dissolving DHBDC in a solvent, stirring uniformly, adding europium nitrate, and continuously stirring until the solution is uniform to obtain a mixed material;
(2) placing the mixed material into a reaction kettle, sealing, placing the reaction kettle into an oven with the temperature of 110-120 ℃, taking out after 90-96 hours, cooling to room temperature, opening the reaction kettle, wherein the light yellow blocky crystal at the bottom in the reaction kettle is { [ Eu ] -2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}n。
5. The two Eu according to claim 43+A method for synthesizing an activated novel fluorescent, luminescent material, characterized in that H is3L、H4-DHBDC. The mass ratio of the solvent to the europium nitrate is 0.022-0.044: 0.025 to 0.050: 4-8: 0.045-0.090.
6. The two Eu according to claim 43+The synthesis method of the activated novel fluorescent and luminescent material is characterized in that the reaction kettle is a polytetrafluoroethylene high-pressure reaction kettle.
7. The two Eu according to claim 43+The synthesis method of the activated novel fluorescent and luminescent material is characterized in that the solvent is secondary distilled water.
Technical Field
The invention relates to the technical field of fluorescent materials, namely two Eu3+Activated fluorescent and luminescent materials and their synthesis.
Background
Coordination polymers (coordination polymers) are one of the fastest growing directions in coordination chemistry in the last decade, and are a new research topic related to multiple disciplines such as inorganic chemistry, organic chemistry and coordination chemistry. The material has the characteristics of rigidity of inorganic materials and flexibility of organic materials, so that the material has great development potential and attractive development prospect in the aspect of modern material research. The metal-organic complex is an excellent fluorescent material which is most widely researched and most applied at present, and can show visible light (400-800 nm) with various colors according to the types and contents of metals and activators in the pigment under the irradiation of ultraviolet light (200-400 nm). With the progress of science and technology, people have more and more researches on fluorescence, and the application range of fluorescent substances is wider and wider. Besides being used as dye, the fluorescent substance can be widely applied to the fields of organic pigment, optical brightening agent, photo-oxidant, paint, chemical and biochemical analysis, solar energy catcher, anti-counterfeiting mark, medicine tracing, laser and the like.
At present, because the specific 4f electrons of the rare earth ions are influenced by the larger shielding effect of outer layer electrons and the stronger magnetic anisotropy of the rare earth ions, the influence of ligand fields on the rare earth ions is small, so that the rare earth compounds generally have narrow fluorescence emission peaks and good color purity. The compound can be used as a photoluminescence material and provides a foundation for researching an electroluminescent material, the obtained complex has various structures and good stability, and is an important direction in the research field of fluorescence and luminescent materials. Therefore, the preparation of stable and efficient novel fluorescent and luminescent materials is one of the challenges in the field of current functional material chemistry.
Disclosure of Invention
In view of the above problems, the present invention provides two Eu3+The activated novel fluorescent and luminescent material and the synthesis method thereof utilize a solvothermal method to design and synthesize the novel fluorescent material, have the advantages of simple process, low cost, easy control of chemical components, good repeatability, high yield and the like, and have wide application prospect in the field of fluorescent solid materials.
Therefore, the invention provides the following technical scheme:
two Eu3+A novel fluorescent, luminescent material activated, said novel fluorescent, luminescent material being { [ Eu ]2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nThe monomer structure is as follows:
wherein H2L is H with one H atom removed3L，H3L has a structural formula ofH2-DHBDC is H with two H atoms removed4-DHBDC，H4-DHBDC has the formula
Further, the novel fluorescent and luminescent material { [ Eu { [2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nIs composed of two Eu3+And H3L、H4-DHBDC in coordination; wherein, the first europium ion Eu1 coordinates with eight oxygen atoms, wherein four oxygen atoms O2E, O5, O14D and O12 are from H4In DHBDC, the other four oxygen atoms O17, O18A, O19B, O20C are derived from H3In L, a micro-deformed square antiprism configuration is formed; the second europium ion Eu2 is coordinated with nine oxygen atoms, wherein seven oxygen atoms O1E, O6, O8, O9, O11, O12 and O15D are derived from H4In DHBDC, O22F fromFrom H3In L, O7 is coordinated from the terminal water molecule to form a triangular prism with a three-cap.
Further, the novel fluorescent and luminescent material { [ Eu { [2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nThe monomer has the molecular formula of C42H30Eu2NO23S, the crystal system belongs to the triclinic system, the space group is P-1, the unit cell parameter is α＝98.658(4)°，β＝99.471(4)°，γ＝91.086(4)°，
The invention provides the two Eu3+Activated novel fluorescent, luminescent materials { [ Eu ]2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nThe synthesis method adopts a solvothermal method for synthesis, and specifically comprises the following steps:
(1) h is to be3L、H4Dissolving DHBDC in a solvent, stirring uniformly, adding europium nitrate, and continuously stirring until the solution is uniform to obtain a mixed material;
(2) placing the mixed material into a reaction kettle, sealing, placing the reaction kettle into an oven with the temperature of 110-120 ℃, taking out after 90-96 hours, cooling to room temperature, opening the reaction kettle, wherein the light yellow blocky crystal at the bottom in the reaction kettle is { [ Eu ] -2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}n。
Further, said H3L、H4The mass ratio of-DHBDC to solvent to europium nitrate is 0.022-0.044: 0.025 to 0.050: 4-8: 0.045-0.090.
Further, the reaction kettle is a polytetrafluoroethylene high-pressure reaction kettle.
Further, the solvent is double distilled water.
H used in the invention3L (4- (N, N' -bis (4-carboxybenzyl) amino) benzenesulfonic acid), H4-DHBDC (2, 5-dihydroxyterephthalic acid), europium nitrate (Eu (NO)3)3·6H2O) are analytically pure reagents, and the reagents used in the invention are purchased from chemical reagent companies at home and abroad and are directly used without continuous purification.
The invention has the following beneficial effects:
1. the invention has the advantages of simple process, short reaction time, safe operation, easy control of chemical components and low cost.
2. The product obtained by the method has good repeatability and stability, high yield and 70 percent of yield.
3. The { [ Eu ] obtained by the invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nUnder the excitation of the wavelength of 300nm, the fluorescence intensity of the large emission wavelength is about 2033a.u. at 509nm, and red fluorescence is presented.
4. The { [ Eu ] obtained by the invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nShows stable and efficient luminescence signals, and the electrochemical luminescence intensity is about 2700a.u.
Drawings
FIG. 1 is a monomer structure diagram of ligand 4- (N, N' -bis (4-carboxybenzyl) amino) benzenesulfonic acid of the present invention.
FIG. 2 is a monomer structure diagram of the ligand 2, 5-dihydroxyterephthalic acid of the present invention.
FIG. 3 shows { [ Eu ] according to the present invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nSchematic of the monomer structure of (free water molecules have been removed); (in the figure, O1, O2, O2A … O22F and O23 represent oxygen atoms at different positions, N1 represents a nitrogen atom and S1 represents a sulfur atom).
FIG. 4 shows { [ Eu ] of the present invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nIndependent coordination configuration diagram of middle metal atom Eu 1.
FIG. 5 shows { [ Eu ] of the present invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nIndependent coordination configuration diagram of middle metal atom Eu 2.
FIG. 6 shows { [ Eu ] of the present invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nSchematic three-dimensional stacking of monomers from c-axis direction.
FIG. 7 shows { [ Eu ] prepared in example 1 of the present invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nThe fluorescence spectrum of the liquid.
FIG. 8 shows { [ Eu ] prepared in example 1 of the present invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nElectrochemiluminescence of (a).
FIG. 9 shows { [ Eu ] prepared in example 1 of the present invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nA PXRD pattern of (1); (in the figure, 1 is a structure simulation curve, and 2 is a product curve of example 1).
FIG. 10 shows { [ Eu ] prepared in example 1 of the present invention2(H2L)(H2-DHBDC)2.5(H2O)]·H2O}nThermogravimetric analysis of (a); (3 is a sample weight loss rate graph; 4 is a reciprocal weight graph).
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention.