Boron-nitrogen compound and organic electroluminescent device comprising same

Abstract

The invention relates to the technical field of preparation of organic photoelectric materials, in particular to a boron-nitrogen compound and an organic electroluminescent device comprising the same. The boron-nitrogen compound disclosed by the invention has good electron and hole receiving capability, and interaction among luminescent molecules can be effectively inhibited by introducing a spirocyclic group with large steric hindrance. And the energy transmission performance between a subject and an object or a sensitizer can be improved by the large conjugated spiro structure unit. Specifically, the boron-nitrogen compound provided by the invention is used as a functional layer, especially as an organic electroluminescent device manufactured by a luminescent layer, the current efficiency is improved, the lighting voltage is reduced, and meanwhile, the service life of the device is greatly prolonged. Therefore, after most electrons and holes are compounded, energy is effectively transferred to the boron-nitrogen compound, so that high luminous efficiency is realized.

Description

Technical Field

[0001] The invention relates to the technical field of organic photoelectric material preparation, and in particular to a boron nitrogen compound and an organic electroluminescent device containing the same. Background Art

[0002] With the development of multimedia technology and the improvement of information requirements, the requirements for panel display performance are getting higher and higher. Among them, OLED has a series of advantages such as autonomous luminescence, low-voltage DC drive, full curing, wide viewing angle, rich colors, etc., and has attracted widespread attention for its potential application in the new generation of display and lighting technology, and its application prospects are very broad. Organic electroluminescent devices are spontaneous luminescent devices. The mechanism of OLED luminescence is that under the action of an external electric field, electrons and holes are injected from the positive and negative electrodes respectively, and then migrate, recombine and decay in the organic material to produce luminescence. The typical structure of OLED includes one or more functional layers of cathode layer, anode layer, electron injection layer, electron transport layer, hole blocking layer, hole transport layer, hole injection layer and light-emitting layer. Although the research progress of organic electroluminescence is very rapid, there are still many problems to be solved. For example, high-efficiency, long-life, narrow-emission green light materials have always been a problem to be solved by technicians in this field. Summary of the invention

[0003] The purpose of the present invention is to provide a boron nitrogen compound and an organic electroluminescent device containing the same in view of the deficiencies in the prior art. The present invention effectively suppresses the interaction between luminescent molecules by introducing a spirocyclic large steric hindering group. By introducing a large conjugated spirocyclic structure to optimize the electron and hole receiving ability of the boron nitrogen compound, the energy transfer performance between the host and the guest can be improved, and the concentration of high-energy excitons in the luminescent layer can be reduced, thereby realizing a highly efficient, long-life, narrow-emission green light material.

[0004] In order to achieve the purpose of the present invention, the technical solution of the present invention is as follows: According to one or more embodiments, the present invention provides a boron nitrogen compound having a general structure shown in the following formula I; ; In Formula I, Ring A and Ring B are each independently selected from substituted or unsubstituted C6-C30 aryl groups and C5-C30 heteroaryl groups, and at least one of Ring A or Ring B is selected from substituted C6-C30 aryl groups; R1-R6 are monosubstituted or polysubstituted; R1-R6 are each independently selected from hydrogen, deuterium, C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C5-C30 heteroaryl groups; R4 and R5 can be selectively connected to form a ring; when Ring A, Ring B, and R1-R6 contain substitutions, the substitutions are independently selected from any one or more of deuterium, C1-C24 alkyl, C3-C24 cycloalkyl, C6-C30 aryl groups, and C5-C30 heteroaryl groups.

[0005] Preferably, in Formula I, Ring A and Ring B are each independently selected from substituted or unsubstituted phenyl, naphthyl or quinoxalinyl; the substitution is selected from one or more of deuterium, phenyl, biphenyl, tert-butylphenyl, tert-butylbiphenyl, tert-phenyl, pyridyl, 4-phenylpyridyl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, N-phenyl-carbazolyl, spirocyclopentanefluorenyl, and 2,4,6-triphenyltriazine; and at least one of Ring A or Ring B is selected from substituted phenyl.

[0006] More preferably, in Formula I, Ring A and Ring B are not simultaneously selected from naphthyl or quinoxalinyl.

[0007] Preferably, in Formula I, R1-R3 are each the same or different and are selected from C1-C10 alkyl groups.

[0008] More preferably, in Formula I, R1-R3 are each identically selected from C1-C5 alkyl.

[0009] Preferably, in Formula I, R4-R5 are each identically selected from tert-butylphenyl, and when R4-R5 are each identically selected from tert-butylphenyl, R6 is selected from hydrogen or deuterium.

[0010] Preferably, R4 and R5 in Formula I are connected to form a ring to form a general structure shown in Formula I-1: ; In formula I-1, the substitution of ring A, ring B, R1-R3, and R6 are as defined in formula I above; R7 is monosubstituted or polysubstituted, and R7 is independently selected from one or more of hydrogen, deuterium, C1-C24 alkyl, C6-C30 aryl, and C5-C30 heteroaryl; R6 and R7 can be selectively connected to form a ring.

[0011] Preferably, when R6 and R7 in Formula I-1 are not connected to form a ring, R6 is independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C30 aryl; the substitution is selected from deuterium, C1-C14 alkyl, C3-C14 cycloalkyl, C5-C18 nitrogen heteroaryl; R7 is independently selected from C1-C14 alkyl.

[0012] Further preferably, when R6 and R7 are not connected to form a ring, R6 is independently selected from substituted or unsubstituted phenyl and biphenyl; the substitution is selected from one or more of deuterium, methyl, ethyl, propyl, tert-butyl, adamantyl, and pyridyl; R7 is independently selected from methyl, ethyl, propyl, butyl, tert-butyl, pentyl, and tert-pentyl.

[0013] Preferably, R6 and R7 in Formula I-1 can form the following structure after being connected into a ring, where * indicates the connection mode: .

[0014] Preferably, one or more hydrogen atoms in Formula I or Formula I-1 may be deuterated.

[0015] Preferably, Formula I or Formula I-1 has a bilaterally symmetrical substitution structure.

[0016] According to one or more embodiments, the present invention provides a specific boron nitrogen compound, wherein the boron nitrogen compound is selected from any one of the chemical structures shown below, wherein "D" represents deuterium: .

[0017] On the one hand, the present invention also provides the use of the boron nitrogen compound with the general structure shown in Formula I or Formula I-1 in the preparation of electronic devices.

[0018] Furthermore, the electronic devices include organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic photoelectric devices, organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs), and organic laser diodes (O-lasers).

[0019] On the other hand, the present invention also provides an organic electroluminescent device, which comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises a boron nitrogen compound having a general structure as shown in Formula I or Formula I-1 above.

[0020] Furthermore, the organic functional layer further comprises a light-emitting layer, wherein the light-emitting layer comprises a boron-nitrogen compound having a general structure as shown in Formula I or Formula I-1 above, wherein the mass percentage of the boron-nitrogen compound is 0.1%-50%.

[0021] In another aspect, the present invention also provides an organic photoelectric device, comprising a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer comprises a boron nitrogen compound having a general structure as shown in Formula I or Formula I-1 above. For example, the boron nitrogen compound can be included in the light-emitting material layer as a dopant.

[0022] The present invention also provides a composition, which comprises a boron-nitrogen compound having a general structure as shown in the above formula I or formula I-1.

[0023] The present invention also provides a preparation, which comprises a boron nitrogen compound having a general structure as shown in Formula I or Formula I-1 above or a composition as described above and at least one solvent. The solvent is not particularly limited, and can be used, for example, unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents, halogenated unsaturated hydrocarbon solvents, ether solvents or ester solvents well known to those skilled in the art; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetralin, n-butylbenzene, sec-butylbenzene or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; the ester solvent is an alkyl benzoate.

[0024] The present invention also provides a display or lighting device, which comprises one or more of the organic electroluminescent devices or organic photoelectric devices described above.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The present invention provides a boron nitrogen compound with good electron and hole receiving ability, which can effectively inhibit the interaction between luminescent molecules by introducing a large sterically hindered spiro ring and a monosubstituted spiro ring group. The large conjugated spiro ring structure and the monosubstituted dibenzofuran, dibenzothiophene, biphenyl, fluorene and other units can make the compound have the ability to enhance the energy transfer performance between the host and the guest (or sensitizer). Specifically, the organic electroluminescent device made of the boron nitrogen compound of the present invention as a functional layer, especially as a light-emitting layer, has a good current efficiency improvement effect, and the life of the device is also greatly improved. It shows that after most electrons and holes recombine, the energy is effectively transferred to the boron nitrogen compound, thereby achieving high luminous efficiency. DETAILED DESCRIPTION

[0027] The content of the present invention is described in detail below. The description of the constituent elements recorded below is sometimes based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples. By referring to the following specific embodiments and the examples contained therein, the present disclosure can be more easily understood. Before disclosing and describing the compounds, devices and / or methods of the present invention, it should be understood that, unless otherwise stated, they are not limited to specific synthetic methods or specific reagents, because this can be varied. It should also be understood that the terms used in the present invention are only used to describe specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used in the practice or test, exemplary methods and materials are now described.

[0028] The term "alkyl" as used herein refers to a monovalent alkyl group having 1 to 24 carbon atoms, preferably 1 to 14 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of this term include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, etc.

[0029] The "cycloalkyl" of the present invention refers to a cyclic alkyl group having 3 to 24 carbon atoms and a monocyclic or polycyclic condensed ring, preferably 3 to 14 carbon atoms, which can be substituted by 1 to 3 alkyl groups at will. Such cycloalkyl groups include, for example, monocyclic structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexane, cyclooctyl, 1-methylcyclopropyl, 2-methylcyclopentyl, 2-methylcyclooctyl, methylcyclohexane, etc., or polycyclic structures such as adamantyl, etc.

[0030] The "aryl" of the present invention refers to an unsaturated aromatic carbocyclic ring having 6-30 carbon atoms and having a monocyclic (such as phenyl) or polycyclic condensation (such as naphthyl or anthracenyl), preferably having 6-18 carbon atoms, more preferably 1-12 carbon atoms. Preferred aryl groups include phenyl, biphenyl, naphthyl, phenanthrenyl, terphenyl, etc. Unless otherwise defined for individual substituents, such aryl groups may be optionally substituted by 1-3 of the following substituents: hydroxyl, acyl, acyloxy, alkyl, alkoxy, alkenyl, alkynyl, amino, aminoacyl, aryl, aryloxy, carboxyl, carboxyl ester, aminocarboxyl ester, cyano, halogen, nitro, heteroaryl, heterocycle, thioalkoxy, trihalomethyl, etc. Preferred substituents include alkyl, alkoxy, halogen, cyano, nitro, trihalomethyl and thioalkoxy. But not limited thereto.

[0031] The "heteroaryl" mentioned in the present invention refers to a general term for a group having 5-30 carbon atoms and one or more aromatic carbon atoms in the aromatic group are replaced by a heteroatom, preferably 5-18 carbon atoms, and the heteroatom includes but is not limited to oxygen (O), sulfur (S) or nitrogen (N), silicon (Si) or germanium (Ge) atoms. The heteroaryl group can be a monocyclic heteroaryl group or a condensed ring heteroaryl group. Examples may include pyridyl, pyrrolyl, pyridyl, thienyl, furanyl, indolyl, quinolyl, isoquinolyl, quinoxalinyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc., but are not limited thereto.

[0032] The substitution in the present invention may be by single bond or fusion. The "connection to form a ring" in the present invention may include a single ring, multiple rings and fused rings, and the ring may be unsubstituted or substituted by one or more identical or different groups.

[0033] As used in the specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes a mixture of two or more components.

[0034] Unless otherwise stated, all commercial reagents involved in the following experiments were used directly after purchase.

[0035] In a preferred embodiment of the present invention, the OLED device of the present invention contains a hole transport layer, and the hole transport material can be preferably selected from known or unknown materials, and is particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures (Ph is phenyl):

[0036] In a preferred embodiment of the present invention, the hole injection layer contained in the OLED device of the present invention. The preferred hole injection layer material of the present invention is the following structure, but it does not mean that the present invention is limited to the following structure:

[0037] In a preferred embodiment of the present invention, the electron transport layer can be selected from at least one of the following compounds, but it does not mean that the present invention is limited to the following structures:

[0038] The preparation method of the boron nitrogen compound, i.e. the guest compound, and the luminescent properties of the device are explained in detail in conjunction with the following examples. The molecular structure formula of the relevant material is shown below:

[0039] Example 1: Synthesis of Compound 1 ; (1) Synthesis of compound 1-3: Compound 1-1 (275 mg, 1 mmoL) and compound 1-2 (290 mg, 1 mmoL) were dissolved in 50 mL DMF solution. Potassium carbonate (691 mg, 5 mmoL), palladium acetate (12 mg, 0.05 mmoL), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmoL) were added under nitrogen atmosphere. The reaction system was heated at 140 degrees Celsius for 24 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography with the eluent being dichloromethane: petroleum ether = 1:7 to obtain product 1-3 (212 mg, yield 49%). Mass spectrum m / z, theoretical value 437.31; measured value M+H: 438.33; (2) Synthesis of compound 1-6: Compound 1-4 (279 mg, 1 mmoL) and compound 1-5 (334 mg, 1 mmoL) were dissolved in 50 mL DMF solution, and potassium carbonate (691 mg, 5 mmoL) was added. The reaction system was heated at 140 degrees Celsius for 24 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:8, to obtain product 1-6 (523 mg, yield 88%). Mass spectrum m / z, theoretical value 592.99; measured value M+H: 594.01; (3) Synthesis of compound 1-8: BuLi (0.5 mL, 1 mmoL, 2M in hexane) was slowly added to a solution of compound 1-6 (593 mg, 1 mmoL) in anhydrous THF (50 mL) at -78°C. After 3 hours of reaction, 1-7 (372 mg, 1 mmoL) was slowly added. After slowly warming to room temperature, the reaction was allowed to proceed overnight, and 1 mL of ice water was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the residue was dissolved in acetic acid (100 mL), and concentrated hydrochloric acid (10 mL) was added dropwise. The reaction system was refluxed overnight and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:1, to obtain product 1-8 (457 mg, yield 55%). Mass spectrum m / z, theoretical value 821.24; measured value M+H: 822.26; (4) Synthesis of compound 1-9: Compound 1-8 (821 mg, 1 mmoL) and compound 1-3 (437 mg, 1 mmoL) were dissolved in 50 mL toluene solution. Under nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmoL), palladium acetate (12 mg, 0.05 mmoL), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmoL) were added. The reaction system was refluxed for 24 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography with the eluent being dichloromethane: petroleum ether = 1:2 to obtain product 1-9 (387 mg, yield 33%). Mass spectrum m / z, theoretical value 1178.62; measured value M+H: 1179.65; (5) Synthesis of compound 1: Under nitrogen atmosphere and zero temperature, tert-butyl lithium (1.25 mL, 1.6 M pentane solution, 2 mmoL) was slowly added dropwise to a solution of compound 1-9 (1178 mg, 1 mmoL) in tert-butylbenzene (100 mL). After the system was reacted at 60 °C for 4 hours, the temperature was lowered to -50 °C, and then BBr3 (494 mg, 2 mmoL) was added. After reacting at room temperature for 1 hour, N,N-diisopropylethylamine (259 mg, 2 mmoL) was added. The temperature was then raised to 120 °C for 12 hours. After cooling to room temperature, 5 mL of sodium acetate aqueous solution (1 M) was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:3, to obtain product 1 (236 mg, yield 20%). Mass spectrum m / z, theoretical value 1152.65; measured value M+H: 1153.68.

[0040] Example 2: Synthesis of Compound 57 ; (1) Synthesis of compound 57-3: Compound 57-1 (270 mg, 1 mmoL) and compound 57-2 (316 mg, 1 mmoL) were dissolved in 50 mL toluene solution. Under nitrogen atmosphere, 10 mL sodium carbonate aqueous solution (2 M) and tetrakis(triphenylphosphine)palladium (57 mg, 0.05 mmoL) were added. The reaction system was refluxed for 24 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography with dichloromethane: petroleum ether = 1:10 as the eluent to obtain product 57-3 (231 mg, yield 61%). Mass spectrum m / z, theoretical value 380.09; measured value M+H: 381.11; (2) Synthesis of compound 57-5: Compound 57-3 (380 mg, 1 mmoL) and compound 57-4 (558 mg, 2 mmoL) were dissolved in 50 mL DMF solution, and potassium carbonate (691 mg, 5 mmoL) was added. The reaction system was heated at 140 degrees Celsius for 48 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:9, to obtain product 57-5 (712 mg, yield 79%). Mass spectrum m / z, theoretical value 898.48; measured value M+H: 899.50; (3) Synthesis of compound 57-7: BuLi (0.5 mL, 1 mmoL, 2M in hexane) was slowly added to a solution of compound 57-5 (898 mg, 1 mmoL) in anhydrous THF (50 mL) at -78°C. After 3 hours of reaction, 57-6 (422 mg, 1 mmoL) was slowly added. After slowly warming to room temperature, the reaction was allowed to proceed overnight, and 1 mL of ice water was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the residue was dissolved in acetic acid (100 mL), and concentrated hydrochloric acid (10 mL) was added dropwise. The reaction system was refluxed overnight and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:3, to obtain product 57-7 (487 mg, yield 40%). Mass spectrum m / z, theoretical value 1224.73; measured value M+H: 1225.75; (4) Synthesis of compound 57-8: Compound 57-7 (1224 mg, 1 mmol) was slowly added to 100 mL of glacial acetic acid at 0°C in the dark, and then NBS (178 mg, 1 mmol) was slowly added and stirred at 0°C for 18 hours. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:4, to obtain product 57-8 (465 mg, yield 36%). Mass spectrum m / z, theoretical value 1302.64; measured value M+H: 1303.66; (5) Synthesis of compound 57: Under nitrogen atmosphere and zero temperature, tert-butyl lithium (1.25 mL, 1.6 M pentane solution, 2 mmol) was slowly added dropwise to a solution of compound 57-8 (1302 mg, 1 mmol) in tert-butylbenzene (100 mL). The system was reacted at 60 °C for 4 hours, then cooled to -50 °C, and then BBr3 (494 mg, 2 mmol) was added. After reacting at room temperature for 1 hour, N,N-diisopropylethylamine (259 mg, 2 mmol) was added. The temperature was then raised to 120 °C and reacted for 12 hours. After cooling to room temperature, 5 mL of sodium acetate aqueous solution (1 M) was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography with dichloromethane: petroleum ether = 1:5 as the eluent to obtain product 57 (248 mg, yield 20%). Mass spectrum m / z, theoretical value 1232.71; measured value M+H: 1233.73.

[0041] Example 3: Synthesis of Compound 99 ; Synthesis of compound 99-3: BuLi (0.5 mL, 1 mmoL, 2M in hexane) was slowly added to a solution of compound 99-1 (898 mg, 1 mmoL) in anhydrous THF (50 mL) at -78 °C. After 3 hours of reaction, 99-2 (230 mg, 1 mmoL) was slowly added. After slowly warming to room temperature, the reaction was allowed to proceed overnight, and 1 mL of ice water was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the residue was dissolved in acetic acid (100 mL), and then concentrated hydrochloric acid (10 mL) was added dropwise. The reaction system was refluxed overnight and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:5, to obtain the product 99-3 (423 mg, yield 46%). Mass spectrum m / z, theoretical value 922.39; measured value M+H: 923.42; Synthesis of compound 99-5: BuLi (0.5 mL, 1 mmoL, 2M in hexane) was slowly added to a solution of compound 99-3 (922 mg, 1 mmoL) in anhydrous THF (50 mL) at -78 °C. After 3 hours of reaction, 99-4 (422 mg, 1 mmoL) was slowly added. After slowly warming to room temperature, the reaction was allowed to proceed overnight, and 1 mL of ice water was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the residue was dissolved in acetic acid (100 mL), and then concentrated hydrochloric acid (10 mL) was added dropwise. The reaction system was refluxed overnight and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:6, to obtain the product 99-5 (504 mg, yield 42%). Mass spectrum m / z, theoretical value 1198.62; measured value M+H: 1199.64; Synthesis of compound 99-6: At 0°C in the dark, compound 99-5 (1198 mg, 1 mmoL) was slowly added to 100 mL of glacial acetic acid, and then NBS (178 mg, 1 mmoL) was slowly added and stirred at room temperature for 18 hours. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:4, to obtain product 99-6 (562 mg, yield 44%). Mass spectrum m / z, theoretical value 1276.53; measured value M+H: 1277.56; Synthesis of compound 99: Under nitrogen atmosphere and zero temperature, tert-butyl lithium (1.25 mL, 1.6 M pentane solution, 2 mmoL) was slowly added dropwise to a solution of compound 99-6 (1276 mg, 1 mmoL) in tert-butylbenzene (100 mL). After the system was reacted at 60 °C for 4 hours, the temperature was lowered to -50 °C, and then BBr3 (494 mg, 2 mmoL) was added. After reacting at room temperature for 1 hour, N,N-diisopropylethylamine (259 mg, 2 mmoL) was added. The temperature was then raised to 120 °C for 12 hours. After cooling to room temperature, 5 mL of sodium acetate aqueous solution (1 M) was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:6, to obtain product 99 (278 mg, yield 23%). Mass spectrum m / z, theoretical value 1206.60; measured value M+H: 1207.63.

[0042] Example 4: Synthesis of Compound 3 Compound 3 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 24%. Mass spectrum m / z, theoretical value 1126.60; measured value M+H: 1127.62.

[0043] Example 5: Synthesis of Compound 5 Compound 5 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 24%. Mass spectrum m / z, theoretical value 1142.57; measured value M+H: 1143.59.

[0044] Example 6: Synthesis of Compound 10 Compound 10 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 21%. Mass spectrum m / z, theoretical value: 1188.65; measured value: M+H: 1189.67.

[0045] Example 7: Synthesis of Compound 11 Compound 11 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 24%. Mass spectrum m / z, theoretical value 1267.67; measured value M+H: 1268.69.

[0046] Example 8: Synthesis of Compound 14 Compound 14 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 25%. Mass spectrum m / z, theoretical value: 1251.66; measured value: M+H: 1252.68.

[0047] Example 9: Synthesis of Compound 17 Compound 17 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 27%. Mass spectrum m / z, theoretical value 1202.67; measured value M+H: 1203.69.

[0048] Example 10: Synthesis of Compound 22 Compound 22 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 25%. Mass spectrum m / z, theoretical value 1176.61; measured value M+H: 1177.63.

[0049] Example 11: Synthesis of Compound 26 Compound 26 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 20%. Mass spectrum m / z, theoretical value 1317.68; measured value M+H: 1318.71.

[0050] Example 12: Synthesis of Compound 32 Compound 32 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 26%. Mass spectrum m / z, theoretical value: 1164.62; measured value: M+H: 1165.65.

[0051] Example 13: Synthesis of Compound 39 Compound 39 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 26%. Mass spectrum m / z, theoretical value 1182.70; measured value M+H: 1183.72.

[0052] Example 14: Synthesis of Compound 44 Compound 44 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 23%. Mass spectrum m / z, theoretical value: 1194.61; measured value: M+H: 1195.63.

[0053] Example 15: Synthesis of Compound 52 Compound 52 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 21%. Mass spectrum m / z, theoretical value 1126.63; measured value M+H: 1127.65.

[0054] Example 16: Synthesis of Compound 60 Compound 60 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 21%. Mass spectrum m / z, theoretical value 1206.66; measured value M+H: 1207.68.

[0055] Example 17: Synthesis of Compound 67 Compound 67 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 26%. Mass spectrum m / z, theoretical value 1166.57; measured value M+H: 1167.59.

[0056] Example 18: Synthesis of Compound 76 Compound 76 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 22%. Mass spectrum m / z, theoretical value: 1178.64; measured value: M+H: 1179.67.

[0057] Example 19: Synthesis of Compound 86 Compound 86 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 24%. Mass spectrum m / z, theoretical value 1214.67; measured value M+H: 1215.69.

[0058] Example 20: Synthesis of Compound 92 Compound 92 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 20%. Mass spectrum m / z, theoretical value 1141.64; measured value M+H: 1142.66.

[0059] Example 21: Synthesis of Compound 104 Compound 104 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 29%. Mass spectrum m / z, theoretical value 1338.70; measured value M+H: 1339.72.

[0060] Example 22: Synthesis of Compound 107 Compound 107 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 23%. Mass spectrum m / z, theoretical value: 1166.57; measured value: M+H: 1167.69.

[0061] Example 23: Synthesis of Compound 108 Compound 108 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 25%. Mass spectrum m / z, theoretical value: 1168.56; measured value: M+H: 1169.58.

[0062] Example 24: Synthesis of Compound 109 Compound 109 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 23%. Mass spectrum m / z, theoretical value: 1216.59; measured value: M+H: 1217.61.

[0063] Example 25: Synthesis of Compound 115 Compound 115 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 26%. Mass spectrum m / z, theoretical value: 1186.60; measured value: M+H: 1187.62.

[0064] Example 26: Synthesis of Compound 116 Compound 116 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 25%. Mass spectrum m / z, theoretical value 1278.70; measured value M+H: 1279.72.

[0065] Example 27: Synthesis of Compound 119 Compound 119 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 23%. Mass spectrum m / z, theoretical value: 1180.55; measured value: M+H: 1181.58.

[0066] Example 28: Synthesis of Compound 129 Compound 129 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 22%. Mass spectrum m / z, theoretical value 1146.51; measured value M+H: 1147.53.

[0067] Example 29: Synthesis of Compound 133 Compound 133 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 26%. Mass spectrum m / z, theoretical value 1146.51; measured value M+H: 1147.53.

[0068] Example 30: Synthesis of Compound 141 Compound 141 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 23%. Mass spectrum m / z, theoretical value: 1218.58; measured value: M+H: 1219.61.

[0069] Example 31: Synthesis of Compound 149 Compound 149 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 24%. Mass spectrum m / z, theoretical value 1117.55; measured value M+H: 1118.57.

[0070] Example 32: Synthesis of Compound 152 Compound 152 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 29%. Mass spectrum m / z, theoretical value: 1168.56; measured value: M+H: 1169.58.

[0071] Example 33: Synthesis of Compound 153 Compound 153 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 27%. Mass spectrum m / z, theoretical value: 1278.66; measured value: M+H: 1279.68.

[0072] Example 34: Synthesis of Compound 157 Compound 157 was prepared by referring to the preparation schemes of Example 1 to Example 3. The yield of the final product was 22%. Mass spectrum m / z, theoretical value: 1072.57; measured value: M+H: 1073.59.

[0073] Fabrication of OLED devices: As a reference preparation method for a device embodiment, the present invention evaporates a p-doped material on the surface of an ITO glass with a light-emitting area of ​​2 mm×2 mm or on an anode, or co-evaporates the p-doped material with a hole transport material at a concentration of 1% to 50% to form a 5-100 nm hole injection layer (HIL), forms a 5-200 nm hole transport layer (HTL) on the hole injection layer, and then co-evaporates a host material (GH-1 and GH-2), GD-Ir and a boron nitrogen compound (guest material) prepared by the present invention on the hole transport layer at a mass ratio of 63:33:3:1 to form a 10-100 nm light-emitting layer (EML), and finally co-evaporates to form a 35 nm electron transport layer (ETL), and then evaporates 70 nm of cathode Al to manufacture an organic electroluminescent diode.

[0074] In a preferred specific embodiment, the structure of the bottom-emitting OLED device provided by the present invention is: glass containing ITO is used as the anode, and HIL is HT-4:P-3 (mass ratio 97:3) evaporated in sequence, with a thickness of 10 nm; HTL is HT-4, with a thickness of 60 nm; EBL is HT-15, with a thickness of 20 nm, EML is the main material (GH-1:GH-2): GD-Ir: the boron nitrogen compound 1 provided by the present invention (mass ratio 63:33:3:1), with a thickness of 35 nm, ETL is ET-5:LiQ (mass ratio 50:50), with a thickness of 35 nm; EIL is a 1 nm LiF layer; then the cathode Al is evaporated to 70 nm to prepare an organic electroluminescent diode, which is recorded as Application Example 1.

[0075] Referring to the device structure provided in Application Example 1, the boron nitrogen compounds listed in Table 1 were selected as the implementation objects to replace Compound 1 to prepare organic electroluminescent diodes, which were respectively recorded as Application Examples 2 to Application Examples 26 and Comparative Examples 1 to 3. The current efficiency and life of the device application examples and comparative examples prepared above were tested by standard methods, and the device luminescence characteristic data are shown in Table 1.

[0076] Table 1. Device luminescence characteristics data table

[0077] As can be seen from Table 1, the compounds of the present invention are used as light-emitting layer materials to prepare electronic devices, which have higher current efficiency and lifespan. Compared with Comparative Examples 1-3, Application Examples 1 to Application Examples 26 all show good device performance in terms of current efficiency and lifespan, and the improvement in the performance of each device is achieved based on the better electron transmission ability of the boron nitrogen compound material of the present invention. This shows that the boron nitrogen compound provided by the present invention has certain commercial application value.

[0078] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A boron-nitrogen compound, characterized in that: The boron nitrogen compound has a general structure shown in the following formula I: ； In Formula I, Ring A and Ring B are each independently selected from substituted or unsubstituted C6-C30 aryl groups and C5-C30 heteroaryl groups, and at least one of Ring A or Ring B is selected from substituted C6-C30 aryl groups; R1-R6 are monosubstituted or polysubstituted; R1-R6 are each independently selected from hydrogen, deuterium, C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C5-C30 heteroaryl groups; R4 and R5 can be selectively connected to form a ring; when Ring A, Ring B, and R1-R6 contain substitutions, the substitutions are independently selected from any one or more of deuterium, C1-C24 alkyl, C3-C24 cycloalkyl, C6-C30 aryl groups, and C5-C30 heteroaryl groups.

2. The boron nitrogen compound according to claim 1, characterized in that Ring A and Ring B are each independently selected from substituted or unsubstituted phenyl, naphthyl or quinoxalinyl; the substitution is selected from one or more of deuterium, phenyl, biphenyl, tert-butylphenyl, tert-butylbiphenyl, terphenyl, pyridyl, 4-phenylpyridyl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, N-phenyl-carbazolyl, spirocyclopentanefluorenyl, and 2,4,6-triphenyltriazine; and at least one of Ring A or Ring B is selected from substituted phenyl.

3. The boron nitrogen compound according to claim 1, characterized in that In Formula I, R4 and R5 are connected to form a ring to form a general structure shown in Formula I-1: ; In formula I-1, the substitution of ring A, ring B, R1-R3, and R6 are as described in claim 1; R7 is monosubstituted or polysubstituted, and R7 is independently selected from one or more of hydrogen, deuterium, C1-C24 alkyl, C6-C30 aryl, and C5-C30 heteroaryl; R6 and R7 can be selectively connected to form a ring.

4. The boron nitrogen compound according to claim 3, characterized in that When R6 and R7 in formula I-1 are not connected to form a ring, R6 is independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C30 aryl; the substitution is selected from deuterium, C1-C14 alkyl, C3-C14 cycloalkyl, C5-C18 nitrogen heteroaryl; R7 is independently selected from C1-C14 alkyl.

5. The boron nitrogen compound according to claim 3, characterized in that When R6 and R7 are not connected to form a ring, R6 is independently selected from substituted or unsubstituted phenyl and biphenyl; the substitution is selected from one or more of deuterium, methyl, ethyl, propyl, tert-butyl, adamantyl, and pyridyl; R7 is independently selected from methyl, ethyl, propyl, butyl, tert-butyl, pentyl, and tert-pentyl.

6. The boron nitrogen compound according to claim 3, characterized in that When R6 and R7 are selectively connected to form a ring, R6 and R7 can form the following structure, where * indicates the connection site: 。 7. The boron nitrogen compound according to claim 1, characterized in that The boron nitrogen compound is selected from any one of the chemical structures shown below, wherein "D" represents deuterium: 。 8. Use of the boron nitrogen compound according to any one of claims 1 to 3 in the preparation of electronic devices.

9. The use according to claim 8, characterized in that: The electronic device is an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic photoelectric device, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell and / or an organic laser diode.

10. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer contains the boron nitrogen compound as claimed in any one of claims 1 to 3.

11. An organic optoelectronic device, characterized in that: The organic photoelectric device comprises a first electrode, a second electrode facing the first electrode, and a light-emitting material layer arranged between the first electrode and the second electrode; the light-emitting material layer contains the boron nitrogen compound as claimed in any one of claims 1 to 3.

12. A composition, characterized in that The composition comprises the boron nitrogen compound according to any one of claims 1 to 3.

13. A preparation, characterized in that The preparation comprises the boron nitrogen compound according to any one of claims 1 to 3 and at least one solvent.

14. A display or lighting device, characterized in that: The device comprises one or more of the organic electroluminescent device according to claim 10 and / or the organic photoelectric device according to claim 11.

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