Cuprous halide complex high-entropy luminescent material as well as preparation method and application thereof

Abstract

The invention discloses a cuprous halide complex high-entropy luminescent material as well as a preparation method and application thereof. In the cuprous halide complex high-entropy luminescent material, cuprous halide is coordinated with phosphorus on a diphenylphosphine group and nitrogen on pyridine, and an electron donating group is connected to a benzene ring; an electron-donating group is connected to a benzene ring, an intramolecular donor-acceptor structure is realized, and regulation and control of a charge transfer path and disorder degree are realized by regulating the type and position of the electron-donating group on the benzene ring, so that the light-emitting color and efficiency are regulated and controlled.

Description

Technical Field

[0001] The invention belongs to the technical field of organic semiconductor luminescent materials, and specifically relates to a cuprous halide complex high-entropy luminescent material and a preparation method and application thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) have become the focus of research in academia and industry because of their advantages such as self-luminescence, wide viewing angle, wide color gamut, and fast response. Among them, the study of luminescent materials has always been an important part of OLED research. Copper cluster luminescent materials have rich coordination modes, low cost, non-toxicity and pollution-free. They are expected to become the next generation of high-performance, low-cost luminescent materials and have great potential in display and lighting applications. At present, common copper cluster materials themselves have problems such as structural distortion, easy quenching, and poor solubility. Therefore, the luminescence efficiency is low, the luminescence spectrum coverage is small, and the color purity is low, which makes it difficult to meet actual usage needs. Summary of the invention

[0003] In order to solve the above problems, the present invention provides a cuprous halide complex high-entropy luminescent material and a preparation method and application thereof. The copper atom in the cuprous halide of the cuprous halide complex high-entropy luminescent material is coordinated with the nitrogen in the pyridine group and the phosphorus in the diphenylphosphine group respectively, and the electron donating group is connected to the benzene ring of the ligand to form an intramolecular donor-acceptor electron structure with the pyridine group. By adjusting the type and position of the electron donating group on the benzene ring, the electron distribution and the path and disorder of the charge transfer are adjusted, so that the process tends to be high-entropy, which is beneficial to improving the exciton utilization rate and adjusting the luminescent color.

[0004] To achieve the above object, the present invention adopts the following technical solutions:

[0005] A cuprous halide complex high entropy luminescent material, wherein cuprous halide is coordinated with phosphorus on a diphenylphosphine group and nitrogen on pyridine, and an electron donating group is connected to the benzene ring; the cuprous halide complex high entropy luminescent material is as shown in formula (1), formula (2) or formula (3):

[0006]

[0007] Wherein, X is a halogen atom; R is an electron donating group.

[0008] Preferably, X is Br or I.

[0009] Preferably, R is a nitrogen-containing fused heterocyclic group, and the nitrogen-containing fused heterocyclic group includes a carbazole group, a 3,6-di-tert-butyl carbazole group, a 1,3,6,8-tetramethyl carbazole group, a 1-alcohol carbazole group, a 2-alcohol carbazole group, a 3-alcohol carbazole group, a 9,9-dimethyl acridine group, a 9,9-diphenyl acridine group and a spiro[acryl-9,9-fluorene] group; the structures of the nitrogen-containing fused heterocyclic groups are shown below:

[0010]

[0011] A method for preparing a cuprous halide complex high entropy luminescent material comprises the following steps:

[0012] S1, using ortho-, meta- or para-halogenated R-based benzene, 2-fluoro-5-boric acid and diphenylphosphine as reactants, and reacting the halogenated R-based benzene with 2-fluoro-5-boric acid by Suzuki condensation to obtain an intermediate; wherein R is an electron-donating group;

[0013] S2, adding sodium amide and diphenylphosphine to anhydrous tetrahydrofuran to react and generate sodium triphenylphosphine;

[0014] S3, heating the sodium triphenylphosphine and the intermediate to react, cooling, quenching the unreacted sodium triphenylphosphine with excess methanol, extracting, washing, drying and separating and purifying to obtain the target ligand;

[0015] S4. Coordinate the target ligand with cuprous halide to obtain a cuprous halide complex high entropy luminescent material.

[0016] An application of a cuprous halide complex high entropy luminescent material, wherein the cuprous halide complex high entropy luminescent material is dissolved in a liquid solvent, and a luminescent film is obtained through a film-forming process.

[0017] Preferably, the film forming process includes spin coating, inkjet printing, transfer printing and thermal evaporation.

[0018] After adopting the above technical solution, the present invention has the following beneficial effects:

[0019] 1. The copper atoms in the cuprous halide complex high-entropy luminescent material of the present invention are coordinated with the nitrogen in the pyridine group and the phosphorus in the diphenylphosphine group, respectively. At the same time, the electron-donating group is connected to the benzene ring of the ligand to form an intramolecular donor-acceptor electron structure with the pyridine group. By adjusting the type and position of the electron-donating group on the benzene ring, the electron distribution and the path and disorder of the charge transfer are adjusted, so that the process tends to be high-entropy, which is beneficial to improving the exciton utilization rate and adjusting the luminescent color.

[0020] 2. In the cuprous halide complex high entropy luminescent material of the present invention, both diphenylphosphine and pyridine provide coordination sites to form a rigid bidentate structure, and a highly efficient luminescent device can be prepared.

[0021] 3. The addition of benzene rings in the present invention can improve the carrier transport capability, regulate the band gap structure, improve the solubility of molecules, and help improve the performance of solution-processed devices.

[0022] 4. The benzene ring connected to pyridine in the present invention enhances the conjugation effect, thereby improving the carrier mobility, and the electron-donating group bridged on the benzene ring forms an intramolecular electron-donating-accepting structure with the pyridine group as an electron-accepting group, which can regulate the charge transfer path and disorder, enhance the charge transfer efficiency, and reduce luminescence quenching. At the same time, the different positions of the adjacent pairs on the benzene ring and the electron-donating structures and interatomic distances of different structures are utilized to achieve the adjustment of the luminescence peak. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The photoluminescence spectra of the cuprous halide complex high entropy luminescent materials prepared in Examples 1, 2 and 3 of the present invention are shown. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0025] like Figure 1 shown.

[0026] Example 1:

[0027]

[0028] Using the Suzuki condensation reaction, o-bromopyridylbenzene (388 mg, 1.2 mmol), 2-fluoro-5-pyridineboronic acid (141 mg, 1 mmol), tetrakis(triphenylphosphine)palladium (58 mg, 0.05 mmol) and K2CO3 (415 mg, 3 mmol) were added to a mixed solvent of 20 ml methanol, 10 ml ethanol and 10 ml water in sequence. Heat to 80 ° C, condense and reflux overnight. After cooling to room temperature, add an appropriate amount of deionized water and extract with dichloromethane, wash with saturated brine, dry with anhydrous magnesium sulfate, spin dry the solvent, and separate and purify by silica gel column chromatography to obtain 2-fluoro-5-pyridylbenzene intermediate (315 mg, yield: 93%).

[0029] Diphenylphosphine (559 mg, 3 mmol) and NaNH2 (117 mg, 3 mmol) were added to 10 ml of anhydrous tetrahydrofuran at -50°C. The reactor was then placed at room temperature, and the solution was slowly heated to room temperature and stirred at room temperature for 5 hours to obtain a NaPPh2 solution.

[0030] The obtained NaPPh2 solution was added to 10ml tetrahydrofuran containing 2-fluoro-5-pyridine intermediate (300mg, 0.88mmol), heated to 90°C, condensed and refluxed overnight. After cooling to room temperature, excessive methanol was added to quench the unreacted NaPPh2. After adding an appropriate amount of deionized water, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was dried by spin drying. The product was separated by column chromatography to obtain a complex based on 2-(diphenylphosphonyl)-5-phenylpyridine analog (197mg, 0.39mmol, 44%).

[0031]

[0032] The complex (50.4 mg, 0.1 mmol) and cuprous bromide (29 mg, 0.2 mmol) were dissolved in 2 ml of dichloromethane and stirred at room temperature for 2 h to obtain a crude solution. After filtering the crude solution, 6 ml of ether was added. After the solvent evaporated, the cuprous halide complex luminescent material (57 mg, 0.036 mmol, 72%) was obtained.

[0033] The structure of the cuprous halide complex high entropy luminescent material prepared in Example 1 is shown below:

[0034]

[0035] Example 2:

[0036]

[0037] Using the Suzuki condensation reaction, m-bromopyridylbenzene (776 mg, 2.4 mmol), 2-fluoro-5-pyridineboronic acid (282 mg, 2 mmol), tetrakis(triphenylphosphine)palladium (119 mg, 0.1 mmol) and K2CO3 (415 mg, 3 mmol) were added to a mixed solvent of 20 ml methanol, 10 ml ethanol and 10 ml water in sequence. Heat to 80 ° C, condense and reflux overnight. After cooling to room temperature, add an appropriate amount of deionized water and extract with dichloromethane, wash with saturated brine, dry with anhydrous magnesium sulfate, spin dry the solvent, and separate and purify by silica gel column chromatography to obtain intermediate 2 (588 mg, yield: 87%).

[0038] Diphenylphosphine (559 mg, 3 mmol) and NaNH2 (117 mg, 3 mmol) were added to 10 ml of anhydrous tetrahydrofuran at -50°C. The reactor was then placed at room temperature, and the solution was slowly heated to room temperature and stirred at room temperature for 5 hours to obtain a NaPPh2 solution.

[0039] The obtained NaPPh2 solution was added to 10ml tetrahydrofuran containing 2-fluoro-5-pyridylbenzene intermediate (300mg, 0.88mmol), heated to 90°C, condensed and refluxed overnight. After cooling to room temperature, excessive methanol was added to quench the unreacted NaPPh2. After adding an appropriate amount of deionized water, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was dried by spin drying. The product was separated by column chromatography to obtain a complex based on 2-(diphenylphosphonyl)-5-phenylpyridine analog (230mg, 0.45mmol, 54%).

[0040]

[0041] The complex (50.4 mg, 0.1 mmol) and cuprous bromide (29 mg, 0.2 mmol) were dissolved in 2 ml of dichloromethane and stirred for 2 h at room temperature to obtain a crude solution. After filtering the crude solution, 6 ml of ether was added. After the solvent evaporated, the cuprous halide complex luminescent material was obtained.

[0042] The structure of the cuprous halide complex high entropy luminescent material prepared in Example 2 is shown below:

[0043]

[0044] Example 3:

[0045]

[0046] Using the Suzuki condensation reaction, p-bromopyridylbenzene (388 mg, 1.2 mmol), 2-fluoro-5-pyridineboronic acid (141 mg, 1 mmol), tetrakis(triphenylphosphine)palladium (58 mg, 0.05 mmol) and K2CO3 (415 mg, 3 mmol) were added to a mixed solvent of 20 ml methanol, 10 ml ethanol and 10 ml water in sequence. Heat to 80 ° C, condense and reflux overnight. After cooling to room temperature, add an appropriate amount of deionized water and extract with dichloromethane, wash with saturated brine, dry with anhydrous magnesium sulfate, spin dry the solvent, and separate and purify by silica gel column chromatography to obtain 2-fluoro-5-pyridylbenzene intermediate (312 mg, yield: 92%).

[0047] Diphenylphosphine (559 mg, 3 mmol) and NaNH2 (117 mg, 3 mmol) were added to 10 ml of anhydrous tetrahydrofuran at -50°C. The reactor was then placed at room temperature, and the solution was slowly heated to room temperature and stirred at room temperature for 5 hours to obtain a NaPPh2 solution.

[0048] The obtained NaPPh2 solution was added to 10ml tetrahydrofuran dissolved with 2-fluoro-5-pyridylbenzene intermediate (300mg, 0.88mmol), heated to 90°C, condensed and refluxed overnight. After cooling to room temperature, excessive methanol was added to quench the unreacted NaPPh2. After adding an appropriate amount of deionized water, it was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was spin-dried. It was separated and purified by silica gel column chromatography to obtain a product separated by column chromatography to obtain a complex based on 2-(diphenylphosphonyl)-5-phenylpyridine analogs (161mg, 0.39mmol, 31%).

[0049]

[0050] The complex (50.4 mg, 0.1 mmol) and cuprous bromide (29 mg, 0.2 mmol) were dissolved in 2 ml of dichloromethane and stirred for 2 h at room temperature to obtain a crude solution. After filtering the crude solution, 6 ml of ether was added. After the solvent evaporated, the cuprous halide complex high entropy luminescent material was obtained.

[0051] The structure of the cuprous halide complex high entropy luminescent material prepared in Example 3 is shown below:

[0052]

[0053] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A cuprous halide complex high entropy luminescent material, characterized in that: In the cuprous halide complex high entropy luminescent material, the cuprous halide is coordinated with the phosphorus on the diphenylphosphine group and the nitrogen on the pyridine, and an electron-donating group is connected to the benzene ring; the cuprous halide complex high entropy luminescent material is as shown in formula (1), formula (2) or formula (3): Wherein, X is a halogen atom; R is an electron donating group.

2. A cuprous halide complex high entropy luminescent material as claimed in claim 1, characterized in that: The X is Br or I.

3. A cuprous halide complex high entropy luminescent material as claimed in claim 1, characterized in that: The R is a nitrogen-containing fused heterocyclic group, and the nitrogen-containing fused heterocyclic group includes a carbazole group, a 3,6-di-tert-butyl carbazole group, a 1,3,6,8-tetramethyl carbazole group, a 1-alcohol carbazole group, a 2-alcohol carbazole group, a 3-alcohol carbazole group, a 9,9-dimethyl acridine group, a 9,9-diphenyl acridine group and a spiro[acryl-9,9-fluorene] group; the structures of the nitrogen-containing fused heterocyclic groups are shown below:

4. A method for preparing a cuprous halide complex high entropy luminescent material as claimed in any one of claims 1 to 3, characterized in that: The following steps are involved: S1, using ortho-, meta- or para-halogenated R-based benzene, 2-fluoro-5-boric acid and diphenylphosphine as reactants, and reacting the halogenated R-based benzene with 2-fluoro-5-boric acid by Suzuki condensation to obtain an intermediate; wherein R is an electron-donating group; S2, adding sodium amide and diphenylphosphine to anhydrous tetrahydrofuran to react and generate sodium triphenylphosphine; S3, heating the sodium triphenylphosphine and the intermediate to react, cooling, quenching the unreacted sodium triphenylphosphine with excess methanol, extracting, washing, drying and separating and purifying to obtain the target ligand; S4. Coordinate the target ligand with cuprous halide to obtain a cuprous halide complex high entropy luminescent material.

5. An application of the cuprous halide complex high entropy luminescent material as claimed in any one of claims 1 to 3, characterized in that: The cuprous halide complex high entropy luminescent material is dissolved in a liquid solvent, and a luminescent thin film is obtained through a film-forming process.

6. The use of a cuprous halide complex high entropy luminescent material as claimed in claim 5, characterized in that: The film forming processes include spin coating, inkjet printing, transfer printing and thermal evaporation.

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