An anthracene compound containing a diphenyl pentaheterocyclic ring substituent, an intermediate and an organic electroluminescent device

Abstract

The application provides an anthracene compound containing a diphenyl pentaheterocyclic substituent, an intermediate and an organic electroluminescent device. The anthracene compound containing the diphenyl pentaheterocyclic substituent has a structure of formula I. The anthracene compound containing the diphenyl pentaheterocyclic substituent provided by the application can be used as a main body material of an OLED light-emitting layer, so that the OLED light-emitting device has a lower driving voltage, a higher current efficiency and a longer service life.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to an anthracene compound containing a dibenzo-p-5 heterocyclic substituent, 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, 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

[0005] To address the shortcomings of existing technologies, the present invention aims to provide anthracene compounds containing dibenzo5-membered heterocyclic substituents. This invention designs the specific structure of anthracene compounds containing dibenzo5-membered heterocyclic substituents to make them the main material for the light-emitting layer of OLED devices, thereby enabling OLED devices to exhibit lower driving voltage, higher current efficiency, and longer lifespan.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides an anthracene compound containing a dibenzo-5-membered heterocyclic substituent, wherein the anthracene compound containing the dibenzo-5-membered heterocyclic substituent has the structure shown in Formula I:

[0008]

[0009] Ar1 is selected from any one of substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C12-C20 heteroaryl groups;

[0010] R4 to R7 are each independently selected from any one of hydrogen atom, deuterium atom, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C12-C20 heteroaryl;

[0011] X is selected from O or S;

[0012] A is selected from any one of substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C12-C20 heteroaryl groups;

[0013] Either B or C is selected from a hydrogen atom or a deuterium atom, and the other is independently selected from any one of substituted or unsubstituted C6-C40 aryl or substituted or unsubstituted C12-C20 heteroaryl.

[0014] The substituents described in R4 to R7, A, B, and C are each independently selected from at least one of -D (deuterium atom), C1-C10 alkyl, C1-C6 alkoxy, or C6-C15 aryl.

[0015] This invention designs the specific structure of anthracene compounds containing dibenzo5-membered heterocyclic substituents to make them 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.

[0016] In this invention, D represents a deuterium atom, and the same applies below.

[0017] In this invention, C6-C40 can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0018] C12-C20 can be C12, C13, C14, C15, C16, C17, C18, C19 or C20.

[0019] C1-C10 can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.

[0020] C6-C15 can be C6, C8, C10, C12, or C15, etc.

[0021] C1-C6 can be C1, C2, C3, C4, C5, or C6.

[0022] 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.

[0023] 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]naphthyl.

[0024] Preferably, the C12-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl.

[0025] Preferably, the C1-C10 alkyl group is selected from any one of methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, octyl, and adamantyl.

[0026] Preferably, the C1-C6 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy.

[0027] Preferably, the C6-C15 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracene, phenanthryl, or fluorenyl.

[0028] As a preferred embodiment of the present invention, the Ar1 is selected from any one of the following groups, whether substituted or unsubstituted: phenyl, biphenyl, naphthyl, dibenzofuranyl or dibenzothiopheneyl;

[0029] The substituent is selected from at least one of phenyl, biphenyl, or naphthyl.

[0030] Preferably, the Ar1 is selected from naphthyl groups.

[0031] Preferably, R4, R5, R6, and R7 are each independently selected from any one of hydrogen atom, deuterium atom, phenyl, biphenyl, or naphthyl, and more preferably hydrogen atom or deuterium atom.

[0032] As a preferred embodiment of the present invention, A and B are each independently selected from any one of substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C12-C20 heteroaryl groups.

[0033] Preferably, A and B represent the same substituent.

[0034] Preferably, A and B represent different substituents.

[0035] Preferably, A and C are each independently selected from any one of substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C12-C20 heteroaryl groups.

[0036] Preferably, A and C represent the same substituent.

[0037] Preferably, A and C represent different substituents.

[0038] As a preferred embodiment of the present invention, C is selected from hydrogen atoms or deuterium atoms, and A and B are each independently selected from substituted or unsubstituted C6-C40 aryl groups.

[0039] Preferably, C is selected from hydrogen or deuterium, and A and B are each independently selected from any one of phenyl, biphenyl, or naphthyl.

[0040] As a preferred embodiment of the present invention, B is selected from hydrogen atoms or deuterium atoms, and A and C are each independently selected from substituted or unsubstituted C6-C40 aryl groups.

[0041] Preferably, B is selected from hydrogen atoms or deuterium atoms, and A and C are each independently selected from any one of phenyl, biphenyl, or naphthyl.

[0042] As a preferred embodiment of the present invention, the compound of Formula I is selected from any one of the following substituted or unsubstituted compounds:

[0043]

[0044]

[0045] The substitution refers to the fact that each hydrogen atom in the above compound can be independently replaced by a deuterium atom.

[0046] Preferably, the compound of formula I is selected from any one of the following compounds:

[0047]

[0048] In a second aspect, the present invention provides an intermediate comprising a compound having the structure shown in the following formula:

[0049]

[0050] Among them, X, A, B, and C have the same definitions as above;

[0051] X1 is selected from any one of H, F, Cl, Br or I;

[0052] The intermediate is used to prepare anthracene compounds containing dibenzo5-membered heterocyclic substituents as described in the first aspect.

[0053] Preferably, the intermediate is selected from the following compounds:

[0054]

[0055] 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 an anthracene compound containing a dibenzo5-membered heterocyclic substituent as described in the first aspect.

[0056] Preferably, the organic thin film layer includes a light-emitting layer, the material of which includes anthracene compounds containing dibenzo-p-5-membered heterocyclic substituents as described in the first aspect.

[0057] 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:

[0058]

[0059] 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, etc.) aryl, substituted or unsubstituted C3-C20 (e.g., C3, C6, C8, C10, C12, C16, or C20, etc.) heteroaryl;

[0060] R 21 R 22 and R 23 Each is independently selected from 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;

[0061] Ar 21 Ar 22 The substituents described herein are each independently selected from C1-C5 (e.g., methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, etc.) straight-chain or branched alkyl groups or C6-C12 (e.g., phenyl, diphenyl, naphthyl, etc.) aryl groups;

[0062] Ar 31 Ar 32 Ar 33 and Ar 34Each is independently selected from any one of substituted or unsubstituted C6-C22 (e.g., C6, C8, C10, C16, C18, or C22, etc.) aryl, substituted or unsubstituted C12-C40 (e.g., C12, C18, C20, C24, C30, C36, or C40, etc.) heteroaryl;

[0063] R 31 Selected from any one of phenyl, naphthyl, or biphenyl;

[0064] a is selected from 0 or 1;

[0065] Ar 31 Ar 32 Ar 33 Ar 34 The substituents described herein are each independently selected from C1-C5 straight-chain or branched alkyl groups (e.g., methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, etc.) or C6-C12 (e.g., C6, C8, C10, or C12, etc.) aryl groups.

[0066] As a preferred technical solution of the present invention, the Ar 21 Ar 22 Each independently selected

[0067] Any of the following, short bonds represent connection sites.

[0068] 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.

[0069] Preferably, the Ar 31 Ar 32 Ar 33 and Ar 34 Each independently selected Any one or at least two of them, short bonds represent connection sites.

[0070] As a preferred embodiment of the present invention, the compound of formula II is selected from any one of the following compounds:

[0071]

[0072]

[0073] As a preferred embodiment of the present invention, the compound of formula III is selected from any one of the following compounds:

[0074]

[0075]

[0076] 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.

[0077] As a preferred embodiment of the present invention, the material of the hole layer includes anthracene compounds containing dibenzo-p-5-membered heterocyclic substituents as described in the first aspect.

[0078] Fourthly, the present invention provides a display device comprising the organic electroluminescent device as described in the third aspect.

[0079] Compared with the prior art, the present invention has the following beneficial effects:

[0080] This invention designs the structure of anthracene compounds containing dibenzo5-membered heterocyclic substituents and uses these anthracene compounds 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

[0081] 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.

[0082] Preparation Example 1

[0083] This preparation example provides intermediate P1-1 and its synthesis method, which is as follows:

[0084]

[0085] (1) Synthesis of intermediate P1-2

[0086] To a three-necked flask, add 3.2 g of the compound shown in P1-0, 30 mL of acetonitrile, and 20 mL of DMF. Add 2.5 g of elemental iodine in portions at 25 °C. After the addition is complete, react at 25 °C for 4 hours, then at 40 °C for 4 hours, and then at 80 °C for 2 hours. Add water, filter to obtain a solid, dry the solid, separate by silica gel column chromatography, and elute with petroleum ether to obtain 0.6 g of intermediate P1-2.

[0087] The obtained intermediate P1-2 was subjected to mass spectrometry, and the mass-to-charge ratio (m / z) was measured to be 447.90.

[0088] The obtained intermediate P1-2 was characterized by NMR data, as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.17 (s, 1H), δ8.02 (m, 1H), δ7.55~7.39 (m, 7H), δ7.29 (m, 1H).

[0089] (2) Synthesis of intermediate P1-1

[0090] Under nitrogen protection, 80 mL of toluene, 30 mL of ethanol, and 15 mL of water were added sequentially to a three-necked flask. Then, 4.5 g of intermediate P1-2, 1.2 g of phenylboronic 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 40 °C and reacted for 2 hours, then heated to 60 °C and reacted for 4 hours. The mixture was cooled to room temperature, and water was 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, eluting with petroleum ether to obtain 2.1 g of intermediate P1-1.

[0091] The obtained intermediate P1-1 was subjected to mass spectrometry analysis, and the mass-to-charge ratio (m / z) was measured to be 398.03.

[0092] Preparation Example 2

[0093] This preparation example provides intermediate P6-1 and its synthesis method, which is as follows:

[0094]

[0095] (1) Synthesis of intermediate P6-2

[0096] Following the synthesis of intermediate P1-2, intermediate P6-2 was prepared.

[0097] The obtained intermediate P6-2 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 447.90.

[0098] The obtained intermediate P6-2 was characterized by NMR data, as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.10 (s, 1H), δ8.03 (m, 1H), δ7.55~7.39 (m, 7H), δ7.29 (m, 1H).

[0099] (2) Synthesis of intermediate P6-1

[0100] Following the synthesis of intermediate P1-1, intermediate P6-1 was prepared.

[0101] The obtained intermediate P6-1 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 398.03.

[0102] Preparation Examples 3-5

[0103] Preparation Examples 3-5 provide an intermediate and its synthesis method, respectively. The synthesis method of the intermediate is the same as that of intermediate P1-1 provided in Preparation Example 1. The intermediate is synthesized by reacting the corresponding iodide and borate compound, and the mass spectrometry of the prepared intermediate is tested. The structural formulas of the corresponding iodide and borate compound, as well as the structural formula and mass spectrometry data of the prepared intermediate are detailed in Table 1 below.

[0104] Table 1

[0105]

[0106] Synthesis Example 1

[0107] This synthetic example provides compound P1 and its synthetic method, which is as follows:

[0108]

[0109] Under nitrogen protection, 50 mL of toluene, 20 mL of ethanol, and 10 mL of water were added sequentially to a three-necked flask. Then, 4.0 g of intermediate P1-1, 3.0 g of 9-phenylanthracene-10-boric 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 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. Elution was performed with petroleum ether:ethyl acetate = 10:0.5 (v / v) to give 1.7 g of compound P1.

[0110] The obtained compound P1 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 572.21.

[0111] Synthesis Examples 2-8

[0112] Synthetic Examples 2-8 provide a compound and its synthetic method, respectively. The synthetic method of the compound is the same as that of compound P1 provided in Synthetic Example 1, using the corresponding brominated derivative and boric acid compound to synthesize the following compounds, and the mass spectra of the prepared compounds were tested. The structural formulas of the corresponding brominated derivative and boric acid compound, as well as the structural formula and mass spectrometry data of the prepared compound, are detailed in Table 2 below.

[0113] Table 2

[0114]

[0115]

[0116]

[0117] 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.

[0118] The specific structures of the compounds used in the following application examples and comparative application examples are shown below:

[0119]

[0120]

[0121] Application Example 1

[0122] This application example provides an organic electroluminescent device with the following structure: ITO / HTL:HI-2(5%) (20nm) / HTL(50nm) / BH:BD-3(5%) (30nm) / TPBI(30nm) / Al(150nm);

[0123] The fabrication method of the above-mentioned organic electroluminescent device is as follows:

[0124] 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-3 (5%) (30nm) refers to the co-evaporation of BH and BD-3 at a volume ratio of 95:5 to form a light-emitting layer with a thickness of 30nm.

[0125] BH is the main material for blue light emission. In this application example, BH is compound P1.

[0126] 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.

[0127] Application Example 2-13

[0128] Application Examples 2-13 provide an organic electroluminescent device, which differs from Application Example 1 only in that the BH material is different (as shown in Table 3 below), while the other preparation steps are the same as in Application Example 1.

[0129] Compare and contrast examples 1-4

[0130] Comparative Application Examples 1-4 provide an organic electroluminescent device, which differs from Application Example 1 only in the BH material (as shown in Table 3 below). The other preparation steps are the same as in Application Example 1.

[0131] Performance testing

[0132] 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. The drive voltage, current efficiency, and LT80 are all relative values.

[0133] The specific test results are shown in Table 3 below:

[0134] Table 3

[0135] Comparative Application Example 1 BH1 1000 1 1 1 Application Example 1 P1 1000 0.90 1.03 1.09 Application Example 2 P2 1000 0.95 1.04 1.19 Application Example 3 P3 1000 0.97 1.06 1.17 Application Example 4 P4 1000 0.97 1.12 1.13 Application Example 5 P5 1000 1.01 1.16 1.05 Application Example 6 P6 1000 0.89 0.98 0.90 Application Example 7 P7 1000 0.73 0.92 1.08 Application Example 8 P8 1000 0.70 0.91 1.31 Application Example 9 P9 1000 0.80 0.99 1.05 Application Example 10 P10 1000 0.51 0.93 1.00

[0136] As can be seen from the above, this invention designs the specific structure of anthracene compounds containing dibenzo-p-5-membered heterocyclic substituents to make them 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.

[0137] A comparison of Application Example 1 and Application Examples 2-3 shows that when the substituents represented by A and B in Compound I are the same (Application Example 1), the driving voltage of the prepared OLED device is lower; when the substituents represented by A and B in Compound I are different (Application Examples 2-3), the current efficiency and lifetime of the prepared OLED device are better.

[0138] A comparison of Application Examples 1-3 and 4-5 shows that when Ar1 in Formula I is selected as naphthyl, the current efficiency of the prepared OLED device is better.

[0139] A comparison of Application Examples 1-5 and Application Examples 6-10 shows that when A and B in Compound I are each independently selected from substituted or unsubstituted C6-C40 aryl groups, the OLED device prepared has good current efficiency. When A and C in Compound I are each independently selected from substituted or unsubstituted C6-C40 aryl groups, the driving voltage of the OLED prepared is lower.

[0140] As can be seen from Application Example 8, when compound P8 is used as the main material for blue light, the OLED devices prepared have better lifespan.

[0141] As can be seen from Application Example 10, when compound P10 is used as the main material for blue light, the resulting OLED device has a lower driving voltage.

[0142] In summary, this invention designs the specific structure of anthracene compounds containing dibenzo5-membered heterocyclic substituents to make them 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.

[0143] 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 dibenzo5-membered heterocyclic substituent, characterized in that, The anthracene compounds containing dibenzo-5-membered heterocyclic substituents 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; The organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes anthracene compounds containing dibenzo-p-5-membered heterocyclic substituents as described in claim 1.

3. The organic electroluminescent device according to claim 2, characterized in that, The light-emitting layer material also includes compounds having the following formula: 。

Images