Anthryl derivatives based on boron-nitrogen multiple resonance skeleton, and preparation and application thereof

Abstract

The invention belongs to the field of preparation and application of organic photoelectric materials, and discloses an anthryl derivative based on a boron-nitrogen multiple resonance skeleton and preparation and application of the anthryl derivative, and the anthryl derivative has a general formula structure as shown in at least one of general formulas A-1 to A-4. According to the present invention, the chemical structure of the anthryl derivative is improved to form the general formulas A-1 to A-4 having the specific chemical structure (R1 and R2 groups in each general formula meet the specific group requirement), and the obtained anthryl derivative can be used for preparing the high-purity anthryl derivative based on the boron-nitrogen multi-resonance effect and the triplet-triplet fusion effect (TTF), particularly, the compound can be applied to a light-emitting layer of an organic light-emitting device (OLED) as a guest light-emitting material, a host light-emitting material and a mixed host light-emitting material, so that a blue light narrow-emission OLED device with high efficiency, low driving voltage and long service life is obtained. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of preparation and application of organic photoelectric materials, and more specifically, relates to an anthracene derivative based on a boron-nitrogen multiple resonance skeleton, and the preparation and application thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) have been widely used in the field of light emission and display due to their outstanding advantages such as high efficiency, long life, and flexible foldability. With the development of OLED, consumer demand for OLED-related technologies continues to increase, which requires a supply-side structural reform of OLED, that is, to improve the performance of OLED products on the supply side, so that they are more in line with consumer expectations and save energy. Current organic light-emitting materials generally face some prominent disadvantages, such as the problem of too wide half-width (FWHM) of the emission spectrum (>50nm), which significantly reduces the color purity of OLED light emission. Therefore, OLED cannot directly achieve high color purity and wide color gamut display, and a corresponding solution is urgently needed.

[0003] The third generation of thermally activated delayed fluorescence materials (TADF) can theoretically fully utilize triplet excitons for delayed fluorescence emission through reverse intersystem crossing (RISC) in organic small molecules, thereby achieving a theoretical internal quantum efficiency of 100%. It is expected to replace existing traditional fluorescent and phosphorescent materials. TADF materials have significant advantages in cost and efficiency. However, most donor-acceptor (DA) TADF materials still have a large FWHM, which is caused by strong structural relaxation within the molecule. In order to solve the problem of wide FWHM, Professor T. Hatakeyama and others from Kwansei Gakuin University developed heteroatom-embedded polycyclic aromatic hydrocarbons (PAHs), which achieve HOMO / LUMO separation at the atomic scale through the opposite resonance effect by embedding electron-withdrawing boron atoms (B) and electron-donating nitrogen atoms (N). This type of material is collectively referred to as thermally delayed fluorescence materials with multiple resonance effects (MR-TADF). The separation of HOMO / LUMO at the atomic scale greatly weakens structural relaxation, so that MR-TADF materials obtain extremely narrow FWHM, greatly improving color purity, and this material also retains the characteristics of TADF, which is currently the TADF material with the greatest potential. However, there is currently a shortage of MR-TADF material systems, especially the lack of choices for blue MR-TADF luminescent molecules, and the poor life of blue OLEDs, so the development of new blue MR-TADF luminescent bodies is urgent.

[0004] The research group of the inventor of the present invention has obtained a class of monoboron derivatives based on fluorene-type aniline fusion donors, their preparation and application (see Chinese patent CN 202210431760.2 for details), which introduces rigid group fluorene derivatives on the basis of retaining electron-rich N atoms to form new fusion donors. This type of monoboron derivative based on fluorene-type aniline fusion donors can achieve a FWHM of less than 30nm based on the BN resonance effect, which can effectively improve the color purity of OLED devices. However, although the triplet excitons in TADF materials can return to the singlet state through reverse intersystem crossing, there is still a serious triplet exciton quenching problem due to the low reverse intersystem crossing rate. Therefore, the lifespan problem is still a major problem restricting the development of blue light OLEDs. A new method is urgently needed to prevent the accumulation of triplet excitons and improve the lifespan of OLED devices. Summary of the invention

[0005] In view of the above defects or improvement needs of the prior art, the purpose of the present invention is to provide a class of anthracene derivatives based on a boron-nitrogen multiple resonance skeleton, and their preparation and application, wherein the chemical structure of the anthracene derivatives is improved to form general formulas A-1 to A-4 with specific chemical structures (the R1 and R2 groups in each general formula meet the requirements of a specific group), and the obtained anthracene derivatives can be simultaneously based on the boron-nitrogen multiple resonance effect and the triplet-triplet fusion effect (TTF), and can be particularly used in the light-emitting layer of an organic electroluminescent device (OLED) as a guest luminescent material, a host luminescent material and a mixed host luminescent material, so as to obtain a high-efficiency, low-driving-voltage, long-life blue-light narrow-emission OLED device.

[0006] To achieve the above object, according to one aspect of the present invention, there is provided an anthracene derivative based on a boron-nitrogen multiple resonance skeleton, characterized in that the anthracene derivative has a general structure as shown in at least one of the general formulas A-1 to A-4:

[0007]

[0008] Wherein, the R1 group is selected from: hydrogen, deuterium, methyl, tert-butyl, trifluoromethyl, phenyl, naphthyl, anthracenyl;

[0009] The R2 group is selected from: hydrogen, deuterium, methyl, phenyl, methoxy, trifluoromethyl, tert-butyl, naphthyl, anthracenyl, silane, halogen, pyrazine, pyridine, pyrimidine, pyrazine, benzimidazole ring, indolecarbazole, carbazole, phenoxazine, phenothiazine, phenoselenazine, phenanthroimidazole, substituted or unsubstituted C2-C 10 Straight chain alkyl, substituted or unsubstituted C2~C 10 Branched alkyl, substituted or unsubstituted C7~C 30 Aryl, substituted or unsubstituted C2~C 10Alkoxy, substituted or unsubstituted C1~C 10 Alkylamino, substituted or unsubstituted C2~C 10 Silane group.

[0010] As a further preferred embodiment of the present invention, the R1 group is hydrogen, methyl, trifluoromethyl, tert-butyl or phenyl;

[0011] The R2 group is a benzimidazole ring, indolecarbazole, carbazole, phenoxazine, phenothiazine, phenoselenazine, methyl, trifluoromethyl, tert-butyl or phenyl.

[0012] As a further preferred embodiment of the present invention, the structural formula of the anthracene derivative is shown in any one of Formula 1 to Formula 132:

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019] According to another aspect of the present invention, the present invention provides the use of the anthracene derivative based on the boron nitrogen multiple resonance skeleton in the light-emitting layer of an organic electroluminescent device.

[0020] As a further preferred embodiment of the present invention, the organic electroluminescent device comprises in sequence: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode;

[0021] Preferably, an electron blocking layer or an exciton blocking layer is further provided between the hole transport layer and the light emitting layer; and a hole blocking layer or an exciton blocking layer is further provided between the light emitting layer and the electron transport layer.

[0022] As a further preferred embodiment of the present invention, the anthracene derivative based on the boron nitrogen multiple resonance skeleton is specifically used as a guest luminescent material, a host luminescent material or a mixed host luminescent material in the light-emitting layer of an organic electroluminescent device.

[0023] Through the above technical solutions conceived by the present invention, compared with the prior art (especially compared with the reported MR-TADF compounds), the anthracene derivatives of the boron nitrogen resonance skeleton in the present invention have multiple induced resonance effects, thermally delayed fluorescence characteristics and triplet-triplet exciton annihilation (TTF) capabilities. This enables it to achieve narrowing of the half-peak width of the luminescence spectrum and efficient fluorescence emission. Therefore, it is applied in the light-emitting layer structure of organic electroluminescent devices (OLEDs) (as a luminescent object or host) to improve the OLED luminescent color purity, efficiency and life. In addition, the introduction of large-volume anthracene groups can also inhibit intermolecular stacking, thereby inhibiting concentration quenching, which allows the device efficiency to remain high in devices doped with relatively high concentrations of luminescent molecules, and weakens the efficiency roll-off.

[0024] On the basis of maintaining the boron nitrogen multi-resonance skeleton, a new blue light emitting material (luminescence wavelength meets 430nm to 495nm) is formed by introducing anthracene groups. This type of anthracene derivative based on multi-resonance has a large volume and rigidity, and the anthracene group will have a certain angle offset relative to the multi-resonance skeleton, thereby enhancing the steric hindrance of the molecule and inhibiting π-π stacking, thereby inhibiting concentration quenching. More importantly, since the triplet exciton lifetime of MR-TADF molecules is generally long, the reverse intersystem crossing process is weak, and triplet exciton quenching is prone to occur, while the triplet energy level of traditional anthracene derivatives is low, and its usual luminescence mechanism is triplet-triplet exciton annihilation (TTF), the principle of which is that two low-energy triplet exciton molecules (energy level relationship generally meets 2T1>S1) collide with each other to generate a high-energy singlet exciton molecule and a ground state molecule, which helps to avoid triplet exciton quenching, thereby improving the life and stability of OLED devices. Therefore, the present invention combines the anthracene structure with the MR structure for the first time to create a new MR-TADF-TTF type molecule, which can be used in both luminescent objects and luminescent hosts. The triplet exciton utilization mechanism based on the synergistic effect of RISC and TTF not only suppresses concentration quenching, but also suppresses triplet exciton quenching of MR-TADF molecules due to the TTF characteristics of the anthracene itself. The anthracene derivatives in the present invention can achieve a half-maximum width (FWHM) of less than 30nm based on the boron nitrogen multiple resonance effect and the triplet-triplet fusion effect (TTF), which can effectively improve the color purity and life of OLED devices, and can be used to prepare high-efficiency, low-driving voltage, and long-life blue narrow-emission OLED devices.

[0025] Specifically, the present invention can achieve the following beneficial effects:

[0026] (1) The anthracene derivatives based on the boron-nitrogen multi-resonance skeleton described in the present invention can expand the MR-TADF-TTF type new luminescent molecular system by combining the anthracene group with the multi-resonance BN structure to solve the problem of the current shortage of multi-resonance BN structure material systems.

[0027] (2) The present invention coats the anthracene group on the outside of the boron-nitrogen conjugated skeleton. When used as a guest luminescent material, a triplet exciton utilization mechanism of the synergistic effect of RISC and TTF can be constructed to timely export the accumulated triplet excitons, thereby avoiding the annihilation caused by the accumulation of a large amount of excitons, so that the MR-TADF material can utilize more triplet excitons to emit light, thereby improving the overall life and efficiency of the device, and ultimately realizing a high-efficiency, low roll-off, and long-life narrow-emission OLED blue light device.

[0028] (3) The anthracene derivatives based on the boron-nitrogen multiple resonance skeleton described in the present invention are based on the introduction of anthracene groups whose lowest triplet excited state energy level is only 1.8 eV. When used as a host luminescent material or a mixed host luminescent material, it is beneficial to derive triplet excitons accumulated in the guest material, thereby improving the efficiency and life of the OLED device. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Schematic diagram of the structure of an electroluminescent device.

[0030] Figure 2 The external quantum efficiency-current density relationship characteristic curves of device embodiments 1, 4, 7, and 10.

[0031] Figure 3 It is a driving voltage comparison diagram of device embodiments 1, 4, 7, 10 and device comparative example 1.

[0032] Figure 4 It is a comparison chart of device life LT95 of device embodiments 1, 4, 7, 10 and device comparative example 1.

[0033] Figure 5 It is a comparison chart of device life LT95 of device embodiments 13 to 20 and device comparative example 1. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0035] In general, the anthracene derivatives based on the boron-nitrogen multiple resonance skeleton in the present invention have a general structure as shown in at least one of the general formulas A-1 to A-4:

[0036]

[0037] wherein the R1 group is selected from the group consisting of hydrogen, deuterium, methyl, tert-butyl, trifluoromethyl, phenyl, naphthyl, and anthracenyl; and the R2 group is selected from the group consisting of hydrogen, deuterium, methyl, phenyl, methoxy, trifluoromethyl, tert-butyl, naphthyl, anthracenyl, silane, halogen, pyrazine, pyridine, pyrimidine, pyrazine, benzimidazole ring, indolecarbazole, carbazole, phenoxazine, phenothiazine, phenoselenazine, phenanthroimidazole, substituted or unsubstituted C2-C 10 Straight chain alkyl, substituted or unsubstituted C2~C 10 Branched alkyl, substituted or unsubstituted C7~C 30 Aryl, substituted or unsubstituted C2~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Alkylamino, substituted or unsubstituted C2~C 10 The group consisting of silane groups.

[0038] Based on the present invention, 132 specific anthracene derivatives can be obtained, and their structural formulas are as follows:

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045] Among them, the compounds of Formula 1 to Formula 32 satisfy the general formula A-1, the compounds of Formula 33 to Formula 64 satisfy the general formula A-2, the compounds of Formula 65 to Formula 96 satisfy the general formula A-3, and the compounds of Formula 97 to Formula 132 satisfy the general formula A-4.

[0046] The following are synthetic examples (the raw materials used, unless otherwise specified, are commercially available):

[0047] Synthesis Example 1

[0048] The anthracene derivative 1 of the boron-nitrogen multiple resonance skeleton of the present invention conforms to the general formula A-1 and has the following structure:

[0049]

[0050] The preparation method comprises the following steps:

[0051]

[0052] (1) DABNACl (synthesized by referring to the prior art, ref: Li, H.; Yan, H.; Meng, L.; Zhang, X.; Kuang, C.; Meng, Z.; He, Y.; Xu, H.; Zhang, X.; Zheng, Y.; et al.Regioisomeric effects of dibenzofuran on the properties of boron-nitrogen multiple resonance emissive materials. J. Mater. Chem. C 2023,11(44),15548-15554)(5.00 g, 10.99 mmol), bis(4-chlorophenyl)amine (2.88 g, 12.09 mmol), tridibenzylideneacetone dipalladium (0.50 g, 0.55 mmol), tri-tert-butylphosphine tetrafluoroborate (0.32 g, 1.10 mmol), sodium tert-butoxide (3.17 g, 32.98 mmol) and dry toluene (60 mL) were added into a 250 ml three-necked flask, purged with nitrogen for 15 minutes, then heated to 120 ° C in a nitrogen environment and refluxed for 12 hours. After the reaction was complete, it was cooled to room temperature, the organic layer was collected by extraction with dichloromethane and water, dried and concentrated, and initially purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 77%.

[0053]

[0054] (2) The above first step product (5.00 g, 7.62 mmol), 10-chloroanthracene-9-boric acid (3.91 g, 15.24 mmol), tetrakis(triphenylphosphine)palladium (0.44 g, 0.38 mmol), potassium carbonate (6.32 g, 45.72 mmol), toluene (60 mL), ethanol (20 mL), and water (20 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 100 ° C. in a nitrogen environment and refluxed for 20 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water washing extraction. After drying, it was concentrated and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 85%.

[0055]

[0056] (3) The above-mentioned second step product (5.00 g, 4.96 mmol), phenoxazine (1.82 g, 9.92 mmol), tridibenzylideneacetone dipalladium (0.23 g, 0.25 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 g, 0.50 mmol), sodium tert-butoxide (2.86 g, 29.76 mmol), and dry toluene (60 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 120 ° C in a nitrogen environment and refluxed for 18 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water extraction, dried and concentrated, and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 80%.

[0057] The characterization results of the anthracene derivative 1 of the boron nitrogen multiple resonance skeleton are as follows: mass spectrum is 1302.49; NMR results are as follows:

[0058] 1 H NMR(500MHz,Chloroform-d)δ8.18(dd,J=7.5,1.6Hz,1H),8.11-8.05(m,1H),7.59(td,J=8.0,1.4Hz,1H),7.53(td,J=7.7,1.4Hz,1H ),7.52-7.46(m,1H),7.44-7.34(m,2H),7.37-7.13(m,4H),7.09-7.03(m,1H),7.07-6.98(m,1H),6.92(ddd,J=15.9,8.0,1.2Hz,1H).

[0059] Synthesis Example 2

[0060] The anthracene derivative 33 of the boron-nitrogen multiple resonance skeleton of the present invention conforms to the general formula A-2 and has the following structure:

[0061]

[0062] The preparation method comprises the following steps:

[0063]

[0064] (1) DABNACl (5.00 g, 10.99 mmol), bis(4-chlorophenyl)amine (2.88 g, 12.09 mmol), tridibenzylideneacetone dipalladium (0.50 g, 0.55 mmol), tri-tert-butylphosphine tetrafluoroborate (0.32 g, 1.10 mmol), sodium tert-butoxide (3.17 g, 32.98 mmol), and dry toluene (60 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 120° C. in a nitrogen environment and refluxed for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and the organic layer was collected by extraction with dichloromethane and water, dried, concentrated, and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 77%.

[0065]

[0066] (2) The above first step product (5.00 g, 7.62 mmol), boric acid pinacol ester (7.74 g, 30.48 mmol), tridibenzylideneacetone dipalladium (0.44 g, 0.38 mmol), tri-tert-butylphosphine tetrafluoroborate (0.22 g, 0.76 mmol), sodium acetate (1.25 g, 15.24 mmol), and 1,4-dioxane (60 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 110 ° C. in a nitrogen environment and refluxed for 18 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water extraction, dried and concentrated, and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 90%.

[0067]

[0068] (3) The above-mentioned second step product (5.00 g, 5.96 mmol), 1,2-dibromoethane (2.35 g, 12.56 mmol), tetrakistriphenylphosphine palladium (0.35 g, 0.30 mmol), potassium carbonate (2.47 g, 17.88 mmol), toluene (60 mL), ethanol (20 mL), and water (20 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 100 ° C. in a nitrogen environment and refluxed for 24 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water extraction, dried and concentrated, and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 50%.

[0069]

[0070] (4) The product of the third step (5.00 g, 6.24 mmol), 10-chloroanthracene-9-boric acid (3.36 g, 13.10 mmol), tetrakistriphenylphosphine palladium (0.35 g, 0.30 mmol), potassium carbonate (3.42 g, 18.72 mmol), toluene (60 mL), ethanol (20 mL), and water (20 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 100 ° C. in a nitrogen environment and refluxed for 20 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water washing extraction. After drying, it was concentrated and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 59%.

[0071]

[0072] (5) The product of the fourth step (5.00 g, 4.70 mmol), phenoxazine (1.81 g, 9.86 mmol), tridibenzylideneacetone dipalladium (0.23 g, 0.25 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 g, 0.50 mmol), sodium tert-butoxide (2.86 g, 29.76 mmol), and dry toluene (60 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 120 ° C. in a nitrogen environment and refluxed for 22 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by extraction with dichloromethane and water, dried and concentrated, and initially purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 87%.

[0073] The characterization results of the anthracene derivative 33 of the boron nitrogen multiple resonance skeleton are as follows: mass spectrum is 1357.55; NMR results are as follows:

[0074] 1 H NMR(500MHz,chloroform-d)δ8.06(dd,J=8.3,1.4Hz,2H),7.83(dd,J=7.7,1.5Hz,2H),7.61-7.54(m,2H),7.46-7.18(m,14H ),7.09-6.88(m,11H),6.55(s,1H),3.43(dt,J=16.7,8.0Hz,1H),3.30(dt,J=16.8,8.0Hz,1H),2.99(tt,J=8.0,1.0Hz,2H).

[0075] Synthesis Example 3

[0076] The anthracene derivative 65 of the boron-nitrogen multiple resonance skeleton of the present invention conforms to the general formula A-3 and has the following structure:

[0077]

[0078] The preparation method comprises the following steps:

[0079]

[0080] (1) BNCzBr (synthesized by referring to the prior art, ref: Zou, Y.; Yu, M.; Xu, Y.; Xiao, Z.; Song, X.; Hu, Y.; Xu, Z.; Zhong, C.; He, J.; Cao, X.; et al. Acceleration of reverse intersystem crossing in multi-resonance TADF emitter. Chem 2024,10,1485-1501)(5.00g,6.95mmol),bis(4-chlorophenyl)amine (1.73g,7.30mmol),tridibenzylideneacetonedipalladium (0.32g,0.35mmol),tri-tert-butylphosphinetetrafluoroborate (0.20g,0.70mmol),sodium tert-butoxide (2.00g,20.85mmol) and dry toluene (60mL) were added into a 250ml three-necked flask, purged with nitrogen for 15 minutes, then heated to 120℃ under reflux and stirred in a nitrogen environment for 10 hours. After the reaction was complete, it was cooled to room temperature, the organic layer was collected by extraction with dichloromethane and water, dried and concentrated, and initially purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 88%.

[0081]

[0082] (2) The above first step product (5.00 g, 5.70 mmol), 10-chloroanthracene-9-boric acid (3.07 g, 11.97 mmol), tetrakis(triphenylphosphine)palladium (0.43 g, 0.34 mmol), potassium carbonate (4.73 g, 34.20 mmol), toluene (60 mL), ethanol (20 mL), and water (20 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 100 ° C. in a nitrogen environment and refluxed for 24 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water washing extraction. After drying, it was concentrated and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 84%.

[0083]

[0084] (3) The above-mentioned second step product (5.00 g, 4.07 mmol), phenoxazine (1.57 g, 8.55 mmol), tridibenzylideneacetone dipalladium (0.18 g, 0.20 mmol), tri-tert-butylphosphine tetrafluoroborate (0.12 g, 0.40 mmol), sodium tert-butoxide (2.35 g, 24.42 mmol), and dry toluene (60 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 120 ° C in a nitrogen environment and refluxed for 23 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water extraction, dried and concentrated, and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 85%.

[0085] The characterization results of the anthracene derivative 65 of the boron nitrogen multiple resonance skeleton are as follows: mass spectrum is 1522.71; NMR results are as follows:

[0086] 1 H NMR(500MHz,Chloroform-d)δ8.48(d,J=2.2Hz,1H),8.18(dd,J=7.5,1.6Hz,1H),8.11-8.05(m,1H ),7.90(t,J=1.9Hz,1H),7.62-7.46(m,4H),7.35-7.13(m,6H),6.92(ddd,J=15.9,8.0,1.2Hz,1H).

[0087] Synthesis Example 4

[0088] The anthracene derivative 99 of the boron-nitrogen multiple resonance skeleton of the present invention conforms to the general formula A-4 and has the following structure:

[0089]

[0090] The preparation method comprises the following steps:

[0091]

[0092] (1) BNCzBr (5.00 g, 6.95 mmol), bis(4-chlorophenyl)amine (1.73 g, 7.30 mmol), tridibenzylideneacetone dipalladium (0.32 g, 0.35 mmol), tri-tert-butylphosphine tetrafluoroborate (0.20 g, 0.70 mmol), sodium tert-butoxide (2.00 g, 20.85 mmol), and dry toluene (60 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 120 ° C in a nitrogen environment and refluxed for 10 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water extraction, dried and concentrated, and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 88%.

[0093]

[0094] (2) The above first step product (5.00 g, 5.70 mmol), boric acid pinacol ester (5.79 g, 22.80 mmol), tridibenzylideneacetone dipalladium (0.34 g, 0.29 mmol), tri-tert-butylphosphine tetrafluoroborate (0.17 g, 0.58 mmol), sodium acetate (0.94 g, 11.4 mmol), and 1,4-dioxane (60 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 110 ° C. in a nitrogen environment and refluxed for 24 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water extraction, dried and concentrated, and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 92%.

[0095]

[0096] (3) The above-mentioned second step product (5.00 g, 4.71 mmol), 1,2-dibromoethane (1.76 g, 9.42 mmol), tetrakistriphenylphosphine palladium (0.28 g, 0.24 mmol), potassium carbonate (1.95 g, 14.13 mmol), toluene (60 mL), ethanol (20 mL), and water (20 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 100 ° C. in a nitrogen environment and refluxed for 28 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by dichloromethane and water extraction. After drying, it was concentrated and preliminarily purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 53%.

[0097]

[0098] (4) The product of the third step (5.00 g, 4.90 mmol), 10-chloroanthracene-9-boric acid (2.51 g, 9.80 mmol), tetrakistriphenylphosphine palladium (0.29 g, 0.25 mmol), potassium carbonate (2.69 g, 14.70 mmol), toluene (60 mL), ethanol (20 mL), and water (20 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 100 ° C. in a nitrogen environment and refluxed for 18 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by extraction with dichloromethane and water. After drying, it was concentrated and initially purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 64%.

[0099]

[0100] (5) The product of the fourth step (5.00 g, 3.89 mmol), phenoxazine (2.19 g, 11.93 mmol), tridibenzylideneacetone dipalladium (0.28 g, 0.30 mmol), tri-tert-butylphosphine tetrafluoroborate (0.18 g, 0.61 mmol), sodium tert-butoxide (3.46 g, 36.00 mmol), and dry toluene (60 mL) were added to a 250 ml three-necked flask, purged with nitrogen for 15 minutes, and then heated to 120 ° C. in a nitrogen environment and refluxed for 24 hours. After the reaction was complete, it was cooled to room temperature, and the organic layer was collected by extraction with dichloromethane and water, dried and concentrated, and initially purified by column chromatography. The crude product was further recrystallized with dichloromethane and methanol to obtain a bright yellow solid powder with a yield of 90%.

[0101] The characterization results of the anthracene derivative 99 of the boron nitrogen multiple resonance skeleton are as follows: mass spectrum is 1577.77; NMR results are as follows:

[0102] 1 H NMR(500MHz,Chloroform-d)δ8.48(d,J=2.2Hz,1H),8.06(dd,J=8.4,1.4Hz,1H),7 .90(t,J=1.9Hz,1H),7.83(dd,J=7.6,1.4Hz,1H),7.61-7.54(m,2H),7.43(td,J=7 .8,1.3Hz,1H),7.35-7.18(m,4H),7.06-6.88(m,3H),3.43(dt,J=16.6,8.0Hz,1H) ,3.30(dt,J=16.8,8.1Hz,1H),2.99(tt,J=8.0,1.0Hz,1H),1.35(d,J=0.7Hz,10H).

[0103] Similarly, the other anthracene derivatives of the boron nitrogen multiple resonance skeleton can be synthesized similarly, wherein, for the compound of general formula A-1, it is only necessary to use the DABNACl derivative to react with bis(4-chlorophenyl)amine and then continue to react with the corresponding anthracene boronic acid derivative to obtain it. For the compound of general formula A-2, it is only necessary to use the DABNACl derivative to react with bis(4-chlorophenyl)amine, esterify it, and then react with 1,2-dibromoethane, and then continue to react with the corresponding anthracene boronic acid derivative to obtain it. For the compound of general formula A-3, it is only necessary to use the BNCzBr derivative to react with bis(4-chlorophenyl)amine, and then continue to react with the corresponding anthracene boronic acid derivative to obtain it. For the compound of general formula A-4, it is only necessary to use the BNCzBr derivative to react with bis(4-chlorophenyl)amine, esterify it, and then react with 1,2-dibromoethane, and then continue to react with the corresponding anthracene boronic acid derivative to obtain it.

[0104] The anthracene derivatives of the boron nitrogen multiple resonance skeleton can be used in organic electroluminescent devices. For example, any one of the anthracene derivatives of the boron nitrogen multiple resonance skeleton can be used as a guest luminescent material, a host luminescent material or a mixed host luminescent material of the luminescent layer in the organic electroluminescent device. Figure 1 The schematic diagram of the structure of an electroluminescent device is shown in Figure 1. The organic electroluminescent device obtained accordingly comprises a counter electrode and a transmission layer, a light-emitting layer and an injection layer between the counter electrodes, wherein the light-emitting layer is an anthracene derivative containing the boron-nitrogen multiple resonance skeleton of the present invention.

[0105] Any of the anthracene derivatives of the boron nitrogen multiple resonance skeleton described in the present invention can be used as a guest luminescent material, a host luminescent material or a mixed host luminescent material in an OLED electroluminescent device. Taking the use of an ITO (indium tin oxide) glass substrate as an example, the specific device preparation process may include: (1) substrate pretreatment, the ITO glass substrate is ultrasonically cleaned in an ITO cleaning agent, isopropanol, acetone, ethanol, and deionized water for 30 minutes, and then dried in an oven at 120°C for 2 hours after being blown dry with dry nitrogen. Before preparing the device, the ITO glass substrate is surface treated with oxygen plasma for 5 minutes, and then transferred to an organic vacuum chamber to evaporate the organic functional layer material (such as TAPC, mCP and other materials between MoO3 and Al in the device embodiment 1 below), and after completion, it is vacuum transferred to a metal vacuum chamber to evaporate a metal electrode (such as Al in the device embodiment 1 below). In the specific preparation process, the optimal main material, exciton blocking layer material or injection transport layer material can be selected according to the intrinsic properties of the anthracene derivatives of the boron nitrogen multiple resonance skeleton, such as the luminescence peak position, the lowest singlet and triplet energy level values; in addition, the film thickness of each functional layer and the concentration of host and guest doping are also systematically optimized.

[0106] The following is a device embodiment (each organic functional layer is optimized):

[0107] Device Comparison Example 1:

[0108] ITO / MoO3(10nm) / TAPC(60nm) / mCP(10nm) / PPF: Dopant(9wt%, 20nm) / PPF(10nm) / TmPyPB(30nm) / LiF(1nm) / Al(100nm).

[0109] The guest luminescent material (Dopant) of the luminescent layer is a conventional MR-TADF compound PAB (PAB is a typical MR-TADF material, for example, see ref: Wang, Y.; Duan, Y.; Guo, R.; Ye, S.; Di, K.; Zhang, W.; Zhuang, S.; Wang, L. A periphery cladding strategy to improve the performance of narrowband emitters, achieving deep-blue OLEDs with CIEy<0.08 and external quantum efficiency approaching 20%. Org. Electron. 2021, 97, 106275.), the device has an electroluminescence peak wavelength of 452 nm, a half-peak width (FWHM) of 28 nm, and a maximum external quantum efficiency (EQE max ) is 21.6%, the driving voltage is 4.0V, and the device life LT95 is 75 hours @ initial brightness 2000cd / m 2 .

[0110] Device Example 1:

[0111] ITO / MoO3(10nm) / TAPC(50nm) / mCP(10nm) / PPF: Dopant(3wt%, 20nm) / PPF(10nm) / TmPyPb(30nm) / LiF(1nm) / Al(100nm).

[0112] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 1 of the boron nitrogen multi-resonance described in the present invention. The peak wavelength of electroluminescence of the device is 448nm (deep blue light; in the art, the wavelength of "deep blue light" is 430nm to 460nm), the FWHM is 22nm, and the maximum external quantum efficiency (EQE max ) is 31.1%, the driving voltage is 3.5V, and the device life LT95 is 130 hours @ initial brightness 2000cd / m 2 .

[0113] Device Example 2:

[0114] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / mCP:Dopant(3wt%,20nm) / PPF(10nm) / TPBi(30nm) / LiF(1nm) / Al(100nm).

[0115] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 2 of the boron nitrogen multi-resonance described in the present invention. The electroluminescence peak wavelength of the device is 455nm, the FWHM is 21nm, and the EQE max The device life LT95 is 140 hours @ initial brightness 2000cd / m 2 .

[0116] Device Example 3:

[0117] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / PPF: Dopant(6wt%, 20nm) / PPF(5nm) / TmPyPb(35nm) / LiF(1nm) / Al(100nm).

[0118] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 3 of the boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 442nm, the FWHM is 18nm, and the EQE max The device life LT95 is 147 hours @ initial brightness 2000cd / m 2 .

[0119] Device Example 4:

[0120] ITO / MoO3(10nm) / TAPC(50nm) / mCP(10nm) / PPF: Dopant(6wt%, 20nm) / PPF(5nm) / TmPyPb(40nm) / LiF(1nm) / Al(100nm).

[0121] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 33 of boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 458nm, the FWHM is 21nm, and the EQE max The device life LT95 is 150 hours @ initial brightness 2000cd / m 2 .

[0122] Device Example 5:

[0123] ITO / MoO3(10nm) / TAPC(50nm) / TCTA(10nm) / PPF: Dopant(6wt%, 20nm) / PPF(5nm) / TmPyPb(40nm) / Liq(1nm) / Al(100nm).

[0124] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 34 of boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 445nm, the FWHM is 21nm, and the EQE max The device life LT95 is 154 hours @ initial brightness 2000cd / m 2 .

[0125] Device Example 6:

[0126] ITO / MoO3(10nm) / TAPC(60nm) / TCTA(5nm) / PPF: Dopant(6wt%, 20nm) / PPF(10nm) / TmPyPb(30nm) / Liq(1nm) / Al(100nm).

[0127] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 35 of boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 459nm, the FWHM is 24nm, and the EQE max The device life LT95 is 164 hours @ initial brightness 2000cd / m 2 .

[0128] Device Example 7:

[0129] ITO / MoO3(10nm) / TAPC(60nm) / TCTA(5nm) / PPF: Dopant(6wt%, 20nm) / PPF(10nm) / TmPyPb(30nm) / Liq(1nm) / Al(80nm).

[0130] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 65 of boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 463nm, the FWHM is 20nm, and the EQE max The device life LT95 is 159 hours @ initial brightness 2000cd / m 2 .

[0131] Device Example 8:

[0132] ITO / MoO3(10nm) / TAPC(60nm) / TCTA(5nm) / PPF: Dopant(6wt%, 20nm) / PPF(10nm) / TmPyPb(30nm) / Liq(1nm) / Al(80nm).

[0133] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 66 of boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 467nm, the FWHM is 25nm, and the EQE max The device life LT95 is 150 hours @ initial brightness 2000cd / m 2 .

[0134] Device Example 9:

[0135] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / PPF: Dopant(6wt%, 20nm) / PPF(5nm) / TmPyPb(35nm) / LiF(1nm) / Al(100nm).

[0136] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 67 of boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 464nm, the FWHM is 23nm, and the EQE max The device life LT95 is 170 hours @ initial brightness 2000cd / m 2 .

[0137] Device Example 10:

[0138] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / PPF: Dopant(3wt%, 20nm) / PPF(5nm) / TmPyPb(40nm) / Liq(1nm) / Al(100nm).

[0139] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 99 of boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 470nm, the FWHM is 18nm, and the EQE max The device life LT95 is 168 hours @ initial brightness 2000cd / m 2 .

[0140] Device Example 11:

[0141] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / PPF: Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0142] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 100 of the boron nitrogen multi-resonance described in the present invention. The electroluminescent peak wavelength of the device is 478nm, the FWHM is 18nm, and the EQE max The device life LT95 is 160 hours @ initial brightness 2000cd / m 2 .

[0143] Device Example 12:

[0144] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / PPF: Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0145] The guest luminescent material (Dopant) of the luminescent layer is the anthracene derivative 101 of the boron nitrogen multi-resonance described in the present invention. The peak electroluminescence wavelength of the device is 481nm, the FWHM is 22nm, and the EQE max The device life LT95 is 156 hours @ initial brightness 2000cd / m 2 .

[0146] Device Example 13:

[0147] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / Host:Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0148] The host luminescent material (Host) of the luminescent layer is the anthracene derivative 1 of the boron nitrogen multi-resonance described in the present invention, and the guest luminescent material (Dopant) of the luminescent layer is the conventional MR-TADF compound PAB. The electroluminescence peak wavelength of the device is 452nm, the FWHM is 28nm, and the EQE max The device life LT95 is 130 hours @ initial brightness 2000cd / m 2 .

[0149] Device Example 14:

[0150] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / Host:Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0151] The host luminescent material (Host) of the luminescent layer is the anthracene derivative 33 of the boron nitrogen multi-resonance described in the present invention, and the guest luminescent material (Dopant) of the luminescent layer is the conventional MR-TADF compound PAB. The electroluminescence peak wavelength of the device is 452nm, the FWHM is 28nm, and the EQE max The device life LT95 is 128 hours @ initial brightness 2000cd / m 2 .

[0152] Device Example 15:

[0153] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / Host:Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0154] The host luminescent material (Host) of the luminescent layer is the anthracene derivative 65 of the boron nitrogen multi-resonance described in the present invention, and the guest luminescent material (Dopant) of the luminescent layer is the conventional MR-TADF compound PAB. The electroluminescence peak wavelength of the device is 452nm, the FWHM is 27nm, and the EQE max The device life LT95 is 140 hours @ initial brightness 2000cd / m 2 .

[0155] Device Example 16:

[0156] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / Host:Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0157] The host luminescent material (Host) of the luminescent layer is the anthracene derivative 97 of boron nitrogen multi-resonance described in the present invention, and the guest luminescent material (Dopant) of the luminescent layer is the conventional MR-TADF compound PAB. The electroluminescence peak wavelength of the device is 453nm, the FWHM is 28nm, and the EQE max The device life LT95 is 145 hours @ initial brightness 2000cd / m2 .

[0158] Device Example 17:

[0159] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / Host:Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0160] The host luminescent material (Host) of the luminescent layer is a mixture of the boron nitrogen multi-resonance anthracene derivative 1 described in the present invention and the commercial host material PPF, and the mixing ratio is 1:1 (mass ratio, the same below). The guest luminescent material (Dopant) of the luminescent layer is a conventional MR-TADF compound PAB. The electroluminescence peak wavelength of the device is 451nm, the FWHM is 27nm, and the EQE max The device life LT95 is 127 hours @ initial brightness 2000cd / m 2 .

[0161] Device Example 18:

[0162] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / Host:Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0163] The host luminescent material (Host) of the luminescent layer is a mixture of the boron nitrogen multi-resonance anthracene derivative 33 described in the present invention and the commercial host material PPF, the mixing ratio is 1:1, and the guest luminescent material (Dopant) of the luminescent layer is a conventional MR-TADF compound PAB. The peak wavelength of electroluminescence of the device is 453nm, the FWHM is 28nm, and the EQE max The device life span LT95 is 125 hours @ initial brightness 2000cd / m 2 .

[0164] Device Example 19:

[0165] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / Host:Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0166] The host luminescent material (Host) of the luminescent layer is a mixture of the boron nitrogen multi-resonance anthracene derivative 65 described in the present invention and the commercial host material PPF, the mixing ratio is 1:1, and the guest luminescent material (Dopant) of the luminescent layer is the conventional MR-TADF compound PAB. The electroluminescence peak wavelength of the device is 452nm, the FWHM is 26nm, and the EQE max The device life LT95 is 137 hours @ initial brightness 2000cd / m 2 .

[0167] Device Example 20:

[0168] ITO / MoO3(10nm) / TAPC(60nm) / mCP(5nm) / Host:Dopant(3wt%, 20nm) / PPF(5nm) / TPBi(30nm) / Liq(1nm) / Al(100nm).

[0169] The host luminescent material (Host) of the luminescent layer is a mixture of the boron nitrogen multi-resonance anthracene derivative 97 described in the present invention and the commercial host material PPF, the mixing ratio is 1:1, and the guest luminescent material (Dopant) of the luminescent layer is the conventional MR-TADF compound PAB. The electroluminescence peak wavelength of the device is 453nm, the FWHM is 27nm, and the EQE max The device life LT95 is 141 hours @ initial brightness 2000cd / m 2 .

[0170] The above examples demonstrate that the anthracene derivatives based on the boron nitrogen multiple resonance of the present invention have extremely narrow half-peak width, which can effectively improve the color purity of the device. In addition, due to the introduction of the anthracene group with TTF effect, a synergistic effect of TTF and RISC is formed, thereby suppressing the quenching of triplet excitons. The OLED device prepared based on the anthracene derivatives of the boron nitrogen multiple resonance of the present invention can obtain a higher device efficiency (EQE max ), lower drive voltage and longer device life. At the same time, longer device life also reflects the reduction of roll-off (that is, the smaller the roll-off, the longer the life).

[0171] Attached Figure 2 The external quantum efficiency-current density relationship characteristic curves of device embodiments 1, 4, 7, and 10. From the device external quantum efficiency curves, it can be clearly concluded that the luminous efficiency of the boron nitrogen multiple resonance anthracene derivatives described in the present invention as guest luminescent materials is at a relatively high level, which meets the requirements for the industrial application of organic electroluminescent materials. Figure 3The driving voltage comparison diagram of device examples 1, 4, 7, 10 and device comparative example 1 shows that the OLED device prepared by the anthracene derivative of boron nitrogen multiple resonance described in the present invention has a lower driving voltage than the conventional MR-TADF material, which meets the requirements of the industrial application of organic electroluminescent materials. Figure 4 The device life LT95 comparison diagram of device examples 1, 4, 7, 10 and device comparative example 1 shows that the OLED device prepared by the anthracene derivative of boron nitrogen multiple resonance described in the present invention has better device stability and life than conventional MR-TADF materials, and meets the requirements for industrial application of organic electroluminescent materials. Figure 5 This is a comparison chart of the device life LT95 of device embodiments 13 to 20 and device comparison example 1. It can be seen that when the boron-nitrogen multiple resonance anthracene derivatives described in the present invention are used as the main light-emitting material or the mixed main light-emitting material, the stability and life of the OLED device can be significantly improved, which meets the requirements for the industrial application of organic electroluminescent materials.

[0172] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. An anthracene derivative based on a boron-nitrogen multiple resonance skeleton, characterized in that: The anthracene derivative has a general structure as shown in at least one of the general formulas A-1 to A-4: Wherein, the R1 group is selected from: hydrogen, deuterium, methyl, tert-butyl, trifluoromethyl, phenyl, naphthyl, anthracenyl; The R2 group is selected from: hydrogen, deuterium, methyl, phenyl, methoxy, trifluoromethyl, tert-butyl, naphthyl, anthracenyl, silane, halogen, pyrazine, pyridine, pyrimidine, pyrazine, benzimidazole ring, indolecarbazole, carbazole, phenoxazine, phenothiazine, phenoselenazine, phenanthroimidazole, substituted or unsubstituted C2-C 10 Straight chain alkyl, substituted or unsubstituted C2~C 10 Branched alkyl, substituted or unsubstituted C7~C 30 Aryl, substituted or unsubstituted C2~C 10 Alkoxy, substituted or unsubstituted C1~C 10 Alkylamino, substituted or unsubstituted C2~C 10 Silane group.

2. The anthracene derivative based on the boron-nitrogen multiple resonance skeleton according to claim 1, characterized in that: The R1 group is hydrogen, methyl, trifluoromethyl, tert-butyl or phenyl; The R2 group is a benzimidazole ring, indolecarbazole, carbazole, phenoxazine, phenothiazine, phenoselenazine, methyl, trifluoromethyl, tert-butyl or phenyl.

3. The anthracene derivative based on the boron-nitrogen multiple resonance skeleton according to claim 1, characterized in that: The structural formula of the anthracene derivative is shown in any one of Formula 1 to Formula 132:

4. Use of the anthracene derivative based on the boron nitrogen multiple resonance skeleton as claimed in any one of claims 1 to 3 in the light-emitting layer of an organic electroluminescent device.

5. The use according to claim 4, characterized in that: The organic electroluminescent device comprises in sequence: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode; Preferably, an electron blocking layer or an exciton blocking layer is further provided between the hole transport layer and the light emitting layer; and a hole blocking layer or an exciton blocking layer is further provided between the light emitting layer and the electron transport layer.

6. The use according to claim 4, characterized in that: The anthracene derivative based on the boron-nitrogen multiple resonance skeleton is specifically used as a guest luminescent material, a host luminescent material or a mixed host luminescent material in the luminescent layer of an organic electroluminescent device.

Images