Anthracene compound, intermediate, organic electroluminescent device and display device

Abstract

The invention provides an anthracene compound, an intermediate, an organic electroluminescent device and a display device, and relates to the technical field of organic electroluminescent materials. The anthracene compound disclosed by the invention is used as a main body material of a light-emitting layer of the organic light-emitting device, so that the organic light-emitting device has relatively low driving voltage, relatively high current efficiency and relatively long service life.

Description

Technical Field

[0001] The invention belongs to the field of organic photoelectric technology, and specifically relates to an anthracene compound, an intermediate, an organic electroluminescent device and a display device. Background Art

[0002] In today's information age, human-computer interaction and communication between people cannot be achieved without the hardware support of display screens. Display screens play an increasingly important role in people's daily lives. As people's requirements for the performance of display screens continue to increase, display technology is also constantly improving and innovating. In the past few decades, the research and technology development of the new generation of display technology, organic electroluminescent display (OLED), has developed rapidly in academia and industry.

[0003] After decades of development, the structure of OLED devices has gradually evolved from the initial single-layer and double-layer structures to the current multi-layer structure, which mainly includes anode, hole injection layer, hole transport layer, electron blocking / exciton blocking layer, organic light-emitting layer, hole blocking / exciton blocking layer, electron transport layer, electron injection layer and metal cathode. Its luminescence mechanism is that holes and electrons are generated by the anode and cathode respectively, and reach the light-emitting layer through the injection layer and transport layer, and then recombine into excitons in the light-emitting layer. The excitons radiate and transition to generate photons and emit light. The entire luminescence process goes through the injection and transmission of carriers, the formation of excitons, the decay of excitons and luminescence.

[0004] Currently, OLED has become the mainstream display technology, and accordingly, various new OLED materials have also been developed. Therefore, the field is in urgent need of developing more types of higher performance organic thin film materials to meet people's higher requirements for organic electroluminescent devices.

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

[0006] In a first aspect, the present invention provides an anthracene compound having a structure as shown in formula BH-A:

[0007]

[0008] In the formula BH-A, Ar1 and Ar2 are each independently selected from substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C 12 ~C 20 Any one of heteroaryl groups; wherein the C6-C40 aryl group may be, for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, C40 aryl, C 12 ~C 20 Heteroaryl can be, for example, C12, C14, C16, C18, C20 heteroaryl;

[0009] In the formula BH-A, the substituents in Ar1 and Ar2 are each independently selected from -D, -F, -CN, C1 to C 10 Alkyl, C1-C5 alkoxy, C6-C 15 At least one of the aromatic groups; wherein C1~C 10 The alkyl group may be, for example, methyl, ethyl, propyl, tert-butyl, cyclopentyl, or cyclohexyl; the C1-C5 alkoxy group may be, for example, methoxy, ethoxy, or propoxy; the C6-C15 aryl group may be, for example, phenyl or naphthyl;

[0010] The hydrogen atoms in the formula BH-A can be independently replaced by -D, -F, -CN, C1-C5 alkyl, C1-C5 alkoxy, C6-C 20 Aryl, C 12 ~C 20 wherein the C1-C5 alkyl group may be, for example, methyl, ethyl, or propyl; the C1-C5 alkoxy group may be, for example, methoxy, ethoxy, or propoxy; 12 ~C 20 The heteroaryl group may be, for example, dibenzothienyl or dibenzofuranyl.

[0011] In the present invention, "D" represents a deuterium atom, and the same shall apply hereinafter.

[0012] In the present invention, an anthracene compound with a specific structure is obtained by designing the structure of the anthracene compound and controlling the specific substituents on the anthracene compound and the positions where the substituents are connected. The anthracene compound provided by the present invention can be used as a main material of the light-emitting layer of an OLED light-emitting device, so that the OLED light-emitting device has a lower driving voltage, a higher current efficiency and a longer life.

[0013] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0014] Preferably, Ar1 is selected from C6 to C 40 Aryl, C 12 ~C 20 Any of the heteroaryl groups.

[0015] Preferably, the C6~C 40 The aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl, and benzonaphthofluorenyl.

[0016] Preferably, the C 12 ~C 20 The heteroaryl group is selected from any one of dibenzofuranyl, dibenzothienyl, benzodibenzofuranyl, benzodibenzothienyl, dinaphthofuranyl and dinaphthothienyl.

[0017] Preferably, the C6~C 20 The aryl group is selected from any one of phenyl, biphenyl or naphthyl.

[0018] Preferably, Ar1 and Ar2 are each independently selected from any one of phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, triphenylene, fluoranthene, dibenzofuranyl, dibenzothienyl, naphthodibenzofuranyl and naphthodibenzothienyl.

[0019] Preferably, the hydrogen atoms in the formula BH-A can be independently substituted by at least one of -D, methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, phenyl, naphthyl, dibenzothienyl, and dibenzofuranyl.

[0020] Preferably, the anthracene compound includes any one of the following compounds:

[0021]

[0022]

[0023]

[0024]

[0025] Preferably, the anthracene compound includes any one of the following compounds 1 to 15:

[0026]

[0027] In a second aspect, the present invention provides an intermediate, wherein the intermediate comprises any one of the following compounds:

[0028]

[0029] The intermediate is used to synthesize the anthracene compound.

[0030] In a third aspect, the present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;

[0031] The material of the organic thin film layer includes the anthracene compound.

[0032] Preferably, the organic thin film layer includes a light-emitting layer; the material of the light-emitting layer includes a host material, and the host material includes the anthracene compound.

[0033] In a fourth aspect, the present invention provides a display device, comprising the organic electroluminescent device.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The present invention obtains an anthracene compound with a specific structure by designing the structure of the anthracene compound and controlling the specific substituents on the anthracene compound and the positions where the substituents are connected. The anthracene compound is used as a light-emitting layer material of an organic electroluminescent device, and the prepared organic electroluminescent device has a lower driving voltage, a higher current efficiency and a longer lifespan. DETAILED DESCRIPTION

[0036] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0037] Preparation Example 1

[0038] This preparation example provides an intermediate M-3 and a synthesis method thereof. The synthesis method of the intermediate M-3 is as follows:

[0039]

[0040] (1) Synthesis of intermediate M-1

[0041] Under nitrogen protection, 200 mL of toluene, 100 mL of ethanol and 100 mL of water were added to a 1L three-necked flask in sequence, and then 1-bromo-4-iodonaphthalene (33.30 g, 100.0 mmol), 3-chloro-2-hydroxyphenylboric acid (17.24 g, 100.0 mmol), potassium carbonate (20.70 g, 150.0 mmol) and tetrakistriphenylphosphine palladium (1.155 g, 1.0 mmol) were added, and the temperature was slowly raised to reflux for reaction for 8 h, and the temperature was lowered to room temperature. Water was added to separate the mixture, and the aqueous phase was extracted once with toluene. The organic phases were combined, washed with water, dried with magnesium sulfate, filtered to remove the magnesium sulfate, and the solvent was removed under reduced pressure. The mixture was crystallized with a mixed solvent of toluene and ethanol to obtain intermediate M-1 (14.2 g).

[0042] The intermediate M-1 was detected by mass spectrometry, and the two peaks with the largest mass-to-charge ratio (m / z) were 331.96 and 333.96.

[0043] (2) Synthesis of intermediate M-2

[0044] Under nitrogen protection, 90 mL of hexafluorobenzene and 60 mL of 1,3-dimethyl-2-imidazolidinone were added to a 500 mL three-necked flask in sequence, and then intermediate M-1 (13.34, 40.0 mmol), palladium acetate (0.90 g, 4.0 mmol), tert-butyl perbenzoate (23.28 g, 120.0 mmol) and 3-nitropyridine (0.50 g, 4.0 mmol) were added. The temperature was slowly raised to reflux for 24 h, and the temperature was lowered to room temperature. Water was added to separate the mixture, and the aqueous phase was extracted once with toluene. The organic phases were combined, washed with water, dried with magnesium sulfate, filtered to remove the magnesium sulfate, and the solvent was removed under reduced pressure. The mixture was crystallized with a mixed solvent of toluene and ethanol to obtain intermediate M-2 (4.2 g).

[0045] The intermediate M-2 was detected by mass spectrometry, and the two peaks with the largest mass-to-charge ratio (m / z) were 329.94 and 331.94.

[0046] The intermediate M-2 was subjected to NMR detection, and the data are as follows: 1H-NMR (Bruker, Switzerland, AvanceⅡ400MHz NMR spectrometer, CDCl3), δ8.92 (m, 1H), δ8.36 (s, 1H), δ7.89-7.76 (m, 2H), δ7.65-7.61 (m, 1H), δ7.52-7.47 (m, 1H), δ7.30~7.22 (m, 2H).

[0047] (3) Synthesis of intermediate M-3

[0048] Under nitrogen protection, 100 mL of toluene, 50 mL of ethanol and 50 mL of water were added to a 500 mL three-necked flask in sequence, and then intermediate M-2 (4.00 g, 12.0 mmol), phenylboric acid (1.61 g, 13.2 mmol), potassium carbonate (2.48 g, 18.0 mmol) and tetrakistriphenylphosphine palladium (0.139 g, 0.12 mmol) were added, and the temperature was slowly raised to reflux for 8 h, and the temperature was lowered to room temperature. Water was added to separate the mixture, and the aqueous phase was extracted once with toluene. The organic phases were combined, washed with water, dried with magnesium sulfate, filtered to remove the magnesium sulfate, and the solvent was removed under reduced pressure. The mixture was crystallized with a mixed solvent of toluene and ethanol to obtain intermediate M-3 (3.1 g).

[0049] The intermediate M-3 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 328.07.

[0050] Preparation Examples 2 to 4

[0051] Preparation Examples 2 to 4 respectively provide intermediates, and their synthesis methods refer to the synthesis method of intermediate M-3, with the only difference that the phenylboric acid in step (3) of Preparation Example 1 is replaced by other boronic acid compounds of the same substance amount (the structures of boronic acid compounds and prepared intermediates are detailed in Table 1), and other conditions are the same as the synthesis method of intermediate M-3. The intermediate is subjected to mass spectrometry detection, and the test data are detailed in Table 1 below.

[0052] Table 1

[0053]

[0054] Synthesis Example 1

[0055] This synthesis example provides a compound 1, and its synthesis method is as follows:

[0056]

[0057] Under nitrogen protection, 60 mL of toluene and 6 mL of water were added to a 250 mL three-necked flask in sequence, and then intermediate M-3 (3.29 g, 10.0 mmol), 10-phenyl-9-anthraceneboric acid (3.58 g, 12.0 mmol), potassium phosphate (6.37 g, 30.0 mmol), Pd2(dba)3 (0.18 g, 0.2 mmol) and X-Phos (0.19 g, 0.4 mmol) were added, and the temperature was slowly raised to reflux for 12 h, and the temperature was lowered to room temperature. Water was added to separate the organic layer, and the organic layer was washed with water and dried with magnesium sulfate. After filtering to remove the magnesium sulfate, the solvent was removed under reduced pressure and crystallized with a mixed solvent of toluene and ethanol to obtain compound 1 (2.7 g).

[0058] The mass spectrometry of compound 1 showed a mass-to-charge ratio (m / z) of 546.20.

[0059] Synthesis Examples 2 to 15

[0060] Synthesis Examples 2 to 15 provide compounds 2 to 15 respectively, and their synthesis methods refer to the synthesis method of compound 1, with the only difference that the intermediate M-3 is replaced by other intermediates (M4 to M6) of equal amount (see Table 2 for details), and 10-phenyl-9-anthraceneboric acid is replaced by other boronic acid compounds of equal amount (see Table 2 for details). Other conditions are the same as the synthesis method of compound 1. The synthesized compounds (see Table 2 for details) are subjected to mass spectrometry detection, and the test data are shown in Table 2 for details.

[0061] Table 2

[0062]

[0063]

[0064]

[0065]

[0066]

[0067] Other compounds whose specific synthesis methods are not listed can be synthesized by referring to the above embodiments in combination with common knowledge in the art.

[0068] The specific structures of some of the substances used in the following application examples and comparative application examples are as follows:

[0069]

[0070] Application Example 1

[0071] This application example provides an organic electroluminescent device, using the compound 1 provided in Synthesis Example 1 of the present invention as the main material of the light-emitting layer;

[0072] The structure of the organic electroluminescent device is: ITO / HT (40 nm) / luminescent layer main material: BD-23% (30 nm) / TPBI (30 nm) / LiF (0.5 nm) / Al (150 nm).

[0073] The preparation method of the organic electroluminescent device is as follows:

[0074] The glass substrate coated with an ITO transparent conductive layer (as an anode) was ultrasonically treated in a cleaning agent, then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, and then baked in a clean environment until the water was completely removed. It was cleaned with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam to improve the surface properties and enhance the bonding ability with the hole layer.

[0075] Place the glass substrate in a vacuum chamber and evacuate to 1×10 -5 ~1×10 -6 Pa is vacuum-deposited onto the cleaned ITO substrate in sequence, the steps are as follows:

[0076] HT with a thickness of 40 nm was vacuum-deposited on the anode as a hole transport layer.

[0077] Subsequently, a light-emitting layer with a thickness of 30 nm was obtained by vacuum evaporation on the hole transport layer. The components of the light-emitting layer included a main material of the light-emitting layer and a doping material BD-2. The volume ratio of the main material of the light-emitting layer to BD-2 was 97:3.

[0078] Then, TPBI with a thickness of 30 nm was vacuum-deposited on the light-emitting layer as an electron transport layer.

[0079] Next, lithium fluoride (LiF) was vacuum-deposited to a thickness of 0.5 nm on the electron transport layer as an electron injection layer, and finally, aluminum (Al) was vacuum-deposited to a thickness of 150 nm on the electron injection layer as a cathode layer.

[0080] Application Examples 2 to 10

[0081] Application Examples 2 to 10 respectively provide an organic electroluminescent device, which differs from Application Example 1 only in that the main material of the light-emitting layer is different (see Table 3 for details), and other conditions are the same as those of Application Example 1.

[0082] Application Comparative Examples 1 to 4

[0083] Comparative Application Examples 1 to 4 respectively provide an organic electroluminescent device, which is different from Application Example 1 only in that the main material of the light-emitting layer is different (see Table 3 for details), and other conditions are the same as those of Application Example 1.

[0084] Performance Testing

[0085] Test the driving voltage, current efficiency and life LT90 of the OLED devices provided above; LT90 refers to the time required for the brightness to drop to 90% of the original brightness while maintaining the current density at the initial brightness of 1000nit. The test items include the brightness, driving voltage and current efficiency of the organic electroluminescent device. The driving voltage, current efficiency and LT90 data are all based on a brightness of 1000cd / m 2 The relative value when (based on the application of comparative example 1).

[0086] The performance test results of the organic electroluminescent device are shown in Table 3.

[0087] Table 3

[0088]

[0089] It can be seen from the contents of Table 3 that the present invention obtains anthracene compounds with specific structures by designing the structure of anthracene compounds. The anthracene compounds provided by the present invention can be used as the main material of the light-emitting layer of an organic electroluminescent device, so that the organic electroluminescent device has a lower driving voltage, higher current efficiency and longer life.

[0090] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An anthracene compound, characterized in that: The anthracene compound has a structure as shown in formula BH-A: In the formula BH-A, Ar1 and Ar2 are each independently selected from substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C 12 ~C 20 Any of the heteroaryl groups; In the formula BH-A, the substituents in Ar1 and Ar2 are each independently selected from -D, -F, -CN, C1 to C 10 Alkyl, C1-C5 alkoxy, C6-C 15 at least one of aromatic groups; The hydrogen atoms in the formula BH-A can be independently replaced by -D, -F, -CN, C1-C5 alkyl, C1-C5 alkoxy, C6-C 20 Aryl, C 12 ~C 20 At least one of the heteroaryl groups is substituted.

2. The anthracene compound according to claim 1, characterized in that Ar1 is selected from C6 to C 40 Aryl, C 12 ~C 20 Any of the heteroaryl groups.

3. The anthracene compound according to claim 1, characterized in that C6~C 40 The aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl, and benzonaphthfluoroenyl; The C 12 ~C 20 The heteroaryl group is selected from any one of dibenzofuranyl, dibenzothienyl, benzodibenzofuranyl, benzodibenzothienyl, dinaphthofuranyl and dinaphthothienyl; C6~C 20 The aryl group is selected from any one of phenyl, biphenyl or naphthyl.

4. The anthracene compound according to claim 1, characterized in that Ar1 and Ar2 are each independently selected from any one of phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, triphenylene, fluoranthene, dibenzofuranyl, dibenzothienyl, naphthodibenzofuranyl and naphthodibenzothienyl.

5. The anthracene compound according to claim 1, characterized in that The hydrogen atoms in the formula BH-A can be independently substituted by at least one of -D, methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, phenyl, naphthyl, dibenzothienyl, and dibenzofuranyl.

6. The anthracene compound according to claim 1, characterized in that The anthracene compound includes any one of the following compounds:

7. An intermediate, characterized in that The intermediate includes any one of the following compounds: The intermediate is used to synthesize the anthracene compound as claimed in any one of claims 1 to 6.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic thin film layer arranged between the anode and the cathode; The material of the organic thin film layer includes the anthracene compound according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic thin film layer includes a light-emitting layer; the material of the light-emitting layer includes a main material, and the main material includes the anthracene compound.

10. A display device, characterized in that: The display device comprises the organic electroluminescent device according to claim 8 or 9.

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