Benzanthracene compound, intermediate and organic electroluminescent device

Abstract

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

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronic technology, specifically relating to a benzanthracene compound, an intermediate, and an organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are devices fabricated by depositing one or more layers of organic material between two metal electrodes via spin coating or vacuum evaporation. A classic three-layer OLED comprises a hole transport layer, an emissive layer, and an electron transport layer. Holes generated by the anode combine with electrons generated by the cathode via the electron transport layer in the emissive layer to form excitons, which then emit light. OLEDs can be tuned to emit various desired light colors by changing the material of the emissive layer.

[0003] Organic electroluminescent devices, as a novel display technology, possess unique advantages such as self-illumination, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, fast response speed, wide applicable temperature range, low driving voltage, the ability to manufacture flexible, bendable, and transparent display panels, and environmental friendliness. They can be applied to flat panel displays and next-generation lighting, and can also be used as backlights for LCDs.

[0004] Since their invention in the late 1980s, organic light-emitting diodes (OLEDs) have been used in various industries, such as as screens in cameras and mobile phones. However, current OLED devices suffer from low efficiency and short lifespan, limiting their wider application, especially in large-screen displays. Therefore, improving device efficiency is crucial. One significant limiting factor is the performance of the organic light-emitting materials used in OLEDs. Consequently, it is necessary to develop stable and efficient organic light-emitting materials to improve the current efficiency and lifespan of OLED devices. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a benzene-anthracene compound, an intermediate, and an organic electroluminescent device. The present invention designs the structure of the benzene-anthracene compound to make it suitable as the main material for the light-emitting layer of an OLED light-emitting device, resulting in an OLED light-emitting device with lower driving voltage, higher current efficiency, and longer lifespan.

[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a benzanthracene compound having the structure shown in Formula I:

[0007] Formula I; One of Ar1 and Ar2 is selected from substituted or unsubstituted biphenyl, and the other is selected from any one of substituted or unsubstituted dibenzofuran and substituted or unsubstituted dibenzothiophene. In Ar1 and Ar2, the substituents are each independently selected from -D, -F, cyano, C1~C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) alkyl, C1~C6 (e.g., C1, C2, C3, C4, C5, C6) alkoxy, and C6~C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, C40) aryl.

[0008] This invention designs the structure of benzene-anthracene compounds to make them suitable as the main material for the light-emitting layer of OLED light-emitting devices, thereby enabling OLED light-emitting devices to have lower driving voltage, higher current efficiency, and longer lifespan.

[0009] In this invention, D represents a deuterium atom, and the same applies below.

[0010] Preferably, each hydrogen atom in Formula I can be independently substituted by any one of -D, -F, cyano, C1~C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) alkyl, C1~C6 (e.g., C1, C2, C3, C4, C5, C6) alkoxy, C6~C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, C40) aryl.

[0011] Preferably, Ar1 is selected from substituted or unsubstituted biphenyl, and Ar2 is selected from substituted or unsubstituted dibenzofuranyl.

[0012] Preferably, the C1-C10 alkyl group is selected from any one of methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, octyl, and adamantyl.

[0013] Preferably, the C1-C6 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy.

[0014] Preferably, the C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, fluorenyl, benzo[a]fluorenyl, pyrene, perylene, spirofluorenyl, triphenylene, and fluoranyl.

[0015] Preferably, the benzanthracene compound is selected from any one of the following substituted or unsubstituted compounds:

[0016]

[0017]

[0018] The substitution refers to the fact that each hydrogen atom in the above compound can be independently replaced by a deuterium atom.

[0019] Preferably, the benzanthracene compound is selected from any one of the following compounds P1 to P10: , , , , , , , , , .

[0020] Secondly, the present invention provides an intermediate, the structural formula of which is shown in P1-1 or P6-1 as follows: , ; The intermediate is used to prepare benzene-anthracene compounds as described in the first aspect.

[0021] Thirdly, 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, the organic thin film layer comprising a benzene-anthracene compound as described in the first aspect.

[0022] Preferably, the organic thin film layer includes a light-emitting layer, which includes a host material and a dopant material, wherein the host material includes the aforementioned benzene-anthracene compound.

[0023] Preferably, the doped material comprises a compound represented by Formula II and / or a compound represented by Formula III:

[0024] Formula II

[0025] Formula III In Formula II, the Ar 21 Ar 22Each is independently selected from any one of substituted or unsubstituted C6~C20 (e.g., C6, C8, C10, C12, C16, C20) aryl or substituted or unsubstituted C3~C20 (e.g., C3, C6, C8, C10, C12, C16, C20) heteroaryl; R 21 R 22 and R 23 Each is independently selected from any one of hydrogen, C1~C12 (e.g., C1, C2, C4, C6, C8, C10, C12) straight-chain or branched alkyl groups, and C6~C12 (e.g., C6, C8, C10, C12) cycloalkyl groups; Ar 21 Ar 22 In this context, each of the substituents is independently selected from C1-C5 straight-chain or branched alkyl groups (e.g., methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl) or C6-C12 aryl groups (e.g., phenyl, biphenyl, naphthyl). In Formula III, Ar 31 Ar 32 Ar 33 Ar 34 Each is independently selected from any one of substituted or unsubstituted C6~C22 (e.g., C6, C8, C10, C16, C18, C22) aryl groups and substituted or unsubstituted C12~C40 (e.g., C12, C18, C20, C24, C30, C36, C40) heteroaryl groups; R 31 Selected from any one of phenyl, naphthyl, or biphenyl; a is selected from 0 or 1; Ar 31 Ar 32 Ar 33 Ar 34 In this context, each of the substituents is independently selected from C1-C5 straight-chain or branched alkyl groups (e.g., methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl) or C6-C12 (e.g., C6, C8, C10, C12) aryl groups; Preferably, in formula II, the Ar 21 Ar 22 Each independently selected , , , , , , , , , , , , , , , , Any of the following, where a short bond represents a connection point; Preferably, in formula II, R 21 R 22 R 23 Each is independently selected from any one of hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, and adamantyl; Preferably, in formula III, Ar 31 Ar 32 Ar 33 and Ar 34 Each independently selected , , , , , , , , , Any one or at least two of the following, short bonds represent connection sites; Preferably, the compound represented by Formula II is selected from any one of the following compounds:

[0026]

[0027]

[0028]

[0029]

[0030] Preferably, the compound represented by Formula III is selected from any one of the following compounds:

[0031]

[0032]

[0033] Preferably, the organic thin film layer further includes a hole layer, which includes at least one of a hole transport layer, a hole injection layer, and an electron blocking layer.

[0034] Fourthly, the present invention provides a display device comprising the organic electroluminescent device as described in the third aspect.

[0035] Compared with the prior art, the present invention has the following beneficial effects: This invention designs the structure of benzene-anthracene compounds and uses them as the main material for the light-emitting layer of OLED devices, thereby enabling OLED devices to have lower driving voltage, higher current efficiency, and longer lifespan. Detailed Implementation

[0036] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0037] This preparation example provides intermediate P1-1 and its synthesis method, which is as follows:

[0038] Under nitrogen protection, 100 mL of toluene, 30 mL of ethanol, and 25 mL of water were added sequentially to a three-necked flask. Then, 3.5 g of intermediate M1, 2.1 g of intermediate M2, 2.12 g (0.02 mol) of sodium carbonate, and 0.23 g (0.0002 mol) of tetrakis(triphenylphosphine)palladium were added. The mixture was slowly heated to reflux and reacted for 7 h. After cooling to room temperature, water was added to dissolve the mixture. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and crystallized with toluene to obtain 2.7 g of intermediate P1-1.

[0039] The obtained intermediate P1-1 was subjected to mass spectrometry, and the mass-to-charge ratio (m / z) was measured to be 419.15.

[0040] This preparation example provides intermediate P6-1 and its synthesis method, which is as follows:

[0041] Following the preparation method of intermediate P1-1, intermediate P6-1 was prepared.

[0042] The obtained intermediate P6-1 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 428.10.

[0043] Synthesis Example 1 This synthetic example provides compound P1 and its synthetic method, which is as follows:

[0044] Under a nitrogen atmosphere, 130 mL of toluene was added to a three-necked flask, followed by 4.2 g of intermediate P1-1, 2.2 g of dibenzo[b,d]furan-2-boronic acid, 2.12 g of sodium carbonate, and 0.1 g of dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (CAS No. 887919-35-9). The mixture was slowly heated to reflux and reacted for 8 h. After cooling to room temperature, water was added to liquefy the mixture. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and crystallized three times with toluene to obtain compound P1 (2.0 g).

[0045] The obtained compound P1 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 551.23.

[0046] This synthetic example provides compound P6 and its synthetic method, which is as follows:

[0047] Compound P6 was prepared using the same method as compound P1.

[0048] The obtained compound P6 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 546.20.

[0049] Other compounds for which specific synthetic steps are not listed can be prepared using common knowledge in the field, combined with the above synthetic examples.

[0050] The specific structures of the compounds used in the following application examples and comparative application examples are shown below: , , , , , , , , , , , , , , , , , .

[0051] Application Example 1 This application example provides an organic electroluminescent device with the following structure: ITO / HTL (80nm) / BH:BD-2 (5%) (30nm) / ET-1 (30nm) / Al (150nm); The fabrication method of the above-mentioned organic electroluminescent device is as follows: Each layer of material was placed inside a vacuum chamber, and the vacuum was evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto the cleaned ITO substrate. BH:BD-2 (5%) (30nm) refers to the co-evaporation of BH and BD-2 at a volume ratio of 95:5 to form a light-emitting layer with a thickness of 30nm.

[0052] BH is the main material for blue light emission. In this application example, BH is compound P5.

[0053] In the device provided in this application example, HTL is the hole transport layer and ET-1 is the electron transport layer.

[0054] Application Examples 2-4 each provide an organic electroluminescent device, which differs from Application Example 1 only in that the BH material is different (as described in Table 1 below), while the other preparation steps are the same as in Application Example 1.

[0055] Comparative Application Examples 1 and 2 provide an organic electroluminescent device, which differs from Application Example 1 only in the BH material (as described in Table 1 below), while the other preparation steps are the same as in Application Example 1.

[0056] The test items include the brightness, driving voltage, current efficiency, and LT80 of the organic electroluminescent device; where LT80 refers to maintaining the device's initial brightness of 1000 cd / m². 2 With the current density remaining constant, the device efficiency drops to the initial luminance of 1000 cd / m². 2 The time required to achieve 80% of the corresponding efficiency. Among them, the drive voltage, current efficiency, and LT80 are all relative values ​​(based on Comparative Application Example 1).

[0057] The specific test results are shown in Table 1 below: Table 1

[0058] As can be seen from the above, this invention designs the structure of benzene-anthracene compounds and uses them as the main material of the light-emitting layer of OLED devices, thereby enabling OLED devices to have lower driving voltage, higher current efficiency and longer lifespan.

[0059] Application Examples 5 and 6 provide an organic electroluminescent device, which differs from Application Example 1 only in that the BH material is different (as described in Table 2 below), while the other preparation steps are the same as in Application Example 1.

[0060] Comparative Application Example 3 provides an organic electroluminescent device, which differs from Application Example 1 only in the BH material (as described in Table 2 below), while the other preparation steps are the same as in Application Example 1.

[0061] The test items include the brightness, driving voltage, current efficiency, and LT80 of the organic electroluminescent device; where LT80 refers to maintaining the device's initial brightness of 1000 cd / m². 2 With the current density remaining constant, the device efficiency drops to the initial luminance of 1000 cd / m². 2 The time required to achieve 80% of the corresponding efficiency. Among them, the drive voltage, current efficiency, and LT80 are all relative values ​​(based on comparative application example 3).

[0062] The specific test results are shown in Table 2 below: Table 2

[0063] Application Examples 7-10 each provide an organic electroluminescent device, which differs from Application Example 1 only in that the BH material is different (as described in Table 3 below), while the other preparation steps are the same as in Application Example 1.

[0064] The test items include the brightness, driving voltage, current efficiency, and LT80 of the organic electroluminescent device; where LT80 refers to maintaining the device's initial brightness of 1000 cd / m². 2 With the current density remaining constant, the device efficiency drops to the initial luminance of 1000 cd / m². 2 The time required to achieve 80% of the corresponding efficiency. Among them, the drive voltage, current efficiency, and LT80 are all relative values ​​(based on Application Example 7).

[0065] The specific test results are shown in Table 3 below: Table 3

[0066] In summary, this invention designs the structure of benzene-anthracene compounds and uses them as the main material for the light-emitting layer of OLED devices, resulting in OLED devices with lower driving voltage, higher current efficiency, and longer lifespan.

[0067] The present invention has been illustrated with the above embodiments to describe the detailed process flow of the present invention. However, the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the 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. A benzanthracene compound, characterized in that, The benzanthracene compounds have the structure shown in Formula I: Formula I; One of Ar1 and Ar2 is selected from substituted or unsubstituted biphenyl, and the other is selected from any one of substituted or unsubstituted dibenzofuran and substituted or unsubstituted dibenzothiophene. In Ar1 and Ar2, the substituents are each independently selected from any one of -D, -F, cyano, C1~C10 alkyl, C1~C6 alkoxy, and C6~C40 aryl.

2. The benzanthracene compound according to claim 1, characterized in that, Each hydrogen atom in Formula I can be independently substituted by any one of -D, -F, cyano, C1~C10 alkyl, C1~C6 alkoxy, or C6~C40 aryl.

3. The benzanthracene compound according to claim 1, characterized in that, Ar1 is selected from substituted or unsubstituted biphenyl, and Ar2 is selected from substituted or unsubstituted dibenzofuranyl.

4. The benzanthracene compound according to claim 1, characterized in that, The C1-C10 alkyl group is selected from any one of methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, octyl, and adamantyl. Preferably, the C1-C6 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy. Preferably, the C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, fluorenyl, benzo[a]fluorenyl, pyrene, perylene, spirofluorenyl, triphenylene, and fluoranyl.

5. The benzanthracene compound according to claim 1, characterized in that, The benzanthracene compounds are selected from any one of the following substituted or unsubstituted compounds: ； The substitution refers to the fact that each hydrogen atom in the above compound can be independently replaced by a deuterium atom.

6. The benzanthracene compound according to claim 1, characterized in that, The benzanthracene compound is selected from any one of the following compounds P1 to P10: 、 、 、 、 、 、 、 、 、 。 7. An intermediate, characterized in that, The structural formula of the intermediate is shown in P1-1 or P6-1 as follows: 、 ； The intermediate is used to prepare the benzene-anthracene compound as described in claim 1.

8. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode, wherein the organic thin film layer includes a benzene-anthracene compound as described in 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, which comprises a host material and a dopant material, wherein the host material includes the aforementioned benzene-anthracene compounds.

10. The organic electroluminescent device according to claim 9, characterized in that, The doped material includes compounds represented by Formula II and / or compounds represented by Formula III: Formula II Formula III In Formula II, the Ar 21 Ar 22 Each is independently selected from any one of substituted or unsubstituted C6-C20 aryl groups or substituted or unsubstituted C3-C20 heteroaryl groups; R 21 R 22 and R 23 Each is independently selected from any one of hydrogen, C1-C12 straight-chain or branched alkyl, and C6-C12 cycloalkyl; Ar 21 Ar 22 In this context, each of the substituents is independently selected from C1-C5 straight-chain or branched alkyl groups or C6-C12 aryl groups; In Formula III, Ar 31 Ar 32 Ar 33 Ar 34 Each is independently selected from any one of substituted or unsubstituted C6-C22 aryl groups or substituted or unsubstituted C12-C40 heteroaryl groups; R 31 Selected from any one of phenyl, naphthyl, or biphenyl; a is selected from 0 or 1; Ar 31 Ar 32 Ar 33 Ar 34 In this context, each of the substituents is independently selected from C1-C5 straight-chain or branched alkyl groups or C6-C12 aryl groups; Preferably, in formula II, the Ar 21 Ar 22 Each independently selected Preferably, in formula II, R 21 R 22 R 23 Each is independently selected from any one of hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, and adamantyl; Preferably, in formula III, Ar 31 Ar 32 Ar 33 and Ar 34 Each independently selected Preferably, the compound represented by Formula II is selected from any one of the following compounds: #imgpt45##imgpt46# #imgpt47# #imgpt48# #imgpt49#; Preferably, the compound represented by Formula III is selected from any one of the following compounds: #imgpt50##imgpt51# #imgpt52#.

Images