CN113024598A - Novel efficient blue room-temperature phosphorescent material and preparation method thereof - Google Patents
Novel efficient blue room-temperature phosphorescent material and preparation method thereof Download PDFInfo
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- CN113024598A CN113024598A CN202011207810.6A CN202011207810A CN113024598A CN 113024598 A CN113024598 A CN 113024598A CN 202011207810 A CN202011207810 A CN 202011207810A CN 113024598 A CN113024598 A CN 113024598A
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
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Abstract
The invention belongs to the technical field of luminescent material synthesis, and relates to a novel efficient blue room temperature phosphorescent material and a preparation method thereof, based on a coordination driving strategy, organic N/O units with potential phosphorescent behaviors are coordinately dispersed in a metal phosphonic acid supermolecule building block, coordination anchoring is carried out on the organic units through a rigid metal phosphonate base, meanwhile, objects with matched charges and sizes are introduced by virtue of host-object chemistry, and the interaction of the host-object is utilized to further enhance and limit the organic luminescent units to inhibit non-radiative transition and optimize the room temperature phosphorescent performance of the organic luminescent units.
Description
The technical field is as follows:
the invention belongs to the technical field of luminescent material synthesis, and relates to a novel efficient blue room temperature phosphorescent material and a preparation method thereof.
Background art:
room Temperature Phosphorescence (RTP) materials have important applications in the fields of display imaging, anti-counterfeiting, biomedicine, and the like. Most of the traditional RTP materials are inorganic compounds, such as transition metal sulfides, alkaline earth metal aluminates/silicates and the like, and the inorganic RTP materials have various defects, such as poor processability, high cost, high biotoxicity, difficulty in large-area preparation and the like. In contrast, a pure organic phosphorescent material is easy to modify, has good processability, low toxicity and good biocompatibility, however, spin-orbit coupling (SOC) of a singlet excited state (Sn) and a triplet excited state (Tn) of a pure organic compound is weak, and an intersystem crossing (ISC) process is difficult to realize; meanwhile, the triplet exciton has high activity, and is easy to be inactivated at room temperature through non-radiative transition ways such as self vibration and rotation of molecules, oxygen quenching in air and the like, so that the generation of RTP is greatly weakened. The long-lived organic RTP materials reported earlier were mainly limited to noble metal complex materials. In view of the scarce resource and high price of noble metal elements, the development of cheap metal room temperature phosphorescent materials and an assembly strategy thereof are very important.
In the design and synthesis of RTP materials, the ISC rate needs to be improved and the non-radiative decay is effectively inhibited, and the strategy adopted for improving the ISC rate is to introduce inorganic heavy atoms and organic heteroatoms with lone electron pairs. At low temperature the molecular motion/vibration is limited and the non-radiative decay is reduced, most organic molecules exhibit phosphorescence at 77K. Therefore, constructing a rigid environment to simulate low temperature conditions to effectively limit the molecular motion/vibration of organic luminophores is crucial to the development of new RTP materials. In recent years, metal ions and organic light-emitting units are coordinated to construct hybrid RTP materials, but in most hybrid RTP materials, adjacent organic units are relatively close to each other and have a coupling effect, RTP colors are mostly in a yellow-green area, and the blue hybrid RTP material is prepared with great difficulty. Blue is one of three primary colors, and the blue RTP material has important significance in the field of photoelectric application. Therefore, the development of a method for constructing the high-efficiency blue RTP has important scientific and practical significance for enriching the variety of RTP materials and expanding the application range of the RTP materials.
The invention content is as follows:
the invention aims to overcome the defects of the prior art, designs a novel high-efficiency blue room temperature phosphorescent material and a preparation method thereof based on a crystal engineering strategy and a molecular level design, coordinately disperses an organic N/O unit with potential phosphorescent behavior in a metal phosphonic acid supermolecule building block based on a coordination driving strategy, coordinates and anchors the organic unit through a rigid metal phosphonate base, meanwhile, an object with matched charges and sizes is introduced by means of host-object chemistry, the interaction (electrostatic interaction, pi … pi and the like) of the host and the object is utilized to further strengthen and limit the organic light-emitting unit to inhibit non-radiative transition and optimize the RTP performance of the organic light-emitting unit, a series of novel hybrid metal phosphonates with blue light characteristics are obtained, a new thought is provided for the development of novel RTP materials and optical functional materials, and references are provided for the design synthesis and application research of the materials.
In order to achieve the above object, the novel blue room temperature phosphorescent material of the present invention has a chemical formula of [ A]·[Zn2(HEDP)(TPA)0.5(H2O)2]·nH2O, wherein A ═+NH3Me, n-0 (labeled as Compound 1) and A-0+NH2(Me)2N-1 (labeled as compound 2) or a-1+NH2(Et)2N-2 (labeled compound 3), all of which have a three-dimensional structure with an organophosphonic acid linked to Zn2+Forming a layer, connecting the adjacent layers by organic carboxylic acid to form a column layer structure, and filling the protonated organic amine as a guest between the layers.
In the novel blue RTP material, A ═ is+NH3When Me, n is 0, the asymmetric unit comprises two Zn2+An organophosphonic acid ligand, a deprotonated terephthalic acid unit (0.5 occupancy), two coordinated water molecules and a free protonated guest amine, two Zn2+Are all in [ ZnO ]6]In octahedron, the organophosphonic acid ligand is connected with Zn in a chelate-bridge mode2+Forming hybrid layers, connecting the hybrid layers through organic carboxylic acid ligands to form a column layer structure with negative charges, and arranging protonated organic amine between the layers to balance the negative charges of the main body framework.
The novel blue room temperature phosphorescent material A ═ of the invention+NH2(Me)2N is 1 and A is+NH2(Et)2When n is 2, with A+NH3The material framework when Me, n-0 is isomorphic, differing only in free water and organic amines.
The specific preparation process of the novel blue room temperature phosphorescent material comprises the following steps:
(1) uniformly mixing 1-2 mmol of metal source, 0.5-1 mmol of organic phosphine source, 5mL or 10mL of water, 0.7-0.9 mL of methylamine or 5mL of LN, N-dimethylformamide or 5mL of LN, N-diethylformamide and 0.2mL of hydrofluoric acid to obtain a mixture;
(2) putting the mixture prepared in the step (1) into a stainless steel high-pressure reaction vessel with a polytetrafluoroethylene reaction kettle, and crystallizing at 80 ℃ or 145 ℃ for 7 days to obtain a flaky colorless crystal with good crystallinity;
(3) and (3) washing the flaky colorless crystal obtained in the step (2) by deionized water, performing suction filtration, and drying at room temperature to obtain the organic-inorganic hybrid delayed fluorescence crystal material.
The metal source is zinc oxide; the organic phosphine source is hydroxyethylidene diphosphonic acid; the volume of the stainless steel reaction vessel was 20 mL.
Compared with the prior art, the three blue-light RTP materials with excellent performance are prepared, the preparation method is simple, the raw materials are easy to obtain, the cost is low, the time consumption is low, the yield of the phosphorescence quantum in the prepared room-temperature phosphorescence material is as high as 80.7%, and the object induction is adjustable.
Description of the drawings:
FIG. 1 is a diagram showing the coordination pattern of metal ions and ligands in the compound 1 of the present invention.
FIG. 2 is a three-dimensional stacking scheme of Compound 1(a), Compound 2(b), and Compound 3(c) according to the present invention.
FIG. 3 is Compound 1 prepared according to an embodiment of the invention: (a) PL spectrum (black dashed line) and phosphorescence spectrum (red solid line), the inset is a photograph of the uv lamp when switched on; (b) lifetime diagrams and phosphorescence efficiency; (c) CIE coordinates; (d) phosphorescence in three-dimensional spectrum.
FIG. 4 is a schematic view of the structures of compounds 2 and 3 prepared by an example of the present invention (a); (b) PL (black dashed line) and phosphorescence spectrum (red solid line); (c) and (d) lifetime and phosphorescent quantum yield; (e) and (f) a monodisperse state.
FIG. 5 is the CIE coordinates of Compounds 2 and 3 prepared according to the examples of the present invention.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples in conjunction with the accompanying drawings.
The chemical formula of the novel blue room temperature phosphorescent material in the embodiment is [ A ]]·[Zn2(HEDP)(TPA)0.5(H2O)2]·nH2O, wherein A ═+NH3Me, n-0 (labeled as Compound 1) and A-0+NH2(Me)2N-1 (labeled as compound 2) or a-1+NH2(Et)2N-2 (labeled compound 3), all of which have a three-dimensional structure with an organophosphonic acid linked to Zn2+Forming a layer, connecting the adjacent layers by organic carboxylic acid to form a column layer structure, and filling the protonated organic amine as a guest between the layers.
In the novel efficient blue room temperature phosphorescent material described in this example, a ═+NH3When Me, n is 0, the asymmetric unit comprises two Zn2+An organophosphonic acid ligand, a deprotonated terephthalic acid unit (0.5 occupancy), two coordinated water molecules, a free protonated guest amine, two Zn2+Are all in [ ZnO ]6]In octahedron, the organophosphonic acid ligand is connected with Zn in a chelate-bridge mode2+Forming hybrid layers, connecting the hybrid layers through organic carboxylic acid ligands to form a column layer structure with negative charges, and arranging protonated organic amine between the layers to balance the negative charges of the main body framework.
In the novel efficient blue room temperature phosphorescent material described in this example, a ═+NH2(Me)2N is 1 or A is+NH2(Et)2And when n is 2, with A+NH3The framework for Me, n-0 is isomorphic (as shown in figure 1), differing only in free water and organic amine.
The specific process for preparing the novel efficient blue room temperature phosphorescent material comprises the following steps:
(1) uniformly mixing 1-2 mmol of metal source, 0.5-1 mmol of organic phosphine source, 5mL or 10mL of water, 0.7-0.9 mL of methylamine or 5mL of LN, N-dimethylformamide or 5mL of LN, N-diethylformamide and 0.2mL of hydrofluoric acid to obtain a mixture;
(2) putting the mixture prepared in the step (1) into a stainless steel high-pressure reaction vessel with a polytetrafluoroethylene reaction kettle, and crystallizing at 80 ℃ or 145 ℃ for 6-7 days to obtain a flaky colorless crystal with good crystallinity;
(3) and (3) washing the flaky colorless crystal obtained in the step (2) by deionized water, performing suction filtration, and drying at room temperature to obtain the organic-inorganic hybrid efficient blue room-temperature phosphorescent crystal material.
The metal source described in this example is zinc oxide; the organic phosphine source is hydroxyethylidene diphosphonic acid; the volume of the stainless steel reaction vessel was 20 mL.
Example 1:
in the embodiment, zinc oxide (0.080-0.166 g, 1-2 mmol) and terephthalic acid (0.080-0.166 g, 1-2 mmol) are added into a stainless steel reaction kettle with a lining made of polytetrafluoroethylene and dissolved by a mixed solution of 10mL of water and methylamine (0.7-0.9 mL), hydroxyethylidene diphosphonic acid monohydrate (0.11-0.22 g, 0.5-1 mmol) and hydrofluoric acid (0.2mL) are added while stirring, after full stirring, the stainless steel reaction kettle containing reaction liquid is sealed and crystallized in an oven at 80 ℃ for 6-7 days, after the reaction is finished, the stainless steel reaction kettle is taken out and naturally cooled at room temperature, crystals generated in the stainless steel reaction kettle are removed and repeatedly cleaned for 5 times by deionized water, and dried at room temperature to obtain colorless flaky crystals, which are marked as a compound 1.
This example was conducted by subjecting the prepared Compound 1 to single crystal diffraction, and analysis of the data revealed that the Compound 1 had a column layer structure in which organophosphonic acid chelate-bridges Zn2+Forming a hybrid layer with a terephthalic acid ligand through interlayer Zn2+Coordination forms the final framework structure. The protonated methylamine is filled between the layers as an object.
Example 2:
in this example, zinc oxide (0.080-0.166 g, 1-2 mmol) and terephthalic acid (0.080-0.166 g, 1-2 mmol) are added into a stainless steel reaction kettle with a 20mL polytetrafluoroethylene lining, dissolved by a mixed solution (1:1) of 5mL water and 5mL N, N-dimethylformamide, and hydroxyl ethylidene diphosphonic acid monohydrate (0.11-0.22 g, 0.5-1 mmol) and hydrofluoric acid (0.2mL) are added while stirring, after sufficient stirring, the stainless steel reaction kettle containing the reaction solution is sealed and crystallized in an oven at 145 ℃ for 6-7 days, after the reaction is completed, compound 2 is obtained by cooling, washing and drying methods as in example 1, and the characteristics of the obtained target product are the same as those of example 1.
In this example, single crystal diffraction of compound 2 was performed, and data analysis thereof showed that compound 2 was isomorphic with compound 1 and had a column layer structure, and protonated dimethylamine was filled between the layers as a guest.
Example 3:
in this example, zinc oxide (0.080-0.166 g, 1-2 mmol) and terephthalic acid (0.080-0.166 g, 1-2 mmol) are added into a stainless steel reaction kettle with a 20mL polytetrafluoroethylene lining, dissolved by using 5mL of a mixed solution (1:1) of water and 5mL of N, N-diethylformamide, and hydroxyl ethylidene diphosphonic acid monohydrate (0.11-0.3 g, 0.5-1.5 mmol) and hydrofluoric acid (0.2mL) are added while stirring, after sufficient stirring, the stainless steel reaction kettle containing the reaction solution is sealed and crystallized in an oven at 145 ℃ for 6-7 days, after the reaction is completed, compound 3 is obtained by cooling, washing and drying methods as in example 1, and the characteristics of the obtained target product are the same as those in example 1.
In this example, single crystal diffraction was performed on compounds 2 and 3, and data analysis thereof showed that compound 3 was isomorphic with compound 1, having a column layer structure, with protonated dimethylamine and diethylamine as guests filled between the layers (fig. 2).
In this example, three examples of hybrid high-efficiency blue room temperature phosphorescent materials synthesized in examples 1 to 3 were subjected to related experiments, and ultrastable triplet excitons were obtained, and the experiments show that the obtained compounds all exhibit excellent room temperature phosphorescent properties. The quantum efficiency of deep blue phosphorescence represented by the hybrid compound 3 is as high as 80.70%, the ultra-long service life is as high as 186ms (figures 4 and 5), and the adjustable room temperature phosphorescence performance in terms of service life and quantum efficiency is generated by changing the steric hindrance of organic amine in the isomorphic hybrid framework (figures 3 and 4).
Claims (5)
1. A novel high-efficiency blue room temperature phosphorescent material is characterized in that: having a chemical formula of [ A]·[Zn2(HEDP)(TPA)0.5(H2O)2]·nH2O, wherein A ═+NH3Me，n＝0、A＝+NH2(Me)2N ═ 1 or A ═ 1+NH2(Et)2N-2, said materials all having a three-dimensional structure, the organophosphonic acid being linked to Zn2+Forming a layer, connecting the adjacent layers by organic carboxylic acid to form a column layer structure, and filling the protonated organic amine as a guest between the layers.
2. The novel efficient blue room temperature phosphorescent material as claimed in claim 1, wherein: in the novel blue room temperature phosphorescent material, A ═ is+NH3When Me, n is 0, the asymmetric unit comprises two Zn2+An organophosphonic acid ligand, a deprotonated terephthalic acid unit, two coordinated water molecules and a free protonated guest amine, two Zn2+Are all in [ ZnO ]6]In octahedron, the organophosphonic acid ligand is connected with Zn in a chelate-bridge mode2+Hybrid layers are formed and connected through organic carboxylic acid ligands to form a negatively charged column layer structure, and protonated organic amine is positioned between layers to balance the negative charge of the main body framework.
3. The novel efficient blue room temperature phosphorescent material as claimed in claim 2, wherein: the novel blue room temperature phosphorescent material A ═+NH2(Me)2N is 1 and A is+NH2(Et)2When n is 2, with A+NH3Me, where n is 0, is isostructural, differing in free water and organic amines.
4. A method for preparing the novel blue room temperature phosphorescent material as claimed in claim 3, wherein the method comprises the following steps: the preparation process comprises the following steps:
(1) uniformly mixing 1-2 mmol of metal source, 0.5-1 mmol of organic phosphine source, 5mL or 10mL of water, 0.7-0.9 mL of methylamine or 5mL of N, N-dimethylformamide or 5mL of N, N-diethylformamide and 0.2mL of hydrofluoric acid to obtain a mixture;
(2) putting the mixture prepared in the step (1) into a stainless steel high-pressure reaction vessel with a polytetrafluoroethylene reaction kettle, and crystallizing at 80 ℃ or 145 ℃ for 7 days to obtain a flaky colorless crystal with good crystallinity;
(3) and (3) washing the flaky colorless crystal obtained in the step (2) by deionized water, performing suction filtration, and drying at room temperature to obtain the organic-inorganic hybrid delayed fluorescence crystal material.
5. The method for preparing the novel blue room temperature phosphorescent material as claimed in claim 4, wherein the method comprises the following steps: the metal source is zinc oxide; the organic phosphine source is hydroxyethylidene diphosphonic acid; the volume of the stainless steel reaction vessel was 20 mL.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115161014A (en) * | 2022-06-09 | 2022-10-11 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
| CN115267970A (en) * | 2022-08-04 | 2022-11-01 | 南京信息工程大学 | Photon spin directional coupler |
| CN115368311A (en) * | 2022-07-15 | 2022-11-22 | 北京师范大学 | Metal-organic photonic glass material with full-phosphor light output and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060011890A1 (en) * | 2004-07-16 | 2006-01-19 | Keio University | Phosphor and production process for the same |
| CN109608482A (en) * | 2018-12-21 | 2019-04-12 | 青岛大学 | A kind of novel delay fluorescent material and preparation method thereof |
-
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- 2020-11-03 CN CN202011207810.6A patent/CN113024598A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060011890A1 (en) * | 2004-07-16 | 2006-01-19 | Keio University | Phosphor and production process for the same |
| CN109608482A (en) * | 2018-12-21 | 2019-04-12 | 青岛大学 | A kind of novel delay fluorescent material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115161014A (en) * | 2022-06-09 | 2022-10-11 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
| CN115161014B (en) * | 2022-06-09 | 2023-04-07 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
| CN115368311A (en) * | 2022-07-15 | 2022-11-22 | 北京师范大学 | Metal-organic photonic glass material with full-phosphor light output and preparation method thereof |
| CN115267970A (en) * | 2022-08-04 | 2022-11-01 | 南京信息工程大学 | Photon spin directional coupler |
| CN115267970B (en) * | 2022-08-04 | 2023-05-09 | 南京信息工程大学 | Photon spin directional coupler |
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