Anthracene compound and application thereof

Abstract

The application provides an anthracene compound and application thereof, and the anthracene compound has a structure shown in general formula I. The anthracene compound is suitable for being used as a host material of a light-emitting layer of an organic electroluminescent device, so that the organic electroluminescent device has a lower driving voltage, a higher light-emitting efficiency and a longer service life.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescent materials, and in particular relates to an anthracene compound and application thereof. Background Art

[0002] Organic light emitting phenomenon refers to the phenomenon of converting electrical energy into light energy by using organic materials. Organic light emitting devices that utilize organic light emitting phenomenon generally have a structure including a positive electrode, a negative electrode and an organic material layer interposed therebetween. In many cases, the organic material layer has a multilayer structure composed of different materials to improve the efficiency and stability of the organic light emitting device. For example, the organic material layer can be composed of a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer, etc. In the structure of such an organic light emitting device, if a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic material layer and electrons are injected from the negative electrode into the organic material layer. When the injected holes and electrons meet each other, excitons are formed, and when the excitons fall back to the ground state, light is emitted. Such organic light emitting devices are known to have characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle and high contrast. Organic electroluminescent elements are self-luminescent elements that utilize the following principle: by applying an electric field, the fluorescent substance emits light by utilizing the recombination energy of holes injected from the anode and electrons injected from the cathode. It has the following structure: an anode, a cathode, and an organic material layer between them. To improve the efficiency and stability of organic electroluminescent elements, the organic material layer typically includes multiple layers made of different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer, an electron transport layer (ETL), and an electron injection layer (EIL). In such an organic light-emitting element, when a voltage is applied between the anode and cathode, holes from the anode and electrons from the cathode are injected into the organic material layer. The resulting excitons then emit light of a specific wavelength when they migrate to the ground state.

[0003] In order to fully demonstrate the excellent properties of the above-mentioned organic light-emitting devices, the materials that constitute the organic material layer in the device need to be supported by stable and effective materials, such as hole injection materials, hole transport materials, light-emitting materials, electron blocking materials, electron transport materials, electron injection materials, etc. Therefore, there is a constant need to develop new materials. Summary of the Invention

[0004] To address the shortcomings of the prior art, the present invention provides an anthracene compound and its application. By designing the structure of the anthracene compound, the present invention makes it suitable as a host material for the light-emitting layer of an organic electroluminescent device (OLED), thereby enabling the OLED to have a lower driving voltage, higher luminous efficiency, and longer lifespan.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In one aspect, the present invention provides an anthracene compound having a structure shown in Formula I:

[0007]

[0008] in:

[0009] R is selected from R 10 -R 19 independently selected from hydrogen or deuterium;

[0010] R1-R8 are the same as or different from each other and are independently selected from hydrogen or deuterium;

[0011] R9 is selected from any one of a phenyl group which may be substituted by deuterium, a naphthyl group which may be substituted by deuterium, a biphenyl group which may be substituted by deuterium, and a terphenyl group which may be substituted by deuterium.

[0012] Preferably, R is selected from

[0013] Preferably, the anthracene compound is selected from any one of the following compounds:

[0014]

[0015]

[0016]

[0017] The present invention lists some specific structural forms of the anthracene compounds, but the anthracene compounds of the present invention are not limited to these listed chemical structures. Any structure based on the structure shown in Formula I where R, R1, R2, and R3 meet the above-mentioned limiting conditions should be included.

[0018] In a second aspect, the present invention provides an organic electroluminescent device, comprising the anthracene compound according to the first aspect.

[0019] Preferably, the organic electroluminescent device comprises a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode; the material of the organic layer comprises the anthracene compound as described in the first aspect.

[0020] Preferably, the organic layer includes a light-emitting layer; the material of the light-emitting layer includes the anthracene compound as described in the first aspect.

[0021] In a third aspect, the present invention provides a display device, comprising the organic electroluminescent device according to the second aspect.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention designs the structure of anthracene compounds to obtain anthracene compounds with good luminescence properties, which can be used to prepare organic electroluminescent devices and are suitable as main materials for organic electroluminescent devices, so that the organic electroluminescent devices have lower driving voltage, higher current efficiency and longer life. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0025] Example 1

[0026]

[0027] The raw materials 1-A (1.0 eq) and 1-B (1.1 eq) were put into a mixed solution of toluene, ethanol and water, followed by nitrogen replacement three times. Potassium carbonate (2.0 eq) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4) (0.02 eq) were added under nitrogen protection, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered and filtered using diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The mixture was slurried twice with ethanol to obtain intermediate 1-1 (yield: 79.8%).

[0028] The mass spectrum data of intermediate 1-1 was tested, and the mass spectrum m / z was measured to be 254.11.

[0029] Under nitrogen protection, intermediate 1-1 (1.0 eq) and N-bromosuccinimide (NBS) (1.5 eq) were dissolved in tetrahydrofuran solution, stirred evenly, heated to reflux, and refluxed for 4 hours; after the reaction, the filtrate was cooled to room temperature, water was added to precipitate the solid, filtered, washed three times with water, and filtered; slurried twice with ethanol and filtered; and then recrystallized twice with a mixed solvent of toluene and ethanol (toluene:ethanol volume ratio = 1:1) to obtain intermediate 1-2 (yield: 75.7%).

[0030] The mass spectrum data of intermediate 1-2 was tested, and the mass spectrum m / z was measured to be 332.02.

[0031] The intermediate 1-2 (1.0 eq) and the raw material 1-C (1.1 eq) were put into a xylene solution, and then nitrogen was replaced three times. Under nitrogen protection, sodium tert-butoxide (2.0 eq), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (0.02 eq), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos) (0.04 eq) were added, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered, and the solution was filtered using diatomaceous earth to remove salts and catalysts. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. After recrystallization from toluene three times, compound 1 was obtained (yield: 81.8%).

[0032] The mass spectrum data of compound 1 was tested, and the mass spectrum m / z was measured to be 469.18.

[0033] Example 2

[0034]

[0035] The raw materials 2-A (1.0 eq) and 2-B (1.1 eq) were put into a mixed solution of toluene, ethanol and water, followed by nitrogen replacement three times. Potassium carbonate (2.0 eq) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4) (0.02 eq) were added under nitrogen protection, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered and filtered using diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The mixture was slurried twice with ethanol to obtain intermediate 2-1 (yield: 78.3%).

[0036] The mass spectrum data of intermediate 2-1 was tested, and the mass spectrum m / z was measured to be 339.20.

[0037] Under nitrogen protection, intermediate 2-1 (1.0 eq) and N-bromosuccinimide (NBS) (1.5 eq) were dissolved in tetrahydrofuran solution, stirred evenly, heated to reflux, and refluxed for 4 hours. After the reaction, the filtrate was cooled to room temperature, water was added to precipitate the solid, filtered, washed three times with water, and filtered; slurried twice with ethanol and filtered; and then recrystallized twice with a mixed solvent of toluene and ethanol (toluene:ethanol volume ratio = 1:1) to obtain intermediate 2-2 (yield: 75.7%).

[0038] The mass spectrum data of intermediate 2-2 was tested, and the mass spectrum m / z was measured to be 416.10.

[0039] The intermediate 2-2 (1.0 eq) and the raw material 2-C (1.1 eq) were put into a xylene solution, and then nitrogen was replaced three times. Under nitrogen protection, sodium tert-butoxide (2.0 eq), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (0.02 eq), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos) (0.04 eq) were added, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered, and the solution was filtered using diatomaceous earth to remove salts and catalysts. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. After recrystallization from toluene three times, compound 2 was obtained (yield: 81.8%).

[0040] The mass spectrum data of compound 2 was tested, and the mass spectrum m / z was measured to be 553.26.

[0041] Example 3

[0042]

[0043] Raw materials 3-A (1.0 eq) and raw materials 3-B (1.1 eq) were put into a mixed solution of toluene, ethanol and water, followed by nitrogen replacement three times. Potassium carbonate (2.0 eq) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4) (0.02 eq) were added under nitrogen protection, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered and filtered using diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The mixture was slurried twice with ethanol to obtain intermediate 1 (yield: 78.8%).

[0044] The mass spectrum data of intermediate 3-1 was tested, and the mass spectrum m / z was measured to be 304.13.

[0045] Under nitrogen protection, intermediate 3-1 (1.0 eq) and N-bromosuccinimide (NBS) (1.5 eq) were dissolved in tetrahydrofuran solution, stirred evenly, heated to reflux, and refluxed for 4 hours. After the reaction, the filtrate was cooled to room temperature, water was added to precipitate the solid, filtered, washed three times with water, and filtered; slurried twice with ethanol and filtered; and then recrystallized twice with a mixed solvent of toluene and ethanol (toluene:ethanol volume ratio = 1:1) to obtain intermediate 3-2 (yield: 75.1%).

[0046] The mass spectrum data of intermediate 3-2 was tested, and the mass spectrum m / z was measured to be 382.04.

[0047] The intermediate 3-2 (1.0 eq) and the raw material 3-C (1.1 eq) were put into a xylene solution, and then nitrogen was replaced three times. Under nitrogen protection, sodium tert-butoxide (2.0 eq), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (0.02 eq), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos) (0.04 eq) were added, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered, and the solution was filtered using diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed with water three times, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. After recrystallization from toluene twice, compound 3 was obtained (yield: 83.6%).

[0048] The mass spectrum data of compound 3 was tested, and the mass spectrum m / z was measured to be 519.20.

[0049] Example 4

[0050]

[0051] The raw materials 4-A (1.0 eq) and 4-B (1.1 eq) were put into a mixed solution of toluene, ethanol and water, followed by nitrogen replacement 3 times. Potassium carbonate (2.0 eq) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4) (0.02 eq) were added under nitrogen protection, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered and filtered using diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The mixture was slurried twice with ethanol to obtain intermediate 4-1 (yield: 75.2%).

[0052] The mass spectrum data of intermediate 4-1 was tested, and the mass spectrum m / z was measured to be 304.13.

[0053] Under nitrogen protection, intermediate 4-1 (1.0 eq) and N-bromosuccinimide (NBS) (1.5 eq) were dissolved in tetrahydrofuran solution, stirred evenly, heated to reflux, and refluxed for 4 hours. After the reaction, the filtrate was cooled to room temperature, water was added to precipitate the solid, filtered, washed three times with water, and filtered; slurried twice with ethanol and filtered; and then recrystallized twice with a mixed solvent of toluene and ethanol (toluene:ethanol volume ratio = 1:1) to obtain intermediate 4-2 (yield: 76.3%).

[0054] The mass spectrum data of intermediate 4-2 was tested, and the mass spectrum m / z was measured to be 382.04.

[0055] The intermediate 4-2 (1.0 eq) and the raw material 4-C (1.1 eq) were put into a xylene solution, and then nitrogen was replaced three times. Under nitrogen protection, sodium tert-butoxide (2.0 eq), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (0.02 eq), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos) (0.04 eq) were added, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered, and the solution was filtered using diatomaceous earth to remove salts and catalysts. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The solution was then recrystallized three times from toluene to obtain compound 4 (yield: 80.2%).

[0056] The mass spectrum data of compound 4 was tested, and the mass spectrum m / z was measured to be 519.20.

[0057] Example 5

[0058]

[0059] The raw materials 5-A (1.0 eq) and 5-B (1.1 eq) were put into a mixed solution of toluene, ethanol and water, and then replaced with nitrogen three times. Potassium carbonate (2.0 eq) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4) (0.02 eq) were added under nitrogen protection, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered and filtered using diatomaceous earth to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The mixture was slurried twice with ethanol to obtain intermediate 5-1 (yield: 77.5%).

[0060] The mass spectrum data of intermediate 5-1 was tested, and the mass spectrum m / z was measured to be 406.17.

[0061] Under nitrogen protection, intermediate 5-1 (1.0 eq) and N-bromosuccinimide (NBS) (1.5 eq) were dissolved in tetrahydrofuran solution, stirred evenly, heated to reflux, and refluxed for 4 hours. After the reaction, the filtrate was cooled to room temperature, water was added to precipitate the solid, filtered, washed three times with water, and filtered; slurried twice with ethanol and filtered; and then recrystallized twice with a mixed solvent of toluene and ethanol (toluene:ethanol volume ratio = 1:1) to obtain intermediate 5-2 (yield: 78.6%).

[0062] The mass spectrum data of intermediate 5-2 was tested, and the mass spectrum m / z was measured to be 484.08.

[0063] The intermediate 5-2 (1.0 eq) and the raw material 5-C (1.1 eq) were put into a xylene solution, and then nitrogen was replaced three times. Under nitrogen protection, sodium tert-butoxide (2.0 eq), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (0.02 eq), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos) (0.04 eq) were added, stirred evenly, heated to reflux, and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered, and the solution was filtered using diatomaceous earth to remove salts and catalysts. After the filtrate was cooled to room temperature, it was washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The solution was then recrystallized three times from toluene to obtain compound 5 (yield: 85.2%).

[0064] The mass spectrum data of compound 5 was tested, and the mass spectrum m / z was measured to be 621.25.

[0065] Device Example 1

[0066] Specifically, the preparation of the organic electroluminescent device includes the following steps:

[0067] a. ITO anode: Wash an ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150nm in distilled water twice, ultrasonically clean it for 30 minutes, then repeatedly clean it with distilled water twice, ultrasonically clean it for 10 minutes. After washing, transfer it to a spin dryer for drying, and finally bake it in a vacuum oven at 220℃ for 2 hours. After baking, cool it down and it can be used. Using this substrate as the anode, use an evaporation machine to carry out the evaporation device process, and then evaporate other functional layers on it in sequence.

[0068] b. HIL (hole injection layer): The hole injection layer materials HT and P-dopant were vacuum evaporated at a deposition rate of 97:3, and the thickness was 10 nm.

[0069] c. HTL (hole transport layer): At a deposition rate of , 120 nm of HT was vacuum evaporated on the hole injection layer as a hole transport layer.

[0070] d. Luminous auxiliary layer: At a deposition rate of , 5 nm of EB was vacuum-deposited on the hole transport layer as a light-emitting auxiliary layer.

[0071] e. EML (light-emitting layer): Then on the above-mentioned light-emitting auxiliary layer, The evaporation rate was 25 nm, and compound 1 was vacuum evaporated to a thickness of 25 nm as the main material (Host) and the dopant material (Dopant) as the light-emitting layer, wherein the evaporation rate ratio of Host to Dopant was 98:2.

[0072] f. HBL (hole blocking layer): The evaporation rate is , and the vacuum evaporated HB with a thickness of 5.0 nm is used as the hole blocking layer.

[0073] g. ETL (Electron Transport Layer): ET and Liq were vacuum evaporated to a thickness of 30 nm as an electron transport layer, wherein the evaporation rate ratio of ET to Liq was 50:50.

[0074] h. EIL (electron injection layer): The evaporation rate is 1.0 nm, and a Yb film layer is evaporated to form an electron injection layer.

[0075] i. Cathode: The evaporation rate ratio of magnesium and silver was 13nm, and the evaporation rate ratio was 1:9 to obtain an OLED device.

[0076] j. Light extraction layer: At a deposition rate of , CPL with a thickness of 65 nm was vacuum-deposited on the cathode as a light extraction layer.

[0077] k. Package the vapor-deposited substrate: First, use the glue coating equipment to coat the cleaned cover with UV glue, then move the coated cover to the pressing section, place the vapor-deposited substrate on the upper end of the cover, and finally bond the substrate and cover with the bonding equipment, and complete the light curing of the UV glue at the same time.

[0078] The structural formulas of the materials mentioned above are as follows:

[0079]

[0080]

[0081] Referring to the method provided in the above device embodiment 1, compounds 2-5 were selected to replace compound 1, and the light-emitting layer was evaporated to prepare the corresponding organic electroluminescent devices, which were respectively recorded as device embodiments 2-5.

[0082] Compound HT-1 was used in place of compound HT, and the hole injection layer and the hole transport layer were evaporated to prepare a corresponding organic electroluminescent device, which was recorded as device example 6.

[0083] Device comparison ratio:

[0084] This comparative example provides an organic electroluminescent device. The only difference in the preparation method of this organic electroluminescent device from that of Device Example 1 is that the organic electroluminescent device is prepared by evaporating existing comparative compounds a, b, c, and d, respectively, instead of the host material (Compound 1) in Device Example 1. Comparative Examples 1-4 are prepared. The chemical structures of comparative compounds a, b, c, and d are:

[0085]

[0086] The driving voltage, luminous efficiency, and lifespan of the organic electroluminescent devices obtained from the device examples 1-6 and the device comparative examples 1-4 were characterized at a brightness of 1000 (nits). (The test results are based on the test data of comparative example 1.) The test results are shown in Table 1 below:

[0087] Table 1

[0088]

[0089]

[0090] As shown in Table 1, the present invention obtains anthracene compounds through molecular design. The anthracene compounds provided by the present invention can be used as the host material of OLED light-emitting devices, resulting in OLED light-emitting devices with lower driving voltage, higher luminous efficiency, and longer life.

[0091] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the anthracene compounds and their applications. However, the present invention is not limited to these embodiments, and it does not mean that the present invention must rely on these embodiments for implementation. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for raw materials in the products of the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. An anthracene compound, characterized in that The anthracene compound has a structure shown in general formula I: ； Formula I in: R is selected from , the wavy line represents the attachment site of the group, R 10 -R 19 independently selected from hydrogen or deuterium; R1-R8 are the same as or different from each other and are independently selected from hydrogen or deuterium; R9 is selected from any one of a phenyl group which may be substituted by deuterium, a naphthyl group which may be substituted by deuterium, a biphenyl group which may be substituted by deuterium, and a terphenyl group which may be substituted by deuterium.

2. The anthracene compound according to claim 1, characterized in that R is selected from or .

3. The anthracene compound according to claim 1, characterized in that The anthracene compound is selected from any one of the following compounds: ； ； ； ； 。 4. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the anthracene compound according to any one of claims 1 to 3.

5. The organic electroluminescent device according to claim 4, characterized in that: The organic electroluminescent device comprises a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode; the material of the organic layer comprises the anthracene compound according to any one of claims 1 to 3.

6. The organic electroluminescent device according to claim 5, characterized in that: The organic layer includes a light-emitting layer; the material of the light-emitting layer includes the anthracene compound according to any one of claims 1 to 3.

7. A display device, characterized in that: The display device comprises the organic electroluminescent device according to claim 4.

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