Anthracene compound, organic electroluminescent device and display device

Abstract

The invention provides an anthracene compound, an organic electroluminescent device and a display device. The anthracene compound has a structure as shown in the following formula BH-A. The structure of the anthracene compound is designed, and the compound is used as the main body material of the light-emitting layer of the organic light-emitting device, so that the organic light-emitting device has lower driving voltage, higher current efficiency and longer service life.

Description

Technical Field

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

[0002] As a new type of display technology, organic electroluminescent devices have unique advantages such as self-luminescence, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, fast response speed, wide applicable temperature range, low driving voltage, the ability to produce flexible, bendable and transparent display panels, and environmental friendliness. They can be used in flat-panel displays and new generation lighting, and can also be used as LCD backlight sources.

[0003] Currently, organic electroluminescence has become the mainstream display technology, and accordingly, various new materials have been developed to prepare organic thin film layers. However, with the development of society and technology, people have put forward higher requirements for the various performances of organic electroluminescent devices, especially in terms of efficiency, life, voltage, etc. Therefore, the field is in urgent need of developing more types of organic thin film materials with higher performance to meet people's higher requirements for organic electroluminescent devices. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide an anthracene compound, an organic electroluminescent device and a display device. The present invention designs the structure of anthracene compounds and uses the anthracene compounds as the main material of the light-emitting layer, so that the organic electroluminescent device has a lower driving voltage, higher current efficiency and longer life.

[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] Among them, in the anthracene compound represented by formula BH-A, R 1 , R 2 Each is independently selected from any one of -H, substituted or unsubstituted C6-C40 aryl, and substituted or unsubstituted C12-C20 heteroaryl; R 1 , R 2 The substituents are each independently selected from at least one of -D, -F, -CN, C1-C10 alkyl, C1-C6 alkoxy or C6-C15 aryl;

[0009] The hydrogen atoms in the anthracene compound represented by the formula BH-A can be independently substituted by at least one of -D, -F, -CN, C1-C6 alkoxy or C6-C15 aryl.

[0010] As a preferred embodiment, in the anthracene compound represented by formula BH-A, R 1 , R 2 Each is independently selected from any one of a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C12-C20 heteroaryl group.

[0011] As a preferred embodiment, the C6 to C40 aromatic group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrene, perylenyl, spirofluorenyl, triphenylene, fluoranthene, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl or benzonaphthofluorenyl.

[0012] As a preferred embodiment, the C12-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl or dinaphthothiophenyl.

[0013] As a preferred embodiment, the anthracene compound is selected from any one of the following compounds:

[0014]

[0015]

[0016]

[0017]

[0018] As a preferred embodiment, the anthracene compound represented by formula BH-A is selected from any one of the following compounds:

[0019]

[0020] It should be noted that there is no special limitation on the preparation method of anthracene compounds in the present invention, and any commonly used preparation methods in the art are applicable.

[0021] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode and an organic thin film layer disposed between the anode and the cathode;

[0022] The material of the organic thin film layer includes the anthracene compound as described in the first aspect.

[0023] As a preferred embodiment, the organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes the anthracene compound as described in the first aspect.

[0024] In a third aspect, the present invention provides a display device, comprising the organic electroluminescent device as described in the second aspect.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] In the present invention, an anthracene compound with excellent performance is prepared by designing the structure of the anthracene compound and controlling the hydrogen atoms on the anthracene compound to be replaced by specific substituents. The anthracene compound is used as the light-emitting layer material of the organic electroluminescent device, and the prepared organic electroluminescent device has a lower driving voltage, a higher current efficiency and a longer life. DETAILED DESCRIPTION

[0027] 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.

[0028] Intermediate Preparation Example 1 Synthesis of Intermediate Z-1

[0029] This intermediate preparation example provides a method for synthesizing intermediate Z-1, and the specific steps are as follows:

[0030]

[0031] (1) Synthesis of intermediate Z-1-1

[0032] Under nitrogen protection, 200 mL of THF and 80 mL of water were added in sequence to a 500 mL three-necked flask, and then the intermediate 9-bromoanthracene (60.0 mmol), phenylboric acid (66.0 mmol), potassium carbonate (90.0 mmol) and tetrakistriphenylphosphine palladium (0.6 mmol) were added, and the temperature was slowly raised to reflux for reaction for 12 h. The temperature was lowered to room temperature, and water was added to separate the mixture. The aqueous phase was extracted once with toluene, and the organic phases were combined. The organic phases were washed with water and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed under reduced pressure. The mixture was separated by silica gel column chromatography and eluted with petroleum ether to obtain the intermediate Z-1-1.

[0033] The intermediate Z-1-1 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 254.11.

[0034] (2) Synthesis of intermediate Z-1-2

[0035] Under nitrogen protection, 300 mL of DMF was added to a 500 mL three-necked flask in sequence, and then intermediate Z-1-1 (70.0 mmol) and NBS (105.0 mmol) were added, and the temperature was controlled at 25 ° C for 6 hours. After the reaction was completed, 800 ml of water was added to a 2L beaker, and the reaction solution was slowly added to the beaker, stirred for 30 minutes, filtered, and the filter cake was recrystallized with a mixed solvent of toluene and ethanol to obtain intermediate Z-1-2.

[0036] The intermediate Z-1-2 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 332.02.

[0037] (3) Synthesis of intermediate Z-1

[0038] Under nitrogen protection, 200 mL of THF and 80 mL of water were added to a 500 mL three-necked flask in sequence, and then intermediate Z-1-2 (60.0 mmol), terephthaloylboronic acid (66.0 mmol), potassium carbonate (90.0 mmol) and tetrakistriphenylphosphine palladium (0.6 mmol) were added, and the temperature was slowly raised to reflux for reaction for 12 h. After the reaction was completed, the temperature was lowered to room temperature, and water and ethyl acetate were added for separation. The aqueous phase was extracted once with ethyl acetate, and the organic phases were combined. The organic phases were washed with water and dried over magnesium sulfate. After the magnesium sulfate was removed by filtration, the solvent was removed under reduced pressure, and the mixture was separated by silica gel column chromatography, and petroleum ether: ethyl acetate = 10:3 (volume ratio) was used as the eluent to obtain intermediate Z-1.

[0039] Intermediate Preparation Examples 2 to 12 Synthesis of Intermediates Z-2 to Z-12

[0040] Intermediates Z-2 to Z-12 are synthesized by referring to the synthesis method of intermediate Z-1, except that phenylboric acid and terephthalenediboric acid are replaced by other boronic acid compounds (see Table 1 for details) in equal amounts. Other conditions are the same as those of the synthesis method of intermediate Z-1. The structures of boronic acid compounds and prepared intermediates are detailed in Table 1 below.

[0041] Table 1 Boric acid compounds of intermediates Z-2 to Z-12 and structures of prepared intermediates

[0042]

[0043]

[0044]

[0045] Intermediate Preparation Example 13 Synthesis of Intermediate H-1

[0046]

[0047] This intermediate preparation example provides a method for synthesizing intermediate H-1, which specifically includes the following steps:

[0048] (1) Synthesis of intermediate H-1-1

[0049] Under nitrogen protection, 200 mL of THF and 80 mL of water were added to a 500 mL three-necked flask in sequence, and then 3-bromonaphtho[1,2-b]furan (60.0 mmol), phenylboric acid (66.0 mmol), potassium carbonate (90.0 mmol) and tetrakistriphenylphosphine palladium (0.6 mmol) were added, and the temperature was slowly raised to reflux for reaction for 12 h. After the reaction was completed, the temperature was lowered to room temperature, and water was added to separate the mixture. The aqueous phase was extracted once with toluene, and the organic phases were combined. The organic phases were washed with water, dried over magnesium sulfate, filtered to remove the magnesium sulfate, and the solvent was removed under reduced pressure. The mixture was separated by silica gel column chromatography and eluted with petroleum ether to obtain intermediate H-1-1.

[0050] The intermediate H-1-1 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 244.09.

[0051] (2) Synthesis of intermediate H-1

[0052] Under nitrogen protection, 300 mL of DMF was added to a 500 mL three-necked flask in sequence, and then the intermediate H-1-1 (70.0 mmol) and NBS (105.0 mmol) were added. The temperature was controlled at 25 °C for 6 h. After the reaction was completed, 800 ml of water was added to a 2 L beaker, and the reaction solution was slowly added to the beaker. The mixture was stirred for 30 min and filtered. The filter cake was recrystallized with a mixed solvent of toluene and ethanol to obtain the intermediate H-1.

[0053] The intermediate H-1 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 322.00.

[0054] The intermediate H-1 was subjected to nuclear magnetic resonance detection: 1H-NMR (Bruker, Switzerland, AvanceⅡ400MHz nuclear magnetic resonance spectrometer, CDCl3), δ7.90~7.83 (m, 2H), δ7.63 (d, 1H), 7.54~7.33 (m, 7H), δ7.20 (m, 1H).

[0055] Intermediate Preparation Examples 14 to 19 Synthesis of Intermediates H-2 to H-7

[0056] The synthesis method of intermediates H-2 to H-7 refers to the synthesis method of intermediate H-1, with the only difference that phenylboronic acid is replaced by other boronic acid compounds of the same amount (see Table 2 for details). Other conditions are the same as the synthesis method of intermediate H-1. The intermediates are subjected to mass spectrometry detection, and the test data are detailed in Table 2 below.

[0057] Table 2 Boric acid compounds of intermediates H-2 to H-7 and structures of prepared intermediates

[0058]

[0059] Synthesis Example 1

[0060] This synthesis example provides a method for synthesizing compound 1, and the specific steps are as follows:

[0061]

[0062] Under nitrogen protection, 150 mL of toluene, 75 mL of water and 75 mL of ethanol were added in sequence to a 500 mL three-necked flask, and then intermediate H-1 (60.0 mmol), intermediate Z-1 (66.0 mmol), potassium carbonate (90.0 mmol) and dichloro, di-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (0.03 mmol) were added, and the temperature was slowly raised to reflux for 6 h. After the reaction was completed, the temperature was lowered to room temperature, 200 ml of ethanol was added, stirred for 30 min, filtered, the filter cake was washed twice with water and once with ethanol, and then recrystallized with a mixed solvent of toluene and ethanol to obtain compound 1.

[0063] Compound 1 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 572.21.

[0064] Synthesis Examples 2 to 16

[0065] Synthesis Examples 2 to 16 provide compounds 2 to 16 respectively, and their synthesis methods refer to the synthesis method of compound 1, with the only difference that intermediate H-1 and intermediate Z-1 are replaced by other intermediates of equal amount (see Table 3 for details), and other conditions are the same as the synthesis method of compound 1. The synthesized compounds are subjected to mass spectrometry detection, and the test data are detailed in Table 3.

[0066] Table 3 Structures of intermediates and synthesized compounds in Synthetic Examples 2 to 16

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] 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.

[0073] The specific structures of some substances used in the following application examples and application comparative examples are as follows:

[0074]

[0075] Application Example 1

[0076] This application example provides an organic electroluminescent device, using Compound 1 provided in Synthesis Example 1 of the present invention as the host material of the light-emitting layer;

[0077] The structure of the organic electroluminescent device is: ITO / HT(40nm) / Host material of the light-emitting layer: BD-23%(30nm) / TPBI(30nm) / LiF(0.5nm) / Al(150nm).

[0078] The preparation method of the above organic electroluminescent device is as follows:

[0079] The glass substrate coated with the ITO transparent conductive layer (as the anode) is ultrasonically treated in a cleaning agent, then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, baked in a clean environment until completely dehydrated, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface to improve the surface properties and enhance the bonding ability with the hole layer.

[0080] Place the materials in a vacuum chamber, evacuate to 1×10 -5 ~1×10 -6 Pa, and vacuum-evaporate them onto the cleaned ITO substrate in sequence. Among them, the host material of the light-emitting layer: BD-23%(30nm) means that in the device, the host material of the light-emitting layer and BD-2 are co-evaporated at a volume ratio of 97:3 to form the light-emitting layer, and the thickness of the light-emitting layer is 30nm.

[0081] Application Examples 2 to 12

[0082] Application Examples 2 to 12 respectively provide an organic electroluminescent device. The difference from Application Example 1 is only that the host material of the light-emitting layer is different (see Table 4 for details), and other conditions are the same as those in Application Example 1.

[0083] Application Comparative Examples 1 to 3

[0084] Application Comparative Examples 1 to 3 respectively provide an organic electroluminescent device. The difference from Application Example 1 is only that the host material of the light-emitting layer is different (see Table 4 for details), and other conditions are the same as those in Application Example 1.

[0085] Performance Test

[0086] 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 of the organic electroluminescent device performance test results are shown in Table 4.

[0087] Table 4 Test results of main materials and device performance of light-emitting layers in application examples 1 to 12 and comparative examples 1 to 3

[0088]

[0089]

[0090] As can be seen from Table 4, 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.

[0091] 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: Wherein, in the anthracene compound represented by formula BH-A, R1 and R2 are independently selected from any one of -H, substituted or unsubstituted C6-C40 aryl, and substituted or unsubstituted C12-C20 heteroaryl; The substituents in R1 and R2 are each independently selected from at least one of -D, -F, -CN, C1-C10 alkyl, C1-C6 alkoxy, and C6-C15 aryl; In the anthracene compound represented by formula BH-A, each hydrogen atom is independently substituted by at least one of -D, -F, -CN, C1-C6 alkoxy or C6-C15 aryl.

2. The anthracene compound according to claim 1, characterized in that In the anthracene compound represented by formula BH-A, R1 and R2 are each independently selected from any one of a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C12-C20 heteroaryl group.

3. The anthracene compound according to claim 1, characterized in that The C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrene, perylenyl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl or benzonaphthofluorenyl.

4. The anthracene compound according to claim 1, characterized in that The C12-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl or dinaphthothiophenyl.

5. The anthracene compound according to claim 1, characterized in that The anthracene compound is selected from any one of the following compounds:

6. 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 comprises the anthracene compound according to any one of claims 1 to 5.

7. The organic electroluminescent device according to claim 6, characterized in that: The organic thin film layer comprises a light-emitting layer, and the material of the light-emitting layer comprises the anthracene compound according to any one of claims 1 to 5.

8. A display device, characterized in that: The display device comprises the organic electroluminescent device according to claim 6 or 7.

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