Anthryl compound with spiro-coupled boron-nitrogen multi-resonance skeleton, organic electroluminescent device, display screen and electronic equipment

Abstract

The invention discloses an anthryl compound of a spiro-coupled boron-nitrogen multi-resonance skeleton, an organic electroluminescent device, a display screen and electronic equipment, and relates to the technical field of organic electroluminescent materials. The anthryl compound provided by the invention has a structure as shown in a formula A. A boron-nitrogen heteromultiple resonance skeleton and an anthryl group are introduced into a spiro skeleton, and through the exciton characteristic of the anthracene group, a triplet state-triplet state up-conversion process is utilized, so that the exciton utilization rate of a light-emitting core is improved, triplet state exciton accumulation is reduced, and the service life of a blue light organic light-emitting device based on the anthryl compound is prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescent materials, in particular to an anthracene compound with a spiro-coupled boron-nitrogen hetero multiple resonance skeleton, an organic electroluminescent device, a display screen and an electronic device. BACKGROUND

[0002] In recent years, thermally activated delayed fluorescence (TADF) materials, especially multiple resonance TADF (MR-TADF) materials, have shown great potential due to their unique exciton regulation mechanism and all-organic characteristics. Traditional TADF materials usually use molecules with twisted donor-acceptor structures to achieve a small singlet-triplet energy level difference (ΔEST), promote reverse inter-system crossing (RISC), and thus achieve an efficient electroluminescent process. However, this twisted structure often leads to wide spectrum emission (half peak width greater than 70 nm) and large efficiency roll-off. In contrast, MR-TADF materials utilize the multiple resonance effect between atoms within a rigid skeleton, which not only breaks through the efficiency limit of traditional fluorescent materials, but also enables high color purity narrow-band emission.

[0003] However, blue MR-TADF materials often have poor material stability and short device lifetime due to higher excited state energy levels and higher exciton density in devices. SUMMARY

[0004] One object of the first aspect of the present application is to provide an anthracene compound with a spiro-coupled boron-nitrogen hetero multiple resonance skeleton, which solves the technical problem of poor material stability and short device lifetime caused by higher excited state energy levels and higher exciton density in devices in the prior art.

[0005] Another object of the first aspect of the present application is to further improve the maximum external quantum efficiency of the anthracene compound when applied to an organic electroluminescent device.

[0006] The object of the second aspect of the present application is to provide an organic electroluminescent device comprising the anthracene compound of any one of the above.

[0007] The object of the third aspect of the present application is to provide a display screen comprising the organic electroluminescent device described above.

[0008] The object of the fourth aspect of the present application is to provide an electronic device comprising the display screen described above.

[0009] According to the first aspect of the present application, the present application provides an anthracene-based compound based on a spiro skeleton and a boron-nitrogen hetero multiple resonance skeleton, the anthracene-based compound having a general structure as shown in general formula A:

[0010]

[0011] wherein Ar1-Ar5 are independently selected from a substituted or unsubstituted aromatic ring or an aromatic heterocycle, and when Ar1-Ar5 have a substituent, the substituent can be independently selected from any one of a deuterium atom, a fluorine atom, a substituted or unsubstituted C1-C15 alkyl group, a substituted or unsubstituted C1-C15 alkoxy group, a substituted or unsubstituted fluorinated C1-C15 alkyl group, a substituted or unsubstituted fluorinated C1-C15 alkoxy group, a substituted or unsubstituted ringed C3-C15 cycloalkyl group, and a substituted or unsubstituted ringed C6-C30 aryl group;

[0012] X and Y are independently selected from any one of a non-bond, a substituted or unsubstituted single bond, a nitrogen atom, a boron atom in Group IIIA elements, a carbon atom or a silicon atom in Group IVA elements, an oxygen atom in Group VIA elements, a sulfur atom, and a selenium atom.

[0013] Optionally, Ar1-Ar5 are a substituted or unsubstituted aromatic ring or an aromatic heterocycle, and when Ar1-Ar5 have a substituent, the substituent can be independently selected from any one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted i-propyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted i-butyl group, a substituted or unsubstituted s-butyl group, a substituted or unsubstituted t-butyl group, a substituted or unsubstituted 2-methylbutyl group, a substituted or unsubstituted n-pentyl group, a substituted or unsubstituted s-pentyl group, a substituted or unsubstituted trifluoromethyl group, a substituted or unsubstituted pentafluoroethyl group, a substituted or unsubstituted 2,2,2-trifluoroethyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted carbazyl group.

[0014] Optionally, Ar1-Ar3 combine with other groups to form various organic compounds, including but not limited to benzene, naphthalene, anthracene, pyrene, azulene, chrysene, biphenyl, phenanthrene, fluorene, spirobifluorene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thianaphthalene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, dithianthrene, 1,5-dithiinanthrene, azacarbazole, benzocarbolin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,5-tetrazine, 1,2,3,4-tetrazine, purine, pteridine, indolizine, or benzothiadiazole.

[0015] Optionally, Ar4 and Ar5 are each independently selected from any substituent group including but not limited to phenyl, phenyl, biphenyl, terphenyl, benzothienocarbazole, benzofuranocarbazole, benzofluoreneocarbazole, benzanthracene, benzophenanthrene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboron, triphenylphosphine oxide, diphenylphosphine oxide, triphenylsilicon, or tetraphenylsilicon.

[0016] Optionally, X and Y are each independently selected from any of the following:

[0017]

[0018]

[0019] Ar6, Ar7, and Ar8 are any of Ar1, Ar2, Ar3, Ar4, or Ar5.

[0020] Optionally, the anthracene-based compound includes any of the following structures:

[0021]

[0022]

[0023]

[0024]

[0025] According to the purpose of the second aspect of the present application, the present application further provides an organic electroluminescent device comprising an anode, a cathode and at least one organic thin film between the anode and the cathode, wherein the organic thin film is any one of the anthracene-based compounds described above.

[0026] Optionally, the organic electroluminescent device comprises a light-emitting layer, the light-emitting layer is an organic thin film, and the mass concentration of the anthracene-based compound in the light-emitting layer is any value in the range of 1wt%-30wt%.

[0027] According to the purpose of the third aspect of the present application, the present application further provides a display screen comprising a cover plate, a back plate and the organic electroluminescent device described above, wherein the organic electroluminescent device is located between the back plate and the cover plate.

[0028] According to the purpose of the fourth aspect of the present application, the present application further provides an electronic device comprising a housing assembly and the display screen described above, wherein the display screen is located inside the housing assembly.

[0029] The present application combines the high fluorescence quantum yield, narrow spectrum emission characteristics of boron-nitrogen hetero multiple resonance skeleton and the inherent high triplet energy level and long triplet exciton lifetime advantages of anthracene group with the spiro ring structure, through the above exciton characteristics of anthracene group, utilizes a triplet-triplet upconversion process to improve the exciton utilization rate of the light-emitting core, reduces the accumulation of triplet excitons, and improves the lifetime of the blue organic electroluminescent device based on anthracene-based compounds.

[0030] Further, by setting the mass concentration of the anthracene-based compound in the light-emitting layer to any value in the range of 1wt%-30wt%, the high triplet energy level (T1≥2.7eV) and long exciton lifetime (τ>100μs) characteristics of the anthracene-based compound can be effectively utilized, the non-radiative triplet excitons are converted into singlet excitons through the triplet-triplet upconversion (TTA-UC) mechanism, the exciton utilization rate is improved, the steric hindrance generated by the spiro ring structure can inhibit exciton quenching, thereby prolonging the service life of the organic electroluminescent device. Moreover, the above concentration window can synergize the energy level advantages of boron-nitrogen hetero MR material (FWHM<30nm) and anthracene group to achieve deep blue light emission with CIEy<0.15. By expanding the π conjugated system through the spiro[anthracene-9,9'-fluorene] structure, the external quantum efficiency of the organic electroluminescent device is improved.

[0031] The above description is only a summary of the technical solutions of the present application. In order to make the technical means of the present application more clearly understood and implemented according to the content of the description, the preferred embodiments of the present application are described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0032] Some specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. The same reference signs in the drawings denote the same or similar components or parts. It should be understood by those skilled in the art that the drawings are not necessarily drawn to scale. In the drawings:

[0033] Figure 1 is an ultraviolet absorption spectrum and a room temperature fluorescence spectrum of Formula 1 according to one embodiment of the present application;

[0034] Figure 2 is a low-temperature fluorescence spectrum and a low-temperature phosphorescence spectrum of Formula 1 according to one embodiment of the present application;

[0035] Figure 3 is an organic electroluminescence spectrum of an organic electroluminescence device prepared according to Example 1 and Comparative Example 1 of the present application;

[0036] Figure 4 is the external quantum efficiency of an organic electroluminescence device prepared according to Example 1 and Comparative Example 1 of the present application;

[0037] Figure 5 is a 95% brightness lifetime spectrum of an organic electroluminescence device prepared according to Example 1 and Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0038] The specific embodiments of the present application are described in further detail below with reference to the accompanying drawings and examples. The following examples are used to illustrate the present application, but are not used to limit the scope of the present application.

[0039] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to explain the present application, but not to limit the present application. In addition, it should be noted that only the parts related to the present application are shown in the drawings, but not all the structures. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0040] The terms "comprising" and "including," and any variations thereof, as used in the present application are intended to cover the respective terms "consisting essentially of" and "consisting of," respectively. Thus, the terms "comprising" and "including" and any variations thereof, shall not be read to exclude additional steps or elements that are in addition to those recited in the claims. For example, processes, methods, articles, or apparatuses that comprise, have, or are implemented

[0041] Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment of the application. The appearances of the phrase "in an embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are they necessarily mutually exclusive of one another. It is expressly understood that any of the embodiments described herein can be incorporated in to other embodiments.

[0042] Figure 1 is an ultraviolet absorption spectrum and a room temperature fluorescence spectrum of Formula 1 according to one embodiment of the present application, Figure 2 is a low temperature fluorescence spectrum and a low temperature phosphorescence spectrum of Formula 1 according to one embodiment of the present application.

[0043] The present application provides a spirocyclic coupled boron-nitrogen hetero multiple resonance skeleton anthracene compound, the anthracene compound has a general structure as shown in general formula A:

[0044]

[0045] wherein, Ar1-Ar5 are independently selected from substituted or unsubstituted aromatic ring or aromatic heterocycle, when Ar1-Ar5 has a substituent, the substituent can be individually selected from any one of deuterium atom, fluorine atom, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted fluorinated C1-C15 alkyl, substituted or unsubstituted C1-C15 fluorinated alkoxy, substituted or unsubstituted ring C3-C15 cycloalkyl, substituted or unsubstituted ring C6-C30 aryl; X and Y are independently selected from any one of non-bond, substituted or unsubstituted single bond, nitrogen atom, boron atom in group IIIA, carbon atom or silicon atom in group IVA, oxygen atom in group VIA, sulfur atom or selenium atom.

[0046] In this embodiment, by combining the boron-nitrogen hetero multiple resonance skeleton and anthracene group with the spiro skeleton, the high fluorescence quantum yield, narrow spectrum emission characteristics of the boron-nitrogen hetero multiple resonance skeleton, and the inherent high triplet energy level and long triplet exciton lifetime of the anthracene group are combined with the spiro structure. Through the above exciton characteristics of the anthracene group, a triplet-triplet upconversion process is used to improve the exciton utilization rate of the light-emitting core, reduce the accumulation of triplet excitons, and improve the lifetime of the blue organic electroluminescent device based on the anthracene compound.

[0047] In this embodiment, the introduction of the spiro structure can not only utilize the orthogonal structure inherent to the spiro unit to impart a large three-dimensional steric hindrance to the material, so that this steric hindrance can effectively improve the strong π-π interaction of the MR-TADF material due to the planar structure, so that the organic electroluminescent device based on the anthracene compound can still realize the characteristics of high-efficiency narrow-spectrum emission under high-doping conditions. Secondly, compared with ordinary single-bond connection, the extension of peripheral modification using the spiro structure as a connecting unit can effectively improve the molecular rigidity. Higher molecular rigidity limits molecular vibration, reduces the non-radiative decay rate of the excited state, which helps to reduce heat generation and material aging, that is, by reducing energy loss, rigid molecules can maintain the stability of the device under high brightness, avoid the shortening of the lifetime caused by exciton quenching (such as triplet-triplet annihilation), and be conducive to improving the long-life blue light of the organic electroluminescent device.

[0048] As shown in Figure 1 and Figure 2 The absorption band of formula 1 below 400 nm can be attributed to π-π* transition of the conjugated structure, and the characteristic absorption peak at 464 nm is closely related to its short-range intramolecular charge transfer characteristics. The PL spectrum presents narrow-spectrum emission at 477 nm, and the 22 nm FWHM confirms the rigid characteristics of the molecular structure. Here, the low-temperature fluorescence spectrum and the low-temperature phosphorescence spectrum are respectively the characterization tests of the low-temperature fluorescence and the low-temperature phosphorescence of the target molecule in 77K frozen toluene solution.

[0049] In a further embodiment, Ar1-Ar5 are substituted or unsubstituted aromatic or heteroaromatic rings, and when Ar1-Ar5 have substituents, the substituents can be individually selected from the group consisting of hydrogen atom, deuterium atom, fluorine atom, cyano group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted n-propyl group, substituted or unsubstituted iso-propyl group, substituted or unsubstituted n-butyl group, substituted or unsubstituted iso-butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted t-butyl group, substituted or unsubstituted 2-methylbutyl group, substituted or unsubstituted n-pentyl group, substituted or unsubstituted sec-pentyl group, substituted or unsubstituted trifluoromethyl group, substituted or unsubstituted pentafluoroethyl group, substituted or unsubstituted 2,2,2-trifluoroethyl group, substituted or unsubstituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, and substituted or unsubstituted carbazolyl group. In this embodiment, the variety of materials and the optimization of optoelectronic properties are achieved by the extension of the π-system and the tuning of the peripheral substituents.

[0050] In a further embodiment, Ar1-Ar3 combine with other groups to form various organic compounds, including but not limited to benzene, naphthalene, anthracene, rylenes, dihydropyrene, chrysene, fluorene, benzofluorene, isobenzofluorene, dibenzofluorene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thianaphthalene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenoxazine, phenothiazine, pyrazole, indazole, imidazole, benzoimidazole, naphthimidazole, phenanthroimidazole, pyridoimidazole, pyrazinimidazole, quinoxalimimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, dianthracene, 1,5-diazanthracene, azacarbazole, benzocarbolin, phenalene, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole,

[0051] 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,5-tetrazine, 1,2,3,4-tetrazine, purine, pteridine, indolizine, or benzothiadiazole.

[0052] In a further embodiment, Ar4and Ar5independently of each other are any substituent including but not limited to phenyl, phenyl, biphenyl, terphenyl, benzothienocarbazole, benzo furanocarbazole, benzofluorene carbazole, benzanthracene, benzophenanthrene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenyl phosphine oxide, diphenyl phosphine oxide, triphenyl silicon, or tetraphenyl silicon.

[0053] In a further embodiment, X and Y are independently of each other any group selected from:

[0054]

[0055] Ar6, Ar7and Ar8are any of Ar1, Ar2, Ar3, Ar4or Ar5.

[0056] In a further embodiment, the anthracene-based compound comprises any of the following structures:

[0057]

[0058]

[0059]

[0060]

[0061] Here, the anthracene-based compound comprises any of the above formula (1) to (32).

[0062] The present application also provides an organic electroluminescent device comprising an anode, a cathode, and at least one organic thin film layer between the anode and the cathode, wherein the organic thin film layer is any of the anthracene-based compounds described above. The anthracene-based compound is not repeated here.

[0063] In a further embodiment, the organic electroluminescent device comprises a light-emitting layer, the light-emitting layer is an organic thin film, and the mass concentration of the anthracene-based compound in the light-emitting layer is any value in the range from 1 wt% to 30 wt%, i.e. the mass concentration of the anthracene-based compound in the light-emitting layer can be 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 10 wt%, 20 wt% or 30 wt%, or any other value in the range from 1 wt% to 30 wt%. In this embodiment, by setting the mass concentration of the anthracene-based compound in the light-emitting layer in the above range, the high triplet energy level (T1≥2.7 eV) and long exciton lifetime (τ>100 μs) characteristics of the anthracene-based compound can be effectively utilized, the non-radiative triplet excitons can be converted into singlet excitons through the triplet-triplet upconversion (TTA-UC) mechanism, the exciton utilization rate can be improved, the steric hindrance produced by the spiro structure can inhibit exciton quenching, and thus the service life of the organic electroluminescent device can be prolonged. Moreover, the above concentration window can synergize the energy level advantages of the boron-nitrogen MR material (FWHM<30 nm) and the anthracene-based group to achieve deep blue light emission with CIEy<0.15. By expanding the π conjugated system through the spiro[anthracene-9,9'-fluorene] structure, the external quantum efficiency of the organic electroluminescent device can be improved.

[0064] The present application also provides a display screen comprising a cover plate, a back plate and the organic electroluminescent device of any one of the above, the organic electroluminescent device being located between the back plate and the cover plate. The organic electroluminescent device is not described again here.

[0065] The present application also provides an electronic device comprising a housing assembly and the display screen of the above, the display screen being located inside the housing assembly. The display screen is not described again here.

[0066] Synthetic examples

[0067] Synthetic example 1: synthesis of formula 1

[0068]

[0069] Synthesis of intermediate 1b: (10-phenyl-9-anthryl)boronic acid pinacol ester (10 g, 26.3 mmol), methyl 2-iodobenzoate (6.9 g, 26.3 mmol), tris(dibenzylideneacetone)dipalladium (722.4 mg, 0.79 mmol), bis(2-diphenylphosphinophenyl)ether (708.9 mg, 1.31 mmol), potassium phosphate (11.2 g, 52.59 mmol) were added to a dry flask, purged with nitrogen three times and quickly sealed with an argon balloon. To this, 150 ml of nitrogen purged toluene / ethanol / water (5:1:2) mixed solvent was added and heated at 105 °C for 24 h. After cooling to room temperature, dichloromethane was added and the organic phase was dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (dichloromethane / petroleum ether 1:3) to obtain the product as a transparent solid (8.0 g, 78%) [M + ] = 388.

[0070] Synthesis of intermediate 1c: Intermediate 1b (5 g, 12.87 mmol), trifluoromethanesulfonic acid (9.66 g, 64.36 mmol) were added to a dry flask, 50 ml of methanesulfonic acid was added as a solvent and reacted at 50 °C for 4 h. After cooling to room temperature, water (200 ml) was added to precipitate, filtered, and the crude product was purified by silica gel column chromatography (dichloromethane / petroleum ether 1:1) to obtain the product as a red solid (3.0 g, 65%) [M + ] = 356.

[0071] Synthesis of intermediate 1e: Carbazole (4.04 g, 24.18 mmol) and cesium carbonate (14.33 g, 43.97 mmol) were added to a dry flask, purged with nitrogen three times and quickly sealed with an argon balloon. To this, 200 ml of super dry N,N’-dimethylformamide solvent was added and stirred at room temperature for 0.5 h. To the reaction solution, 1-bromo-3-chloro-2,4-difluorobenzene (5 g, 21.98 mmol) was added and heated at 150 °C for 24 h. After cooling to room temperature, cesium carbonate was removed by filtration, the solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography (dichloromethane / petroleum ether 1:3) to obtain the product as a white solid (10.32 g, 90%) [M + ] = 522.

[0072] Synthesis of intermediate 1f: Intermediate 1e (2 g, 3.83 mmol) was taken in a dry schlenk tube, purged with nitrogen gas for three times and sealed quickly with argon balloon. To this, super dry THF solvent 100 ml was added, taken in -78 °C environment for 3-5 min, to this n-butyllithium (1.6 M, 4.60 mmol) was added drop wise, stirred for 1 h at -78 °C, to this intermediate 1c (1.5 g, 4.22 mmol) was added, stirred for 12 h at room temperature, to this 10 ml ethanol was added to quench the butyllithium, solvent was removed by rotary evaporation. To this, hydrochloric acid / acetic acid (1:10) mixture 50 ml was added, heated at 110 °C for 12 h, after cooling to room temperature, this was poured into 200 ml water, neutralized to neutral with sodium carbonate, dichloromethane was added for liquid liquid extraction (200 ml), organic layer was dried over anhydrous sodium sulfate, solvent was removed by rotary evaporation and the crude was purified by silica gel column chromatography (dichloromethane / pet ether 2:5) to get the yellow solid product (1.94 g, 65%) [M + ] = 781.

[0073] Synthesis of formula 1: Intermediate 1f (3 g, 3.84 mmol) was taken in a two necked flask, purged with nitrogen gas, argon balloon was attached, THF 50 ml was added, taken in -40 °C cooling bath, n-butyllithium (295.13 mg, 4.61 mmol) was added drop wise, reaction was carried out for 1 h at -40 °C, reaction was carried out for 1 h at 60 °C, reaction was carried out for 2 h at 60 °C, reaction was carried out for 16 h at 160 °C. After cooling to room temperature, solvent was removed by rotary evaporation and the crude was purified by silica gel column chromatography (dichloromethane / pet ether 1:4) to get the yellow solid product (2.1 g, 72%) [M + ] = 755.

[0074] Synthesis of formula 2

[0075]

[0076] Synthesis of intermediate 2a: Intermediate 1e in the synthesis of intermediate 1e was replaced with 3,6-di-tert-butylcarbazole, under the same reaction condition, white solid product (5.21 g, 75%) was obtained. [M + ] = 744.

[0077] Synthesis of intermediate 2b: Intermediate 1e in the synthesis of intermediate 1d was replaced with intermediate 2a, under the same reaction condition, yellow solid product (3.5 g, 36%) was obtained. [M + ] = 1006.

[0078] Synthesis of Formula 2: Intermediate 1f in the synthesis of Formula 1 was replaced by intermediate 2b, and the same reaction conditions could give yellow solid product (1.3 g, 50%).[M + ] = 979.

[0079] Synthesis of Formula 13

[0080]

[0081] Synthesis of Intermediate 3a: Intermediate carbazole in the synthesis of Intermediate 1e was replaced by 3,7-bis(1,1-dimethylethyl)-10H-phenoxazine, and the same reaction conditions could give white solid product (5.21 g, 68%).[M + ] = 776.

[0082] Synthesis of Intermediate 3b: Intermediate 1e in the synthesis of Intermediate 1d was replaced by Intermediate 3a, and the same reaction conditions could give yellow solid product (3.5 g, 42%).[M + ] = 1036.

[0083] Synthesis of Formula 13: Intermediate 1f in the synthesis of Formula 1 was replaced by Intermediate 3b, and the same reaction conditions could give yellow solid product (1.3 g, 45%).[M + ] = 1011.

[0084] The organic electronic device of the present application can be an electroluminescent device of bottom emission type or an electroluminescent device of top emission type. The electroluminescent device of bottom emission type refers to a device structure that emits light through the anode, while the electroluminescent device of top emission type refers to a device structure that emits light through the cathode. The light-emitting layer can comprise a plurality of guest materials and a plurality of host materials. The guest material can be a fluorescent material, a phosphorescent material, and / or a thermally activated delayed fluorescence material. The host material refers to a matrix material that occupies the majority of the composition in the light-emitting layer. The host material doped and combined with the fluorescent material is referred to as a fluorescent host, and the host material doped and combined with the phosphorescent material is referred to as a phosphorescent host. It should be noted that the selection of the host material does not depend on its molecular structure, but is distinguished according to the matrix material as the guest material.

[0085] In a preferred embodiment of the present application, the compound of the present application is used as a light-emitting guest material in the light-emitting layer in the organic electroluminescent device.

[0086] The application effect of the compound of the present application in the organic electroluminescent device is described in detail below by Device Examples 1-3 and Comparative Examples 1-3, to verify the technical progress and beneficial effects of the compound of the present application in the field.

[0087] Device Examples:

[0088] Example 1

[0089] The ITO transparent conductive layer coated glass plate was sequentially subjected to ultrasonic treatment in a cleaning agent, rinsing in deionized water, then cleaning in acetone and ethanol each for three times, and baking in a clean environment until completely removing moisture, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam. The ITO conductive glass was placed in a vacuum chamber, vacuumed to below 5 x 10 -4 Pa. The ITO conductive glass was used as an anode, and a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode were sequentially deposited thereon; wherein the deposition rate of the light-emitting layer was 0.2 nm / s, the deposition rate of the metal electrode was 0.5 nm / s, the material of the hole injection layer was HAT-CN, the material of the hole transport layer was TAPC, the material of the electron blocking layer was TCTA, the material of the electron transport layer was TmPyPB, the material of the electron injection layer was Liq, the anthracene-based compound of the light-emitting layer was formula (1), and the mass concentration of the anthracene-based compound of the light-emitting layer was 15 wt%.

[0090] Example 2

[0091] Example 2 differs from Example 1 only in that the anthracene-based compound of the light-emitting layer is formula (2).

[0092] Example 3

[0093] Example 3 differs from Example 1 only in that the anthracene-based compound of the light-emitting layer is formula (13).

[0094] Example 4

[0095] Example 4 differs from Example 1 only in that the mass concentration of the anthracene-based compound of formula (1) of the light-emitting layer is 1 wt%.

[0096] Example 5

[0097] Example 5 differs from Example 1 only in that the mass concentration of the anthracene-based compound of formula (1) of the light-emitting layer is 30 wt%.

[0098] Comparative Example 1

[0099] Comparative Example 1 differs from Example 1 only in that the organic compound material of the light-emitting layer is DtBuCzB.

[0100] The functional layer compound structures and nomenclatures involved in the device examples are as follows:

[0101]

[0102] The photoelectric properties of the organic electroluminescent devices prepared according to Examples 1-12 and Comparative Examples 1-8 were tested, and the performance data are shown in Table 1.

[0103] Table 1. Device performance data

[0104]

[0105]

[0106] Figure 3 is an organic electroluminescence spectrum diagram of an organic electroluminescent device prepared according to the present application embodiment 1 and comparative example 1.

[0107] As shown in the figure, in the 15wt% PhCzBCz doped thin film, formula 1 has almost no red shift and broadening compared with the spectrum of the solution state, and it can maintain a narrow spectrum electroluminescent property of 25nm compared with comparative example 1, thereby improving the light-emitting purity and light-emitting efficiency of the organic electroluminescent device. Figure 3

[0108] is the external quantum efficiency of the organic electroluminescent device prepared according to the present application embodiment 1 and comparative example 1. Figure 4 As shown in the figure, compared with comparative example 1, embodiment 1 has a higher maximum external quantum efficiency (34.8%), and shows good device efficiency roll-off.

[0109] Figure 4 is the 95% brightness lifetime spectrum diagram of the organic electroluminescent device prepared according to the present application embodiment 1 and comparative example 1.

[0110] Figure 5 As shown in the figure, due to effectively reducing the accumulation quenching of triplet excitons, formula 1 shows better device lifetime, and its LT95 is almost 2.5 times of that of comparative example DtBuCzB.

[0111] According to the comparative analysis of the above data, the organic electroluminescent devices of embodiments 1-3 prepared by using the compounds (formula (1), formula (2) and formula (13)) of the present application have a narrower half-peak width and a larger maximum external quantum efficiency compared with conventional organic luminescent materials, and can reduce the driving voltage of the organic electroluminescent device, improve the quantum light-emitting efficiency and device brightness. At the same time, the effective combination of anthracene-based compounds of the present application can reduce the accumulation of triplet excitons, thereby improving the service life of the organic electroluminescent device, and the preparation method is simple and the raw materials are easy to obtain. Figure 5

[0112]

[0113] ​​​Any combination of the technical features in the above-described embodiments can be made, and for the sake of brevity, not all possible combinations are described, however, as long as the combination of the technical features does not exist in contradiction, it shall be considered within the scope of the present disclosure.

[0114] The above-described embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it shall not be understood as a limitation on the patent scope of the present application. It shall be pointed out that, for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, and these shall be within the protection scope of the present application. Therefore, the protection scope of the present application patent shall be subject to the appended claims.

Claims

1. An anthracene-based compound with a spirocyclic coupled boron-aza multi-resonance framework, characterized in that, The anthracene compound has a general formula structure as shown in formula A: Ar1-Ar5 are each independently selected from substituted or unsubstituted aromatic rings or aromatic heterocycles. When Ar1-Ar5 have substituents, the substituents can be selected independently from any one of the following: deuterium atom, fluorine atom, substituted or unsubstituted C1-C15 alkyl group, substituted or unsubstituted C1-C15 alkoxy group, substituted or unsubstituted C1-C15 fluoroalkyl group, substituted or unsubstituted C1-C15 fluoroalkoxy group, substituted or unsubstituted cycloalkyl group of C3-C15, and substituted or unsubstituted cycloalkyl group of C6-C30. X and Y are independently selected from any one of the following: non-bonded, substituted or unsubstituted single bonds, nitrogen atom, boron atom from Group IIIA, carbon or silicon atom from Group IVA, oxygen atom from Group VIA, sulfur atom or selenium atom.

2. The anthracene-based compound according to claim 1, characterized in that, The Ar1-Ar5 are substituted or unsubstituted aromatic rings or aromatic heterocycles. When Ar1-Ar5 has substituents, the substituents can be selected independently from hydrogen, deuterium, fluorine, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted... Substituted 2-methylbutyl, substituted or unsubstituted n-pentyl, substituted or unsubstituted sec-pentyl, substituted or unsubstituted trifluoromethyl, substituted or unsubstituted pentafluoroethyl, substituted or unsubstituted 2,2,2-trifluoroethyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and substituted or unsubstituted carbazole.

3. The anthracene-based compound according to claim 2, characterized in that, The Ar1-Ar3 groups combine with other groups to form various organic compounds, including but not limited to benzene, naphthalene, anthracene, dinaphthalene, dihydropyrene, perylene, fluoranthene, benzo[a]pyrene, furan, benzo[a]furan, isobenzo[a]furan, dibenzo[a]furan, thiophene, benzo[a]thiophene, isobenzo[a]thiophene, thiofluorene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenotoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthiazole, phenanthreneimidazole, pyridinium pyridimazole, pyrazinium pyridimazole, quinoxaline pyridimazole, oxazole, benzo[a]oxazole, naphthiazole, anthraquinone oxazole, phenanthrene pyridimazole, isoxazole, 1,2-thiazolinone Zyrazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, diazanthracene, 1,5-diazanthracene, nitrogen carbazole, benzocarbline, phenanthrene, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,5-tetraazine, 1,2,3,4-tetraazine, purine, pteridine, indene, or benzothiazole.

4. The anthracene-based compound according to claim 3, characterized in that, The Ar4 and Ar5 positions are each independently substituted with any substituent group, including but not limited to phenyl, phenyl, biphenyl, terphenyl, benzothiophenecarbazole, benzofuranocarbazole, benzofluorenocarbazole, benzoanthracene, benzophenanthrene, fluorenyl, spirobisfluorenyl, triazine, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl, N-phenylcarbazoleyl, indocarbazoleyl, benzimidazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboryl, triphenylphosphoxy, diphenylphosphoxy, triphenylsilyl, or tetraphenylsilyl.

5. The anthracene-based compound according to claim 1, characterized in that, X and Y can each independently select any of the following groups: Ar6, Ar7, and Ar8 are any one of Ar1, Ar2, Ar3, Ar4, or Ar5.

6. The anthracene-based compound according to any one of claims 1-5, characterized in that, The anthracene compound includes any of the following structures:

7. An organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode, and at least one organic thin film located between the anode and the cathode, characterized in that, The organic film is an anthracene-based compound as described in any one of claims 1-6.

8. The organic electroluminescent device according to claim 7, characterized in that, The organic electroluminescent device includes a light-emitting layer, which is an organic thin film, and the mass concentration of anthracene compound in the light-emitting layer is any value between 1 wt% and 30 wt%.

9. A display screen, characterized in that, It includes a cover plate, a back plate, and an organic electroluminescent device as described in any one of claims 7-8, wherein the organic electroluminescent device is located between the back plate and the cover plate.

10. An electronic device, characterized in that, It includes a housing assembly and a display screen as described in claim 9, the display screen being located inside the housing assembly.

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