An anthracene compound containing naphthyl substitution

Abstract

This invention provides an anthracene compound containing a naphthyl substituted group. The naphthyl-substituted anthracene compound has the structure shown in Formula I. The naphthyl-substituted anthracene compound provided by this invention can be used as the main material for the light-emitting layer of an OLED light-emitting device, enabling the OLED light-emitting device to have a lower driving voltage, higher current efficiency, and longer lifetime.

Description

[0001] This application claims preference to patent application number 2023101782749 (the earlier application was filed on February 28, 2023, and is entitled "A Compound"). Technical Field

[0002] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to an anthracene compound containing naphthyl substitution. Background Technology

[0003] 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.

[0004] 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.

[0005] 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, it is necessary to improve the efficiency of these devices. One crucial factor limiting this is the performance of the organic light-emitting materials used in OLEDs. Thus, it is essential to develop stable and efficient organic light-emitting materials to improve the current efficiency and lifespan of OLED devices. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide an anthracene compound containing naphthyl substitution. The anthracene compound containing naphthyl substitution provided by the present invention can be used as the main material for the light-emitting layer of OLED light-emitting devices, enabling the OLED light-emitting devices to have lower driving voltage, higher current efficiency, and longer lifespan.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides an anthracene compound containing a naphthyl substituted group, said anthracene compound having the structure shown in Formula I:

[0009]

[0010] Ar 11 Ar 12 Ar 13 Ar and Ar are each independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C12-C20 heteroaryl; and Ar 11 Ar is not hydrogen; it is neither hydrogen nor deuterium.

[0011] X is selected from O or S;

[0012] m is selected from 0 or 1;

[0013] The phenyl group represented by ring A or ring B can each be independently replaced with a naphthyl group;

[0014] Ar 11 Ar 12 Ar 13 The substituents described in Ar are each independently selected from at least one of -D (deuterium atom), C1-C10 alkyl, C1-C6 alkoxy or C6-C15 aryl;

[0015] In the compound shown in Formula I, the hydrogen atoms can be independently substituted by at least one of -D (deuterium atom), -F, -CN, C1-C10 alkyl, C1-C6 alkoxy or C6-C15 aryl;

[0016] The hydrogen atoms in the compound may be independently substituted by at least one of -D, -F, -CN, C1-C10 alkyl (e.g., methyl, ethyl, propyl, tert-butyl, cyclopentyl, tert-butyl, adamantyl, etc.), C1-C6 alkoxy (e.g., methoxy, ethoxy, propoxy, hexoxy, etc.), or C6-C15 aryl (e.g., phenyl, naphthyl, fluorenyl, etc.).

[0017] In this invention, D represents a deuterium atom, and the same applies below.

[0018] It should be noted that if m is 1, then Ar represents a disubstituted group, that is, Ar is selected from any one of substituted or unsubstituted C6-C40 arylene groups or substituted or unsubstituted C12-C20 heteroarylene groups.

[0019] It should be noted that when ring A or ring B is selected from naphthyl groups, any C atom on the naphthyl group that can participate in bonding can participate in bonding. That is, when ring A is a naphthyl group, any C atom on the naphthyl group that can participate in bonding can bond with Ar. 12 Linkage; when ring B is naphthyl, any C atom on the naphthyl group that can participate in linkage can bond with Ar.13 Ar connection.

[0020] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0021] As a preferred embodiment of the present invention, the C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, naphthyl, pyrene, perylene, spirofluorenyl, triphenylene, fluoranyl, hydrogenated benzo[a]anthrayl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthyl, or benzo[a]naphthylfluorenyl.

[0022] Preferably, the C12-C20 heteroaryl group is selected from any one of dibenzofuran, dibenzothiophene, benzodibenzofuran, benzodibenzothiophene, dinaphthofuran, and dinaphthothiophene.

[0023] Preferably, Ar 11 Ar 12 Ar 13 Each group is independently selected from any one of the following groups that are substituted with no substitution: phenyl, diphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, fluorenyl;

[0024] The Ar 11 Ar 12 Ar 13 The substituents described herein are each independently selected from at least one of -D, methyl, ethyl, tert-butyl, adamantyl, hexoxy, methoxy, isopropoxy, phenyl, or naphthyl.

[0025] Preferably, Ar is selected from any one of the following groups that are substituted with unsubstituted groups: phenylene, diphenylene, naphthylene, dibenzofuranylene, dibenzothiopheneylene, benzodibenzofuranylene, fluoreneylene;

[0026] The substituents in Ar are selected from at least one of -D, methyl, ethyl, tert-butyl, adamantyl, hexoxy, methoxy, isopropoxy, phenyl, or naphthyl.

[0027] Preferably, each hydrogen atom in the compound represented by Formula I can be independently substituted by at least one of -D, methyl, ethyl, tert-butyl, adamantyl, hexoxy, methoxy, isopropoxy, phenyl, or naphthyl.

[0028] Preferably, the compound represented by Formula I includes the compound represented by Formula I-1:

[0029]

[0030] Among them, Ar 11 Ar 12 Ar 13 Rings X, A, and B have the same protection range as described above.

[0031] As a preferred embodiment of the present invention, the compound represented by Formula I is selected from any one of the following substituted or unsubstituted compounds:

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] The substitution refers to the partial or complete replacement of hydrogen atoms in the above-mentioned compound by deuterium atoms.

[0044] Preferably, the compound of formula I is selected from any one of the following compounds:

[0045]

[0046] In a second aspect, the present invention provides an intermediate comprising a compound of formula A:

[0047]

[0048] X1 is selected from F, Cl, Br, I, and Ar. 11 It has the same scope of protection as described above;

[0049] The compound of formula A does not include the following compounds:

[0050]

[0051] Preferably, the intermediate comprises any one of the following compounds:

[0052]

[0053] The intermediate is used to prepare anthracene compounds containing naphthyl substitution as described in the first aspect.

[0054] The general formula for synthesizing the compound of formula I includes the following steps:

[0055]

[0056] X1 and X2 are each independently selected from F, Cl, Br, and I;

[0057] Ar 11 Ar 12 Ar 13 Ar, X, m, ring A and ring B have the same protection range as described above.

[0058] 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 the compound as described in the first aspect.

[0059] Preferably, the organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes the compounds described in the first aspect.

[0060] In this invention, the light-emitting layer material further includes compounds having the structure shown in Formula II and / or compounds having the structure shown in Formula III:

[0061]

[0062] Among them, Ar 21 Ar 22 Each is independently selected from any one of substituted or unsubstituted C6-C20 (e.g., C6, C8, C10, C12, C16, or C20) aryl groups and substituted or unsubstituted C3-C20 (e.g., C3, C6, C8, C10, C12, C16, or C20) heteroaryl groups;

[0063] 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 or C12, etc.) straight-chain or branched alkyl groups, and C6-C12 (e.g., C6, C8, C10 or C12, etc.) cycloalkyl groups;

[0064] Ar21 Ar 22 The substituents described herein are each independently selected from C1 to C5 (e.g., methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, etc.) straight-chain or branched alkyl groups or C6 to C12 (e.g., phenyl, diphenyl, naphthyl, etc.) aryl groups;

[0065] Ar 31 Ar 32 Ar 33 and Ar 34 Each is independently selected from any one of substituted or unsubstituted C6-C22 (e.g., C6, C8, C10, C16, C18, or C22, etc.) aryl groups, or substituted or unsubstituted C12-C40 (e.g., C12, C18, C20, C24, C30, C36, or C40, etc.) heteroaryl groups;

[0066] R 31 Selected from any one of phenyl, naphthyl, or biphenyl;

[0067] a is selected from 0 or 1;

[0068] Ar 31 Ar 32 Ar 33 Ar 34 The substituents described herein are each independently selected from C1 to C5 straight-chain or branched alkyl groups (e.g., methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, etc.) or C6 to C12 aryl groups (e.g., C6, C8, C10, or C12, etc.).

[0069] As a preferred technical solution of the present invention, the Ar 21 Ar 22 Each independently selected Any one of them.

[0070] Preferably, the R 21 R 22 and R 23 Each is independently selected from any one of hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, or adamantyl.

[0071] Preferably, the Ar 31 Ar 32 Ar 33 and Ar 34 Each independently selected Any one or at least two of them.

[0072] As a preferred embodiment of the present invention, the compound having the structure shown in Formula II is selected from any one of the following compounds:

[0073]

[0074]

[0075] As a preferred embodiment of the present invention, the compound having the structure shown in Formula III is selected from any one of the following compounds:

[0076]

[0077]

[0078] Preferably, the organic thin film layer further includes a hole layer, which includes a hole transport layer, a hole injection layer, and an electron blocking layer.

[0079] As a preferred embodiment of the present invention, the material of the cavity layer includes a compound having the formula shown in Formula I.

[0080] Thirdly, the present invention provides a display device comprising the organic electroluminescent device as described in the third aspect.

[0081] Compared with the prior art, the present invention has the following beneficial effects:

[0082] This invention designs the structure of anthracene compounds containing naphthyl substitution and uses them as the main material of 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. Detailed Implementation

[0083] 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.

[0084] Preparation of intermediates

[0085] Synthesis of Intermediate 7-1 in Preparation Example 1

[0086] This preparation example provides intermediate 7-1 and its synthesis method, which is as follows:

[0087]

[0088] Under nitrogen protection, 80 mL of toluene, 30 mL of ethanol, and 15 mL of water were added sequentially to a 250 mL three-necked flask. Then, 3.0 g of 1,8-dibromonaphthalene, 2.0 g of biphenyl-3-boronic acid, 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 8 h. After cooling to room temperature, water was added to separate the organic layer. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and separated by silica gel column chromatography. The product was eluted with petroleum ether to obtain 3.1 g of intermediate 7-1.

[0089] The obtained intermediate 7-1 was subjected to mass spectrometry analysis, and the two peaks with the largest mass-to-charge ratio (m / z) were found to be 358.04 and 360.03.

[0090] Elemental analysis of the obtained intermediate 7-1 yielded the following results: theoretical values: C, 73.55%, H, 4.21%; actual measured values: C, 73.53%, H, 4.20%.

[0091] Preparation Examples 2-4

[0092] Referring to the synthesis method of intermediate 7-1 in Preparation Example 1, the following intermediates were synthesized by reacting the corresponding brominated derivatives and borate compounds. The mass spectra of the prepared intermediates were tested, and the structural formulas of the corresponding brominated derivatives and borate compounds, as well as the structural formulas and mass spectrometry data of the prepared intermediates, are detailed in Table 1 below.

[0093] Table 1

[0094]

[0095] Synthesis of intermediate 14-1 in Preparation Example 5

[0096] This preparation example provides intermediate 14-1 and its synthesis method, which is as follows:

[0097]

[0098] Under nitrogen protection, 100 mL of dioxane and 10 mL of water were added sequentially to a 250 mL three-necked flask. Then, 3.7 g of 4-(8-bromonaphthyl-1-yl)dibenzo[b,d]furan, 2.7 g of anthracene-9,10-diboronic acid, 2.12 g (0.02 mol) of sodium carbonate and 0.23 g (0.0002 mol) of tetraphenylphosphine palladium were added. The mixture was slowly heated to 70 °C and reacted for 18 h. After cooling to room temperature, toluene and water were added to dissolve the organic layer. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and separated by silica gel column chromatography. The mixture was first eluted with petroleum ether:ethyl acetate = 5:1 (v / v) and then with petroleum ether:ethyl acetate = 1:1 (v / v) to obtain 3.9 g of intermediate 14-1.

[0099] To identify the structure of intermediate 14-1, 0.5 g of intermediate 14-1 was taken, and 0.12 g of pinacol and 60 mL of petroleum ether were added. The mixture was refluxed for 4 hours, filtered, and cooled to precipitate crystals, which were identified as 14-2. Mass spectrometry analysis of 14-2 revealed a mass-to-charge ratio (m / z) of 596.25. The reaction equation is shown below:

[0100]

[0101] Synthesis of intermediate 15-1 in Preparation Example 6

[0102] This preparation example provides intermediate 15-1 and its synthesis method, which is as follows:

[0103]

[0104] The synthesis method of intermediate 15-1 is the same as that of intermediate 14-1, the difference being that... Replace with equal amounts of substance

[0105] Intermediate 15-1 was prepared into pinacol ester, and mass spectrometry analysis revealed a mass-to-charge ratio (m / z) of 596.25. The reaction equation is shown below:

[0106]

[0107] Synthesis of Compound 1 in Example 1

[0108] This synthetic example provides compound 1 and its synthetic method, which is as follows:

[0109]

[0110] Under nitrogen protection, 100 mL of toluene, 40 mL of ethanol, and 15 mL of water were added sequentially to a 250 mL three-necked flask. Then, 3.9 g of 10-(dibenzo[b,d]furan-4-yl)anthracene-9-boronic acid, 2.8 g of 1-bromo-8-phenylnaphthalene, 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 12 h. After cooling to room temperature, water was added to separate the organic layer. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and separated by silica gel column chromatography with petroleum ether:ethyl acetate = 10:0.5 (v / v) to give 5.0 g of compound 1.

[0111] The obtained compound 1 was subjected to mass spectrometry, and the mass-to-charge ratio (m / z) was measured to be 546.20.

[0112] Synthesis Examples 2-18

[0113] Referring to the synthesis of compound 1 in Example 1, the following compounds were synthesized by reacting the corresponding brominated derivatives and borate compounds, and the mass spectra of the prepared compounds were measured. The structural formulas of the corresponding brominated derivatives and borate compounds, as well as the structural formulas and mass spectrometry data of the prepared compounds, are detailed in Table 2 below.

[0114] Table 2

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] 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.

[0121] The specific structures of the compounds used in the following application examples and comparative application examples are shown below:

[0122]

[0123] Application Example 1

[0124] This application example provides an organic electroluminescent device with the following structure: ITO / HTL:HI-2(5%) (20nm) / HTL(50nm) / BH:BD-1(5%) (30nm) / TPBI(30nm) / Al(150nm);

[0125] The fabrication method of the above-mentioned organic electroluminescent device is as follows:

[0126] 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. Here, HTL:HI-2 (5%) (20nm) refers to the co-evaporation of HTL and HI-2 at a volume ratio of 95:5 to form a hole injection layer with a thickness of 20nm. BH:BD-1 (5%) (30nm) refers to the co-evaporation of BH and BD-1 at a volume ratio of 95:5 to form a light-emitting layer with a thickness of 30nm.

[0127] BH is the main material for blue light emission. In this application example, BH is compound 1.

[0128] In the device provided in this application example, HTL:HI-2(5%) (20nm) is the hole injection layer, and HTL(50nm) is the hole transport layer.

[0129] Application Example 2-13

[0130] Application Examples 2-13 each provide an organic electroluminescent device, which differs from Application Example 1 only in that the BH material is different (the specific composition is described in Table 3 below), while the other preparation steps are the same as in Application Example 1.

[0131] Compare and contrast examples 1-4

[0132] Comparative Application Examples 1-4 provide an organic electroluminescent device, which differs from Application Example 1 only in the BH material (details are shown in Table 3 below), while the other preparation steps are the same as in Application Example 1.

[0133] Performance testing

[0134] Test Method: The OLED-1000 multi-channel accelerated aging lifetime and photoluminescence performance analysis system manufactured by Hangzhou Yuanfang was used for testing. The test items included 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. The drive voltage, current efficiency, and LT80 are all relative values.

[0135] The specific test results are shown in Table 3 below:

[0136] Table 3

[0137]

[0138] As shown in Table 3, the present invention designs the structure of the compound to contain 1,8-disubstituted naphthalene, which increases the molecular strain of the compound and reduces the intermolecular interaction forces. This allows the compound to be used as the main material, and its energy can be better transferred to the dye (BD-1), thereby improving device efficiency and lifespan.

[0139] Comparing Application Examples 10 and 11, it can be seen that when the general formula of the compound conforms to Formula 1-1, the compound contains two 1,8-disubstituted naphthalene structural units, which further increases the molecular strain of the compound, reduces the intermolecular interaction forces, and allows the energy of the compound to be better transferred to the dye (BD-1) when used as the host material, thus further improving the device efficiency and lifetime.

[0140] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. An anthracene compound containing a naphthyl-substituted group, characterized in that, The anthracene compounds containing naphthyl substitution are selected from the following compounds: 、 、 、 。 2. 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 an anthracene compound containing naphthyl substituted compounds as described in claim 1.

3. The organic electroluminescent device according to claim 2, characterized in that, The organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes anthracene compounds containing naphthyl substituted compounds as described in claim 1.

4. The organic electroluminescent device according to claim 3, characterized in that, The light-emitting layer material also includes .

5. A display device, characterized in that, The display device includes an organic electroluminescent device as described in any one of claims 2-4.

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