CN108250111B - Double-receptor organic light-emitting small molecular material and preparation method and application thereof - Google Patents
Double-receptor organic light-emitting small molecular material and preparation method and application thereof Download PDFInfo
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- CN108250111B CN108250111B CN201810035059.2A CN201810035059A CN108250111B CN 108250111 B CN108250111 B CN 108250111B CN 201810035059 A CN201810035059 A CN 201810035059A CN 108250111 B CN108250111 B CN 108250111B
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- organic light
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- receptor
- emitting small
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- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
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- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
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- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a double-receptor organic light-emitting micromolecule material, which is characterized in that carbonyl and sulfonyl are connected through benzene rings to form a novel double-receptor framework unit, and the two sides of the novel double-receptor framework unit are respectively connected with one benzene ring to increase reaction sites. The invention also discloses a preparation method and application of the double-receptor organic light-emitting small molecular material. The luminescent material connected with the receptor can realize intramolecular charge transfer effect, and the bipolar transmission characteristic of the luminescent material reduces the problem of unbalanced current carriers of the unipolar luminescent material, thereby simplifying the structure of the device and improving the performance of the device. The invention has simple preparation and obtains various target products through a series of simple reactions. The material has definite molecular weight, single structure, high decomposition temperature and low sublimation temperature, and can be applied to organic electroluminescent diodes.
Description
Technical Field
The invention relates to the technical field of materials of an organic electroluminescent device technology, in particular to a double-receptor organic luminescent micromolecule material and a preparation method and application thereof.
Background
Organic electroluminescent devices have been currently used in the field of light emitting displays. Compared with polymer luminescent materials, the small-molecule luminescent materials have the advantages of simple preparation, definite molecular weight, single structure and the like, and therefore, the small-molecule luminescent materials have more potential to be pushed to wider commercial application. At present, techniques for preparing multilayer devices based on evaporation or solution processing of small molecule materials are constantly being developed and advanced, and have made significant progress.
Previous research into organic electroluminescent devices has made significant progress. When the organic light-emitting material is excited by electricity, the theoretical ratio of generated singlet state excitons to generated triplet state excitons is 1: 3. The exciton transition back to the ground state of the singlet level of the general fluorescent material is allowable, and the exciton transition back to the ground state of the triplet level is forbidden, and therefore, its exciton utilization rate is not high. However, in the case of a material having a small difference between the singlet level and the triplet level, triplet excitons, which have a slightly low energy and a long lifetime, can be thermally excited to transit to the singlet level through intersystem crossing, and then emit fluorescence, which is called thermally excited delayed fluorescence. The development of the thermal excitation delayed fluorescence material plays a key role in improving the efficiency of the organic electroluminescent device, can avoid using noble metals of phosphorescent materials, and has positive significance for wider commercial application.
To obtain a high-efficiency and stable organic electroluminescent device with use value, not only the design of the device structure needs to be precisely regulated and controlled, but also very high requirements are put on the materials, particularly luminescent materials, in the device structure. Therefore, it is very important to explore the molecular structure design of the luminescent material and the corresponding performance relationship thereof, and provide guidance for preparing a luminescent molecular design idea which can show high efficiency, stability, low roll-off and long service life in devices.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a double-acceptor organic light-emitting micromolecule material, and two acceptors of carbonyl sulfone group are adopted as a novel electron acceptor unit organic light-emitting micromolecule simultaneously.
The invention also aims to provide a preparation method of the double-acceptor organic light-emitting small molecule material.
The invention further aims to provide application of the double-acceptor organic light-emitting small molecule material.
The purpose of the invention is realized by the following technical scheme:
a double-acceptor organic light-emitting small molecule material has any one of the chemical structures of P1n, P2n, P3n and P4 n:
wherein Ar is any aromatic amine group in the following (1) to (7):
the double-acceptor organic light-emitting small molecular material has any one of the chemical structures of P1-P28:
the preparation method of the double-receptor organic light-emitting small molecular material comprises the following steps:
(1) preparing any one of intermediates having structures (a) to (d):
(2) under the protection of inert gas, adding the intermediate prepared in the step (1), an aromatic amine compound, alkali and a catalyst into an organic solvent, uniformly mixing, heating, refluxing, stirring and reacting, and carrying out cooling, extraction, spin-drying of the solvent and column chromatography to obtain the novel double-acceptor-unit-based organic micromolecule luminescent material;
the molar ratio of the intermediate to the aromatic amine compound is 1 (2-2.5).
The preparation of any one of the intermediates having the structures (a) to (d) in the step (1) specifically comprises the following steps:
under the protection of nitrogen, dissolving a raw material of dibromophenylsulfide into anhydrous tetrahydrofuran, cooling to-70 to-80 ℃, sequentially adding N-butyllithium solution and monobromobenzaldehyde, recovering to room temperature, stirring overnight under the atmosphere of N2, and adding ethanol to terminate the reaction after the reaction is finished; extracting, drying, filtering and separating reactants to obtain colorless liquid;
the dosage of the n-butyl lithium is 1-1.5 times of the molar weight of the dibromophenylsulfide; the dosage of the monobromobenzaldehyde is 1-1.5 times of the molar weight of the dibromophenylsulfide.
Heating, refluxing and stirring for reaction in the step (2), specifically:
the temperature is 90-110 ℃, and the reaction time is 12-24 h.
The aromatic amine compound in the step (2) is any one of carbazole, 9' -dimethylacridine, phenoxazine or phenothiazine.
The alkali in the step (2) is organic alkali, and the using amount of the alkali is 1.8-2.5 times of the molar equivalent of the aromatic amine compound.
The catalyst in the step (2) consists of palladium acetate and tributyl phosphine.
The organic solvent in the step (2) is toluene.
The double-receptor organic light-emitting small molecular material is applied to an electroluminescent diode.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the double-acceptor organic luminescent micromolecule material simultaneously adopts two acceptors of carbonyl sulfone group as a novel electron acceptor unit, and is connected with a commonly used electron donor unit to obtain a molecule with a D-A structure, so that the double-acceptor organic luminescent micromolecule material has the advantages of single structure, definite molecular weight, good repeatability of multiple synthesis and the like.
(2) The double-receptor organic light-emitting small molecular material has a strong intramolecular charge transfer effect, can easily realize a small single-triplet state energy level difference, and simultaneously ensures a high fluorescence quantum yield. Thus, high external quantum efficiency and low efficiency roll-off can be achieved in the device while obtaining thermally activated delayed fluorescence properties.
(3) The double-receptor organic light-emitting small molecular material can adjust the photoelectric device performances such as light color, charge transmission performance and the like of the material by changing the types of the connecting groups.
(4) The structure of the invention can adjust and control the conjugation length, the electron cloud distribution, the carrier transmission characteristic and the film forming property of the material by adjusting the position and the number of the group connection.
(5) The double-receptor organic light-emitting small molecular material can realize intramolecular charge transfer, and the bipolar transmission characteristic of the double-receptor organic light-emitting small molecular material reduces the problem of unbalanced current carriers of the unipolar light-emitting material, thereby simplifying the structure of the device and improving the performance of the device.
(6) The double-receptor organic light-emitting micromolecule material has high decomposition temperature and low sublimation temperature, is easy to sublimate into a high-purity light-emitting material, and can be applied to evaporation type organic micromolecule electroluminescent diodes.
(7) The preparation method is simple, and various target products are obtained through a series of simple reactions.
Drawings
FIG. 1 shows the absorption and emission spectra of P18 and P20 in toluene solution.
Fig. 2 is a current density-voltage-luminance curve of the organic light emitting diode device including P18, P20.
Fig. 3 is a graph of luminance-current efficiency versus luminance-power efficiency for an organic light emitting diode device comprising P18 and P20.
FIG. 4 is a graph of temperature transition transient lifetime spectra of P18 and P20 in thin films.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
This example prepared intermediates 1 to 14 and compound P1:
the preparation steps of the intermediate 1 are as follows:
in a 250mL three-necked flask, under a nitrogen atmosphere, 11.7g (40.0mmol) of p-bromoiodobenzene, 5.8g (24.0mmol) of sodium sulfide nonahydrate, 336mg (0.1equ) of copper iodide (CuI), 5.4g (40.0mmol) of anhydrous potassium carbonate, and 80mL of N, N-Dimethylformamide (DMF) were successively added. The reaction mixture was heated to 120 ℃ and stirred for 18 hours in the dark. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 7g of intermediate of formula 1 in 94% yield, C12H8Br2S M/Z341.87. m/z 343.87 (100.0%), 341.87 (51.4%), 345.87 (48.6%), 344.87 (9.7%), 346.87 (6.3%), 345.87 (4.5%), 342.87 (4.4%), 344.87 (3.2%), 343.87 (2.3%), 342.87 (2.2%), 347.86 (2.2%); elemental analysis: c, 41.89; h, 2.34; br, 46.45; and S, 9.32.
The intermediate 2 comprises the following specific implementation steps:
under a nitrogen atmosphere, in a 250mL three-necked flask, 11.7g (40.0mmol) of m-bromoiodobenzene, 5.8g (24.0mmol) of sodium sulfide nonahydrate, 336mg (0.1equ) of copper iodide (CuI), 5.4g (40.0mmol) of anhydrous potassium carbonate, and 80mL of N, N-Dimethylformamide (DMF) were successively added. The reaction mixture was heated to 120 ℃ and stirred for 18 hours in the dark. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 6.3g of intermediate of formula 1 in 85% yield, C12H8Br2S M/Z341.87. m/s: m/z 343.87 (100.0%), 341.87 (51.4%), 345.87 (48.6%), 344.87 (9.7%), 346.87 (6.3%), 345.87 (4.5%), 342.87 (4.4%), 344.87 (3.2%), 343.87 (2.3%), 342.87 (2.2%), 347.86 (2.2%); elemental analysis: c, 41.89; h, 2.34; br, 46.45; and S, 9.32.
The preparation steps of the intermediate 3 are as follows:
5.1g (15mmol) of Compound 1 was placed in a dry 250mL three-necked flask under a nitrogen atmosphere, and 50mL of freshly distilled tetrahydrofuran was charged. The reactor is cooled to-78 ℃, 6mL of 2.5M n-butyllithium (nBuLi) is added dropwise, the mixture is stirred at low temperature for two hours, 50mL of freshly distilled tetrahydrofuran solution in which 2.7g (15mmol) of p-bromobenzaldehyde is dissolved is slowly added, and the mixture is kept under heat preservation and stirred for one half hour. The reaction was then brought to room temperature and stirred overnight. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 4.2g of intermediate of formula 3 in 62% yield, C19H14Br2OS M/Z450.19. m/z 449.91 (100.0%), 447.91 (51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%); elemental analysis: c, 50.69; h, 3.13; br, 35.50; o, 3.55; and S, 7.12.
The preparation steps of the intermediate 4 are as follows:
5.1g (15mmol) of Compound 2 was placed in a dry 250mL three-necked flask under a nitrogen atmosphere, and 50mL of freshly distilled tetrahydrofuran was charged. The reactor is cooled to-78 ℃, 6mL of 2.5M n-butyllithium (nBuLi) is added dropwise, the mixture is stirred at low temperature for two hours, 50mL of freshly distilled tetrahydrofuran solution in which 2.7g (15mmol) of p-bromobenzaldehyde is dissolved is slowly added, and the mixture is kept under heat preservation and stirred for one half hour. The reaction was then brought to room temperature and stirred overnight. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 4.5g of intermediate of formula 4 in 67% yield, C19H14Br2OS M/Z450.19. m/z 449.91 (100.0%), 447.91 (51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%); elemental analysis: c, 50.69; h, 3.13; br, 35.50; o, 3.55; and S, 7.12.
The preparation steps of the intermediate 5 are as follows:
5.1g (15mmol) of Compound 1 was placed in a dry 250mL three-necked flask under a nitrogen atmosphere, and 50mL of freshly distilled tetrahydrofuran was charged. The reactor is cooled to-78 ℃, 6mL of 2.5M n-butyllithium (nBuLi) is added dropwise, the mixture is stirred at low temperature for two hours, 50mL of a new tetrahydrofuran solution in which 2.7g (15mmol) of M-bromobenzaldehyde is dissolved is slowly added, and the mixture is kept under the condition of heat preservation and stirred for one half hour. The reaction was then brought to room temperature and stirred overnight. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 4g of intermediate of formula 5 in 60% yield, C19H14Br2OS M/Z450.19. m/z 449.91 (100.0%), 447.91 (51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%); elemental analysis: c, 50.69; h, 3.13; br, 35.50; o, 3.55; and S, 7.12.
The specific implementation steps of the intermediate 6 are as follows:
5.1g (15mmol) of Compound 2 was placed in a dry 250mL three-necked flask under a nitrogen atmosphere, and 50mL of freshly distilled tetrahydrofuran was charged. The reactor is cooled to-78 ℃, 6mL of 2.5M n-butyllithium (nBuLi) is added dropwise, the mixture is stirred at low temperature for two hours, 50mL of a new tetrahydrofuran solution in which 2.7g (15mmol) of M-bromobenzaldehyde is dissolved is slowly added, and the mixture is kept under the condition of heat preservation and stirred for one half hour. The reaction was then brought to room temperature and stirred overnight. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 4g of intermediate of formula 6 in 60% yield, C19H14Br2OS M/Z450.19. m/z 449.91 (100.0%), 447.91 (51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%); elemental analysis: c, 50.69; h, 3.13; br, 35.50; o, 3.55; and S, 7.12.
The intermediate 7 comprises the following specific preparation steps:
in a 250mL single-neck flask, 3.4g (7.6mmol) of Compound 3 was placed, followed by addition of 100mL of methylene chloride and dissolution with stirring, followed by addition of 4.92g (22.8mmol) of pyridinium chlorochromate (PCC) and stirring at room temperature for 8 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 3.2g of intermediate of formula 9 in 94% yield, C19H12Br2OS M/Z448.17. m/z 447.90 (100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90 (1.2%); elemental analysis: c, 50.92; h, 2.70; br, 35.66; o, 3.57; and S, 7.15.
The preparation steps of the intermediate 8 are as follows:
in a 250ml single neck flask was added 1g (2.4mmol) of compound 7, 80ml of dichloromethane was added and dissolved with stirring, after which 2ml of additional hydrogen peroxide was added every half hour and the reaction was continued for 6 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 0.9g of intermediate of formula 1 in 80% yield, C19H12Br2O3S M/Z480.17. m/z 479.89 (100.0%), 477.89 (51.4%), 481.88 (48.6%), 480.89 (10.8%), 478.89 (10.6%), 482.89 (10.0%), 480.89 (9.7%), 481.88 (4.5%), 479.88 (2.3%), 483.88 (2.2%), 481.89 (1.5%); elemental analysis: c, 47.53; h, 2.52; br, 33.28; o, 10.00; and S, 6.68.
The preparation steps of the intermediate 9 are as follows:
the reaction step for the preparation of intermediate 7 was changed from compound 3 to compound 4, and the remaining steps were carried out in the same manner as the starting material to give intermediate 3.1g of formula 9 in 91% yield, C19H12Br2OS M/Z448.17. m/z 447.90 (100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90 (1.2%); elemental analysis: c, 50.92; h, 2.70; br, 35.66; o, 3.57; and S, 7.15.
The preparation steps of the intermediate 10 are as follows:
the reaction step for preparing intermediate 8 was changed to compound 9 from compound 7, and the remaining steps were carried out in the same manner as the starting material to give 0.95g of intermediate of formula 10 in 82% yield, C19H12Br2O3S M/Z ═ 480.17. C19H12Br2O3S M/Z480.17. m/z 479.89 (100.0%), 477.89 (51.4%), 481.88 (48.6%), 480.89 (10.8%), 478.89 (10.6%), 482.89 (10.0%), 480.89 (9.7%), 481.88 (4.5%), 479.88 (2.3%), 483.88 (2.2%), 481.89 (1.5%); elemental analysis: c, 47.53; h, 2.52; br, 33.28; o, 10.00; and S, 6.68.
The preparation steps of the intermediate 11 are as follows:
the reaction step for the preparation of intermediate 7 was changed from compound 3 to compound 5, and the remaining steps were the same as the starting material, to give intermediate 3g of formula 11 in 87% yield, C19H12Br2OS M/Z448.17. m/z 447.90 (100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90 (1.2%); elemental analysis: c, 50.92; h, 2.70; br, 35.66; o, 3.57; and S, 7.15. The preparation steps of the intermediate 12 are as follows:
the reaction step for preparing intermediate 8 was changed to compound 11, and the remaining steps were the same as the starting materials, to give 0.9g of intermediate of formula 12 in 78% yield, C19H12Br2O3S M/Z480.17. C19H12Br2O3S M/Z480.17. m/z 479.89 (100.0%), 477.89 (51.4%), 481.88 (48.6%), 480.89 (10.8%), 478.89 (10.6%), 482.89 (10.0%), 480.89 (9.7%), 481.88 (4.5%), 479.88 (2.3%), 483.88 (2.2%), 481.89 (1.5%); elemental analysis: c, 47.53; h, 2.52; br, 33.28; o, 10.00; and S, 6.68.
The preparation steps of the intermediate 13 are as follows:
the reaction step for the preparation of intermediate 7 was changed to compound 6 for compound 3, and the remaining steps were the same as the starting material to give intermediate 3g of formula 13 in 87% yield, C19H12Br2OS M/Z-448.17. m/z 447.90 (100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90 (1.2%); elemental analysis: c, 50.92; h, 2.70; br, 35.66; o, 3.57; and S, 7.15.
The intermediate 14 is prepared by the following steps:
the reaction step for preparing intermediate 8 was changed to compound 13, and the remaining steps were the same as the starting materials, to give 0.92g of intermediate of formula 14 in 80% yield, C19H12Br2O3S M/Z-480.17. C19H12Br2O3S M/Z480.17. m/z 479.89 (100.0%), 477.89 (51.4%), 481.88 (48.6%), 480.89 (10.8%), 478.89 (10.6%), 482.89 (10.0%), 480.89 (9.7%), 481.88 (4.5%), 479.88 (2.3%), 483.88 (2.2%), 481.89 (1.5%); elemental analysis: c, 47.53; h, 2.52; br, 33.28; o, 10.00; and S, 6.68. :
the preparation method of the compound P1 comprises the following steps:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.26g of diphenylamine (2.5equ) were charged in a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 1.30g of product is obtained, yield 85%. The molecular formula is as follows: C43H32N2O 3S; M/Z656.80 theory: M/Z656.21 (100.0%), 657.22 (46.5%), 658.22 (10.6%), 658.21 (4.5%), 659.21 (2.1%); elemental analysis C, 78.63; h, 4.91; n, 4.27; o, 7.31; and S, 4.88.
Example 2
This example prepares compound P2, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent amount of intermediate 10 was substituted for intermediate 14 in example 1 and the other starting materials and procedures were the same as in example 1 to give 1.50g of the product of formula P2 in 76% yield. The molecular formula is as follows: C43H32N2O 3S; M/Z656.80 theory: M/Z656.21 (100.0%), 657.22 (46.5%), 658.22 (10.6%), 658.21 (4.5%), 659.21 (2.1%); elemental analysis C, 78.63; h, 4.91; n, 4.27; o, 7.31; and S, 4.88.
Example 3
This example prepares compound P3, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the intermediate 14 in the preparation of P1 in example 1 was replaced with an equivalent of intermediate 12 and the other starting materials and procedures were the same as in example 1 to give 1.45g of product of formula P3 in 74% yield. The molecular formula is as follows: C43H32N2O 3S; M/Z656.80 theory: M/Z656.21 (100.0%), 657.22 (46.5%), 658.22 (10.6%), 658.21 (4.5%), 659.21 (2.1%); elemental analysis C, 78.63; h, 4.91; n, 4.27; o, 7.31; and S, 4.88.
Example 4
This example prepares compound P4, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
intermediate 14 in the preparation of P1 in example 1 was replaced with an equivalent of intermediate 8 and the other starting materials and procedures were the same as in example 15 to give 1.45g of product of formula P4 in 74% yield. The molecular formula is as follows: C43H32N2O 3S; M/Z656.80 theory: M/Z656.21 (100.0%), 657.22 (46.5%), 658.22 (10.6%), 658.21 (4.5%), 659.21 (2.1%); elemental analysis C, 78.63; h, 4.91; n, 4.27; o, 7.31; and S, 4.88.
Example 5
This example prepares compound P5, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.26g of carbazole (2.5equ) were charged in a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 0.85g of product is obtained, yield 56%. The molecular formula is as follows: C43H28N2O 3S; M/Z652.77 theory: M/Z652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%); elemental analysis C, 79.12; h, 4.32; n, 4.29; o, 7.35; and S, 4.91.
Example 6
This example prepares compound P6, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent amount of intermediate 10 was substituted for intermediate 14 in example 5 and the other starting materials and procedures were the same as in example 5 to give 0.80g of the product of formula P6 in 50% yield. The molecular formula is as follows: C43H28N2O 3S; M/Z652.77 theory: M/Z652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%); elemental analysis C, 79.12; h, 4.32; n, 4.29; o, 7.35; and S, 4.91.
Example 7
This example prepares compound P7, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent amount of intermediate 12 was substituted for intermediate 14 in example 5 and the other starting materials and procedures were the same as in example 5 to give 0.80g of product of formula P7 in 50% yield. The molecular formula is as follows: C43H28N2O 3S; M/Z652.77 theory: M/Z652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%); elemental analysis C, 79.12; h, 4.32; n, 4.29; o, 7.35; and S, 4.91.
Example 8
This example prepares compound P8, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent amount of intermediate 8 was substituted for intermediate 14 in example 5 and the other starting materials and procedures were the same as in example 5 to give 0.95g of product of formula P8 in 62% yield. The molecular formula is as follows: C43H28N2O 3S; M/Z652.77 theory: M/Z652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%); elemental analysis C, 79.12; h, 4.32; n, 4.29; o, 7.35; and S, 4.91.
Example 9
This example prepares compound P9, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.50g of phenothiazine (2.5equ) were charged in a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tri-tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. The product was obtained in 1.21g with a yield of 63%. The molecular formula is as follows: C43H28N2O3S 3; M/Z716.13 theoretical value M/Z716.13 (100.0%), 717.13 (46.5%), 718.12 (13.6%), 718.13 (10.6%), 719.13 (6.3%), 717.13 (2.4%), 720.13 (1.4%), 718.13 (1.1%); elemental analysis C, 72.04; h, 3.94; n, 3.91; o, 6.70; and S, 13.42.
Example 10
This example prepares compound P10, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent amount of intermediate 10 was substituted for intermediate 14 in example 9 and the other starting materials and procedures were the same as in example 9 to give 1.02g of product of formula P10 in 55% yield. The molecular formula is as follows: C43H28N2O3S 3; M/Z716.13 theoretical value M/Z716.13 (100.0%), 717.13 (46.5%), 718.12 (13.6%), 718.13 (10.6%), 719.13 (6.3%), 717.13 (2.4%), 720.13 (1.4%), 718.13 (1.1%); elemental analysis C, 72.04; h, 3.94; n, 3.91; o, 6.70; and S, 13.42.
Example 11
This example prepares compound P11, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent amount of intermediate 12 was substituted for intermediate 14 in example 9 and the other starting materials and procedures were the same as in example 9 to give 0.95g of product of formula P11 in 50% yield. The molecular formula is as follows: C43H28N2O3S 3; M/Z716.13 theoretical value M/Z716.13 (100.0%), 717.13 (46.5%), 718.12 (13.6%), 718.13 (10.6%), 719.13 (6.3%), 717.13 (2.4%), 720.13 (1.4%), 718.13 (1.1%); elemental analysis C, 72.04; h, 3.94; n, 3.91; o, 6.70; and S, 13.42.
Example 12
This example prepares compound P12, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 14 were substituted for equivalent amounts of intermediate 8 in example 9 and the other starting materials and procedures were the same as in example 9 to give 1.21g of product of formula P12 in 61% yield. The molecular formula is as follows: C43H28N2O3S 3; M/Z716.13 theoretical value M/Z716.13 (100.0%), 717.13 (46.5%), 718.12 (13.6%), 718.13 (10.6%), 719.13 (6.3%), 717.13 (2.4%), 720.13 (1.4%), 718.13 (1.1%); elemental analysis C, 72.04; h, 3.94; n, 3.91; o, 6.70; and S, 13.42.
Example 13
This example prepares compound P13, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.40g of phenoxazine (2.5equ) were added to a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added with stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 1.15g of product are obtained, yield 62%. The molecular formula is as follows: C43H28N2O 5S; M/Z684.17 theoretical value M/Z684.17 (100.0%), 685.18 (46.5%), 686.18 (10.6%), 686.17 (4.5%), 687.17 (2.1%), 686.18 (1.0%); elemental analysis C, 75.42; h, 4.12; n, 4.09; o, 11.68; and S, 4.68.
Example 14
This example prepares compound P14, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 10 were substituted for intermediate 14 in example 13 and the other starting materials and procedures were the same as in example 13 to give 1.02g of product of formula P14 in 55% yield. The molecular formula is as follows: C43H28N2O 5S; M/Z684.17 theoretical value M/Z684.17 (100.0%), 685.18 (46.5%), 686.18 (10.6%), 686.17 (4.5%), 687.17 (2.1%), 686.18 (1.0%); elemental analysis C, 75.42; h, 4.12; n, 4.09; o, 11.68; and S, 4.68.
Example 15
This example prepares compound P15, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent amount of intermediate 12 was substituted for intermediate 14 in example 13 and the other starting materials and procedures were the same as in example 13 to give 0.95g of product of formula P15 in 50% yield. The molecular formula is as follows: C43H28N2O 5S; M/Z684.17 theoretical value M/Z684.17 (100.0%), 685.18 (46.5%), 686.18 (10.6%), 686.17 (4.5%), 687.17 (2.1%), 686.18 (1.0%); elemental analysis C, 75.42; h, 4.12; n, 4.09; o, 11.68; and S, 4.68.
Example 16
This example prepares compound P16, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 8 were substituted for intermediate 14 in example 13 and the other starting materials and procedures were the same as in example 13 to give 1.21g of product of formula P16 in 61% yield. The molecular formula is as follows: C43H28N2O 5S; M/Z684.17 theoretical value M/Z684.17 (100.0%), 685.18 (46.5%), 686.18 (10.6%), 686.17 (4.5%), 687.17 (2.1%), 686.18 (1.0%); elemental analysis C, 75.42; h, 4.12; n, 4.09; o, 11.68; and S, 4.68.
Example 17
This example prepares compound P17, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.40g of dimethylacridine (2.5equ) were charged in a three-necked flask under nitrogen atmosphere, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 1.50g of product is obtained, yield 68%. The molecular formula is as follows: C49H40N2O 3S; theoretical value of M/Z736.28 736.28 (100.0%), 737.28 (53.0%), 738.28 (13.8%), 738.27 (4.5%), 739.28 (2.4%), 739.29 (1.5%); elemental analysis C, 79.86; h, 5.47; n, 3.80; o, 6.51; and S, 4.35.
Example 18
This example prepares compound P18, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 10 were substituted for intermediate 14 in example 17 and the other starting materials and procedures were the same as in example 17 to give 1.22g of product of formula P18 in 55% yield. The molecular formula is as follows: C49H40N2O 3S; theoretical value of M/Z736.28 736.28 (100.0%), 737.28 (53.0%), 738.28 (13.8%), 738.27 (4.5%), 739.28 (2.4%), 739.29 (1.5%); elemental analysis C, 79.86; h, 5.47; n, 3.80; o, 6.51; and S, 4.35.
The absorption and emission spectrum of compound P18 prepared in this example in toluene solution is shown in FIG. 1, and it can be seen from the figure that the molecule has weak CT absorption peak, belongs to CT class molecule, and accords with the characteristics of heat-activated delayed fluorescence molecule, and the emission peak of the molecule is 540nm, and belongs to green light emission.
Example 19
This example prepares compound P19, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 12 were substituted for intermediate 14 in example 17 and the other starting materials and procedures were the same as in example 17 to give 1.18g of product of formula P19 in 50% yield. The molecular formula is as follows: C49H40N2O 3S; theoretical value of M/Z736.28 736.28 (100.0%), 737.28 (53.0%), 738.28 (13.8%), 738.27 (4.5%), 739.28 (2.4%), 739.29 (1.5%); elemental analysis C, 79.86; h, 5.47; n, 3.80; o, 6.51; and S, 4.35.
Example 20
This example prepares compound P20, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
example 17 intermediate 14 was replaced with equivalent intermediate 8 and the other starting materials and procedures were the same
Example 17 gave 1.38g of the product of formula P20 in 61% yield. The molecular formula is as follows: C49H40N2O 3S; theoretical value of M/Z736.28 736.28 (100.0%), 737.28 (53.0%), 738.28 (13.8%), 738.27 (4.5%), 739.28 (2.4%), 739.29 (1.5%); elemental analysis C, 79.86; h, 5.47; n, 3.80; o, 6.51; and S, 4.35.
The absorption and emission spectrum of the compound P20 prepared in this example in a toluene solution is shown in FIG. 1, and it can be seen from the figure that the molecule has a weak CT absorption peak, belongs to CT class molecules, and conforms to the characteristics of a thermally activated delayed fluorescence molecule, and the emission peak of the molecule is 550nm, and belongs to yellow-green light emission. The molecule has red-shifted emission peaks due to the altered charge transfer within the molecule.
Example 21
This example prepares compound P21, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.26g of 3, 6-tert-butylcarbazole (2.5equ) were charged in a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tri-tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 0.85g of product is obtained, yield 56%. The molecular formula is as follows: C59H60N2O 3S; M/Z876.43 theoretical value M/Z876.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%); elemental analysis C, 80.79; h, 6.89; n, 3.19; o, 5.47; and S, 3.65.
Example 22
This example prepares compound P22, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent of intermediate 10 was substituted for intermediate 14 in example 21 and the other starting materials and procedures were the same as in example 21 to give 0.80g of the product of formula P22 in 50% yield. The molecular formula is as follows: C59H60N2O 3S; M/Z876.43 theoretical value M/Z876.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%); elemental analysis C, 80.79; h, 6.89; n, 3.19; o, 5.47; and S, 3.65.
Example 23
This example prepares compound P23, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
the equivalent of intermediate 12 was substituted for intermediate 14 in example 21 and the other starting materials and procedures were the same as in example 21 to give 0.80g of the product of formula P23 in 50% yield. The molecular formula is as follows: C59H60N2O 3S; M/Z876.43 theoretical value M/Z876.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%); elemental analysis C, 80.79; h, 6.89; n, 3.19; o, 5.47; and S, 3.65.
Example 24
This example prepares compound P24, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
example 21 intermediate 14 was replaced with equivalent intermediate 8 and the other starting materials and procedures were the same
Example 21 gave 0.95g of the product of formula P24 in 62% yield. The molecular formula is as follows: C59H60N2O 3S; M/Z876.43 theoretical value M/Z876.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%); elemental analysis C, 80.79; h, 6.89; n, 3.19; o, 5.47; and S, 3.65.
Example 25
This example prepares compound P25, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.40g of 3, 6-tert-butyldimethylacridine (2.5equ) were charged in a three-necked flask under nitrogen atmosphere, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tributylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 1.50g of product is obtained, yield 68%. The molecular formula is as follows: C65H72N2O 3S; theoretical M/Z960.53 value 960.53 (100.0%), 961.53 (70.3%), 962.53 (24.3%), 963.54 (4.7%), 962.52 (4.5%), 963.53 (3.2%), 964.53 (1.1%); elemental analysis C, 81.21; h, 7.55; n, 2.91; o, 4.99; s, 3.33.
Example 26
This example prepares compound P26, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 10 were substituted for intermediate 14 in example 25 and the other starting materials and procedures were the same as in example 25 to give 1.22g of product of formula P26 in 55% yield. The molecular formula is as follows: C65H72N2O 3S; theoretical M/Z960.53 value 960.53 (100.0%), 961.53 (70.3%), 962.53 (24.3%), 963.54 (4.7%), 962.52 (4.5%), 963.53 (3.2%), 964.53 (1.1%); elemental analysis C, 81.21; h, 7.55; n, 2.91; o, 4.99; s, 3.33.
Example 27
This example prepares compound P27, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent equivalents of intermediate 12 were substituted for intermediate 14 in example 25 and the other starting materials and procedures were the same as in example 25 to give 1.18g of product of formula P27 in 50% yield. The molecular formula is as follows: C65H72N2O 3S; theoretical M/Z960.53 value 960.53 (100.0%), 961.53 (70.3%), 962.53 (24.3%), 963.54 (4.7%), 962.52 (4.5%), 963.53 (3.2%), 964.53 (1.1%); elemental analysis C, 81.21; h, 7.55; n, 2.91; o, 4.99; s, 3.33.
Example 28
This example prepares compound P28, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 14 were substituted for equivalent amount of intermediate 8 in example 25 and the other starting materials and procedures were the same as in example 25 to give 1.38g of product of formula P28 in 61% yield. The molecular formula is as follows: C65H72N2O 3S; theoretical M/Z960.53 value 960.53 (100.0%), 961.53 (70.3%), 962.53 (24.3%), 963.54 (4.7%), 962.52 (4.5%), 963.53 (3.2%), 964.53 (1.1%); elemental analysis C, 81.21; h, 7.55; n, 2.91; o, 4.99; s, 3.33.
Example 29
This example prepared dicarbonyl comparative compound P29, which had the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of dicarbonyl intermediate (2.99mmol) and 1.26g of 3, 6-tert-butylcarbazole (2.5equ) were charged into a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 0.90g of product is obtained, yield 65%. The molecular formula is as follows: C44H32N2O 2; M/Z620.25 theory: M/Z620.25 (100.0%), 621.25 (47.6%), 622.25 (11.1%); elemental analysis C, 85.14; h, 5.20; n, 4.51; and O, 5.15.
Example 30
The structural formula and the synthetic route of the preparation of the disulfonyl comparison compound P30 are shown as follows:
100ml of toluene, 1g of a disulfonyl intermediate (2.99mmol) and 1.26g of 3, 6-tert-butylcarbazole (2.5equ) were added to a three-necked flask under nitrogen protection, 0.90g of sodium tert-butyl alkoxide was added thereto with stirring, and 59.8mg of palladium acetate and tert-butylphosphine were added thereto, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 0.89g of product is obtained with a yield of 64%. The molecular formula is as follows: C42H32N2O4S 2; M/Z692.18 theoretical value M/Z692.18 (100.0%), 693.18 (45.4%), 694.19 (10.1%), 694.18 (9.0%), 695.18 (4.1%), 693.18 (1.6%); elemental analysis C, 72.81; h, 4.66; n, 4.04; o, 9.24; and S, 9.25.
The following are examples of the use of the compounds of the present invention in Organic Light Emitting Diode (OLED) devices:
examples 30 to 39
The compound of the invention is used as a luminescent material of an OLED device, and the structure of the implemented universal device is as follows:
ITO(95nm)/TAPC(20nm)/Pn(10wt％):CBP(35nm)/TmPyPB(55nm)/LiF(1nm)/Al(100nm)
wherein ITO is an anode, TAPC is a hole injection layer, CBP is a luminescent material doped main body TmPyPB is an electron transport layer, LiF is an electron injection layer, and Al is a cathode.
The structural formula of the used material is as follows:
the device preparation process is as follows: carrying out ultrasonic treatment on the ITO transparent conductive glass in a cleaning agent, and then cleaning the ITO transparent conductive glass by deionized water, wherein the ultrasonic treatment is carried out in the presence of acetone: ultrasonic degreasing in mixed solvent of ethanol, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding with low-energy cations.
The glass with the anode ITO is placed in a vacuum chamber and is vacuumized to 1 multiplied by 10-5～9×10-3Pa on the anode film
The deposition rate of (2) evaporating and plating the organic material layer, wherein in evaporating and plating the luminous layer, the CBP and the luminous material are respectively placed on two evaporation plating sources, and the mixing proportion of the CBP and the luminous material is controlled by a certain deposition rate. Then is followed by
Evaporating LiF at a deposition rate of
The Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.
The current density-voltage-luminance graph, the maximum external current efficiency-luminance graph, and the maximum external power efficiency-luminance graph of the organic light emitting diode device of this example are shown in fig. 2 to 3, and the basic characterization data are shown in table 1.
The temperature-varying transient lifetime spectra of P18 and P20 in the thin film of this example are shown in fig. 4, and the long-life components in the transient spectra increase with increasing temperature, indicating that the long-life components of the molecules have the property of thermal activation, demonstrating that such molecules are molecules with the property of thermal activation delayed fluorescence.
Table 1 test results of OLED devices
Description of the drawings: the double receptor material can achieve high current efficiency and external quantum efficiency in a simple device structure. From the above table, compared with the traditional material with a single acceptor, even though a plurality of donors with different strengths are switched, the combination of two acceptor units makes it easier to realize small single triplet state energy level difference so as to enable the material to obtain the thermal activation delayed fluorescence property, thereby breaking the spin statistic rule, realizing the external quantum efficiency of more than 5%, and simultaneously realizing the light color change from blue green to yellow. Meanwhile, the good bipolar transmission performance of the luminescent molecules enables the lighting voltage of the device to be between 3 and 4 volts, and the low lighting voltage can ensure the high power efficiency of the electroluminescent device. This also allows such light emitting molecules to have a larger application space in OLED devices than known materials.
Compared with double-receptor molecules P29 and P30 containing dicarbonyl or a disulfonyl group with similar structures, the double-receptor molecule P4 composed of different receptors shows obviously higher maximum external quantum efficiency and current efficiency and lower starting voltage under the same device structure, the device performance is obviously improved, and the advancement of the double-receptor organic light-emitting small molecular material in molecular design is highlighted.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A double-acceptor organic light-emitting small molecule material is characterized by having any one chemical structure of P1n, P2n, P3n and P4 n:
wherein Ar is any aromatic amine group in the following (1) to (7):
2. the dual-acceptor organic light-emitting small molecule material according to claim 1, having a chemical structure of any one of P1-P28:
3. the preparation method of the double-receptor organic light-emitting small molecular material as claimed in any one of claims 1-2, which is characterized by comprising the following steps:
(1) preparing any one of intermediates having structures (a) to (d):
(2) under the protection of inert gas, adding the intermediate prepared in the step (1), an aromatic amine compound, alkali and a catalyst into an organic solvent, uniformly mixing, heating, refluxing, stirring and reacting, and carrying out cooling, extraction, spin-drying of the solvent and column chromatography to obtain the novel double-acceptor-unit-based organic micromolecule luminescent material; the aromatic amine compound is any one of carbazole, 9' -dimethylacridine, phenoxazine or phenothiazine;
the molar ratio of the intermediate to the aromatic amine compound is 1 (2-2.5).
4. The method for preparing the dual-acceptor organic light-emitting small molecule material according to claim 3, wherein the heating, refluxing and stirring reaction in the step (2) is specifically:
the temperature is 90-110 ℃, and the reaction time is 12-24 h.
5. The preparation method of the dual-acceptor organic light-emitting small molecular material according to claim 3, wherein the base in the step (2) is an organic base, and the amount of the base is 1.8-2.5 times of the molar equivalent of the aromatic amine compound.
6. The method for preparing the dual-acceptor organic light-emitting small molecule material according to claim 3, wherein the catalyst in the step (2) is composed of palladium acetate and tributyl phosphine.
7. The method for preparing the dual-acceptor organic light-emitting small molecule material according to claim 3, wherein the organic solvent in the step (2) is toluene.
8. The application of the double-receptor organic light-emitting small molecular material of any one of claims 1-2 in an electroluminescent diode.
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