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 large-steric-hindrance azafluorene / benzfluorene / azabenzfluorene / silafluorene / germanium heterofluorene and other groups. The energy transmission performance between a subject and an object or a sensitizer can be improved by a large conjugated spiro structure unit, an sp2 aza-aromatic ring and other structures. 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 shortcomings of the prior art. The present invention effectively inhibits the interaction between luminescent molecules by introducing a spirocyclic large steric hindering group. By introducing a large conjugated spirocyclic structure and sp 2 Optimizing the electron and hole acceptance capacity of boron nitrogen compounds through structures such as nitrogen heteroaromatic rings can enhance the energy transfer performance between the host and the guest and reduce the concentration of high-energy excitons in the light-emitting layer, thereby achieving efficient, long-life, narrow-emission green light materials.

[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 structure shown in the following formula (I); ; In formula (I), X is selected from C, Si or Ge; Ring A is selected from substituted or unsubstituted aryl C6~C30, substituted or unsubstituted C6~C30 heteroaryl; Y1, Y2, Y3, and Y4 are each independently selected from CR or N; R1-R4 are monosubstituted or polysubstituted; the R, R1-R6 are each independently selected from hydrogen, deuterium, C1~C24 alkyl, substituted or unsubstituted C3~C24 cycloalkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C6~C30 heteroaryl; the heteroatom in the heteroaryl is selected from N, O, and S; when there is substitution, the substituent is independently selected from any one or more of deuterium, C1~C24 alkyl, C3~C24 cycloalkyl, and C6~C30 aryl; R, R4, R5, and R6 can be connected with adjacent substituent groups to form a ring.

[0005] Preferably, the boron nitrogen compound has a structure represented by the following formula (I-1) or formula (I-2); ; In formula (I-1) or formula (I-2), X, ring A, Y1-Y4, R1-R4 have the same meanings as defined in formula (I) above; R7, R8, R9 are monosubstituted or polysubstituted; R7, R8, R9 are each independently selected from hydrogen, deuterium, C1~C24 alkyl, C3~C24 cycloalkyl; R4, R7, R8 can be fused with adjacent groups to form a ring.

[0006] In a preferred embodiment, in formula (I-1), R1 is selected from hydrogen; R4 is the same or different and is selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, or is fused with an adjacent substituent group to form a benzene ring or a naphthalene ring; R7 and R8 are the same or different and are selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, cyclohexane, and adamantyl.

[0007] A preferred embodiment, in formula (I-2), R1 is selected from substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted tetrahydronaphthyl; when there is substitution, the substituent is selected from one or more of hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, adamantyl, and pyridyl; R4 and R9 are the same or different and are selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, and adamantyl.

[0008] In a preferred embodiment, R2 and R3 in formula (I) are independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl and tert-pentyl.

[0009] In a preferred embodiment, the ring A in formula (I), formula (I-1) or formula (I-2) is selected from phenyl, pyridyl, naphthyl or any one of the following ring structures: .

[0010] In a more preferred embodiment, when Y1-Y4 in formula (I), formula (I-1) or formula (I-2) are each independently selected from CR, ring A is selected from pyridyl or any one of the following ring structures: .

[0011] In a more preferred embodiment, when at least one or more of Y1-Y4 in formula (I), formula (I-1) or formula (I-2) is selected from N, ring A is selected from phenyl or naphthyl.

[0012] In a preferred embodiment, the R group in formula (I), formula (I-1) or formula (I-2) is independently selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, and R can be fused with an adjacent substituted group to form a substituted or unsubstituted cyclopentane; and R2 and R3 are independently selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, and heptyl when they appear each time.

[0013] 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: .

[0014] On the one hand, the present invention also provides the use of the boron nitrogen compound with the general structure shown in the above formula (I) in electronic devices.

[0015] 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).

[0016] In another aspect, the present invention further provides an organic electroluminescent device, which comprises a boron nitrogen compound having a general structure as shown in the above formula (I).

[0017] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises a boron-nitrogen compound having a general structure as shown in formula (I) above. The mass percentage of the boron-nitrogen compound is 0.1%-50%.

[0018] In another aspect, the present invention further 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) above. For example, the boron nitrogen compound can be included in the light-emitting material layer as a dopant.

[0019] The present invention also provides a composition, which comprises a boron-nitrogen compound having a general structure as shown in the above formula (I).

[0020] The present invention also provides a preparation, which comprises a boron nitrogen compound having a general structure as shown in the above formula (I) 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.

[0021] 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.

[0022] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a boron-nitrogen compound with good electron and hole accepting ability, which can effectively inhibit the interaction between luminescent molecules by introducing large sterically hindered nitrogen heterofluorene / benzofluorene / azabenzofluorene / silicon heterofluorene / germanium heterofluorene and other groups. Large conjugated spirocyclic structural units and sp 2 The structure of nitrogen heteroaromatic ring makes the compound have the ability to improve 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 effect of improving the current efficiency, and the life of the device is also greatly improved. This 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

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] The "heteroaryl" mentioned in the present invention refers to a general term for a group having 6-30 carbon atoms and one or more aromatic carbon atoms in the aromatic group are replaced by a heteroatom, preferably 6-18 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, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc., but are not limited thereto.

[0028] The substitution in the present invention may be by a single bond or by fusion.

[0029] 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.

[0030] Unless otherwise stated, all commercial reagents involved in the following experiments were used directly after purchase.

[0031] 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):

[0032] 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:

[0033] 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:

[0034] 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:

[0035] 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 (232 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 = 1:1, to obtain product 1-8 (418 mg, yield 61%). Mass spectrum m / z, theoretical value 681.16; measured value M+H: 682.18; (4) Synthesis of compound 1-9: Compound 1-8 (681 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 (410 mg, yield 39%). Mass spectrum m / z, theoretical value 1038.54; measured value M+H: 1039.56; (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 (1038 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 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 the eluent being dichloromethane: petroleum ether = 1:3, to obtain product 1 (265 mg, yield 26%). Mass spectrum m / z, theoretical value 1012.56; measured value M+H: 1013.58.

[0036] Example 2: Synthesis of Compound 112 ; (1) Synthesis of compound 112-3: Compound 112-1 (270 mg, 1 mmoL) and compound 112-2 (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 112-3 (231 mg, yield 61%). Mass spectrum m / z, theoretical value 380.09; measured value M+H: 381.11; (2) Synthesis of compound 112-5: Compound 112-3 (380 mg, 1 mmoL) and compound 112-4 (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 112-5 (712 mg, yield 79%). Mass spectrum m / z, theoretical value 898.48; measured value M+H: 899.50; (3) Synthesis of compound 112-7: BuLi (0.5 mL, 1 mmol, 2M in hexane) was slowly added to a solution of compound 112-5 (898 mg, 1 mmol) in anhydrous THF (50 mL) at -78°C. After reacting for 3 hours, 112-6 (232 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 the product 112-7 (456 mg, yield 44%). Mass spectrum m / z, theoretical value 1034.62; measured value M+H: 1035.64; (4) Synthesis of compound 112-8: Compound 112-7 (1034 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 resulting crude product was separated and purified by silica gel chromatography with the eluent being dichloromethane: petroleum ether = 1:5 to obtain product 112-8 (342 mg, yield 31%). Mass spectrum m / z, theoretical value 1112.53; measured value M+H: 1113.55; (5) Synthesis of compound 112: 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 112-8 (1112 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 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 the eluent being dichloromethane:petroleum ether=1:4 to obtain product 112 (259 mg, yield 25%). Mass spectrum m / z, theoretical value 1042.61; measured value M+H: 1043.63.

[0037] Example 3: Synthesis of Compound 5 Compound 5 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 24%. Mass spectrum m / z, theoretical value 1168.66; measured value M+H: 1169.68.

[0038] Example 4: Synthesis of Compound 9 Compound 9 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 23%. Mass spectrum m / z, theoretical value 1052.62; measured value M+H: 1053.64.

[0039] Example 5: Synthesis of Compound 13 Compound 13 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 28%. Mass spectrum m / z, theoretical value 1011.57; measured value M+H: 1012.59.

[0040] Example 6: Synthesis of Compound 19 Compound 19 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 23%. Mass spectrum m / z, theoretical value 1012.56; measured value M+H: 1013.59.

[0041] Example 7: Synthesis of Compound 25 Compound 25 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 29%. Mass spectrum m / z, theoretical value 1011.57; measured value M+H: 1012.59.

[0042] Example 8: Synthesis of Compound 31 Compound 31 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 22%. Mass spectrum m / z, theoretical value 1011.57; measured value M+H: 1012.60.

[0043] Example 9: Synthesis of Compound 37 Compound 37 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 26%. Mass spectrum m / z, theoretical value 1011.57; measured value M+H: 1012.59.

[0044] Example 10: Synthesis of Compound 43 Compound 43 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 24%. Mass spectrum m / z, theoretical value: 1048.56; measured value: M+H: 1049.58.

[0045] Example 11: Synthesis of Compound 46 Compound 46 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 23%. Mass spectrum m / z, theoretical value 1004.52; measured value M+H: 1005.54.

[0046] Example 12: Synthesis of Compound 52 Compound 52 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 21%. Mass spectrum m / z, theoretical value 1005.52; measured value M+H: 1006.55.

[0047] Example 13: Synthesis of Compound 61 Compound 61 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 28%. Mass spectrum m / z, theoretical value 1062.55; measured value M+H: 1063.57.

[0048] Example 14: Synthesis of Compound 64 Compound 64 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 24%. Mass spectrum m / z, theoretical value 1016.43; measured value M+H: 1017.45.

[0049] Example 15: Synthesis of Compound 72 Compound 72 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 27%. Mass spectrum m / z, theoretical value 1178.57; measured value M+H: 1179.59.

[0050] Example 16: Synthesis of Compound 76 Compound 76 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 25%. Mass spectrum m / z, theoretical value 956.50; measured value M+H: 957.52.

[0051] Example 17: Synthesis of Compound 87 Compound 87 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 27%. Mass spectrum m / z, theoretical value 1118.64; measured value M+H: 1119.67.

[0052] Example 18: Synthesis of Compound 91 Compound 91 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 28%. Mass spectrum m / z, theoretical value 1138.70; measured value M+H: 1139.72.

[0053] Example 19: Synthesis of Compound 99 Compound 99 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 23%. Mass spectrum m / z, theoretical value 1170.67; measured value M+H: 1171.69.

[0054] Example 20: Synthesis of Compound 106 Compound 106 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 21%. Mass spectrum m / z, theoretical value 1122.67; measured value M+H: 1123.69.

[0055] Example 21: Synthesis of Compound 121 Compound 121 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 23%. Mass spectrum m / z, theoretical value: 1164.65; measured value: M+H: 1165.67.

[0056] Example 22: Synthesis of Compound 124 Compound 124 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 29%. Mass spectrum m / z, theoretical value: 1098.67; measured value: M+H: 1099.69.

[0057] Example 23: Synthesis of Compound 130 Compound 130 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 24%. Mass spectrum m / z, theoretical value: 1152.72; measured value: M+H: 1153.74.

[0058] Example 24: Synthesis of Compound 142 Compound 142 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 25%. Mass spectrum m / z, theoretical value: 1150.73; measured value: M+H: 1151.75.

[0059] Example 25: Synthesis of Compound 151 Compound 151 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 26%. Mass spectrum m / z, theoretical value: 1176.56; measured value: M+H: 1177.58.

[0060] Example 26: Synthesis of Compound 154 Compound 154 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 27%. Mass spectrum m / z, theoretical value 1174.70; measured value M+H: 1175.73.

[0061] Example 27: Synthesis of Compound 155 Compound 155 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 27%. Mass spectrum m / z, theoretical value 1118.64; measured value M+H: 1119.67.

[0062] Example 28: Synthesis of Compound 156 Compound 156 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 28%. Mass spectrum m / z, theoretical value: 1230.77; measured value: M+H: 1231.79.

[0063] Example 29: Synthesis of Compound 158 Compound 158 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 24%. Mass spectrum m / z, theoretical value: 1121.67; measured value: M+H: 1122.69.

[0064] Example 30: Synthesis of Compound 166 Compound 166 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 29%. Mass spectrum m / z, theoretical value 1041.61; measured value M+H: 1042.63.

[0065] Example 31: Synthesis of Compound 167 Compound 167 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 26%. Mass spectrum m / z, theoretical value: 1069.65; measured value: M+H: 1070.67.

[0066] Example 32: Synthesis of Compound 168 Compound 168 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 22%. Mass spectrum m / z, theoretical value: 1095.66; measured value: M+H: 1096.68.

[0067] Example 33: Synthesis of Compound 170 Compound 170 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 25%. Mass spectrum m / z, theoretical value 1063.60; measured value M+H: 1064.62.

[0068] Example 34: Synthesis of Compound 174 Compound 174 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 29%. Mass spectrum m / z, theoretical value: 1168.65; measured value: M+H: 1169.67.

[0069] Example 35: Synthesis of Compound 175 Compound 175 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 24%. Mass spectrum m / z, theoretical value: 1146.67; measured value: M+H: 1147.69.

[0070] Example 36: Synthesis of Compound 176 Compound 176 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 29%. Mass spectrum m / z, theoretical value 1174.70; measured value M+H: 1175.72.

[0071] Example 37: Synthesis of Compound 177 Compound 177 was prepared by referring to the preparation scheme of Example 1 or Example 2. The yield of the final product was 21%. Mass spectrum m / z, theoretical value: 1223.69; measured value: M+H: 1224.71.

[0072] 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 in a mass ratio of 64:32:3:1 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, thereby manufacturing an organic electroluminescent diode.

[0073] 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-5:P-4 (mass ratio 97:3) evaporated in sequence with a thickness of 10 nanometers; HTL is HT-5 with a thickness of 60 nanometers; EBL is HT-16 with a thickness of 20 nanometers, EML is GH-1:GH-2:GD-Ir: the boron nitrogen compound 1 provided by the present invention (mass ratio 64:32:3:1) with a thickness of 35 nanometers, ETL is ET-6:LiQ (mass ratio 50:50) with a thickness of 35 nanometers; EIL is a 1nm LiF layer; then the cathode Al is evaporated to 70 nanometers to prepare an organic electroluminescent diode, which is recorded as Application Example 1.

[0074] 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 recorded as Application Examples 2 to 33 and Comparative Examples 1 and 2. The current efficiency, voltage, life and other characteristics of the device embodiments and comparative examples prepared above were tested by standard methods, and the device light-emitting characteristic data are shown in Table 1.

[0075] 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 and 2, Application Examples 1 to 33 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.

[0076] 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 structure shown in the following formula (I); ； In formula (I), X is selected from C, Si or Ge; Ring A is selected from substituted or unsubstituted aryl C6~C30, substituted or unsubstituted C6~C30 heteroaryl; Y1, Y2, Y3, and Y4 are each independently selected from CR or N; R1-R4 are monosubstituted or polysubstituted; the R, R1-R6 are each independently selected from hydrogen, deuterium, C1~C24 alkyl, substituted or unsubstituted C3~C24 cycloalkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C6~C30 heteroaryl; the heteroatom in the heteroaryl is selected from N, O, and S; when there is substitution, the substitution is independently selected from any one or more of deuterium, C1~C24 alkyl, C3~C24 cycloalkyl, and C6~C30 aryl; R, R4, R5, and R6 can be connected with adjacent substituents to form a ring.

2. The boron nitrogen compound according to claim 1, characterized in that The boron nitrogen compound has a structure shown in the following formula (I-1) or formula (I-2); ； In formula (I-1) or (I-2), X, ring A, Y1-Y4, R1-R4 have the same meanings as defined in claim 1; R7, R8, R9 are monosubstituted or polysubstituted; R7, R8, R9 are each independently selected from hydrogen, deuterium, C1~C24 alkyl, C3~C24 cycloalkyl; R4, R7, R8 can be fused with adjacent groups to form a ring.

3. The boron nitrogen compound according to claim 2, characterized in that In formula (I-1), R1 is selected from hydrogen; R4 is the same or different and is selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, or is condensed with an adjacent substituent group to form a benzene ring or a naphthalene ring; R7 and R8 are the same or different and are selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, cyclohexane, and adamantyl.

4. The boron nitrogen compound according to claim 2, characterized in that In formula (I-2), R1 is selected from substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted tetrahydronaphthyl; when there is substitution, the substituent is selected from one or more of hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, adamantyl, and pyridyl; R4 and R9 are the same or different and are selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, and adamantyl.

5. The boron nitrogen compound according to claim 1, characterized in that In formula (I), R2 and R3 are each independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl and tert-pentyl.

6. The boron nitrogen compound according to claim 1, characterized in that The ring A in formula (I) is selected from phenyl, pyridyl, naphthyl or any one of the following ring structures: 。 7. The boron nitrogen compound according to claim 1, characterized in that When at least one or more of the Y1-Y4 are selected from N, the ring A is selected from phenyl or naphthyl; when the Y1-Y4 are each independently selected from CR, the ring A is selected from pyridyl or any one of the following ring structures: 。 8. The boron nitrogen compound according to claim 1, characterized in that The R group is independently selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl at each occurrence; R can be fused with an adjacent substituent group to form a substituted or unsubstituted cyclopentane; and R2 and R3 are independently selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, tert-pentyl, hexyl, and heptyl at each occurrence.

9. 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: 。 10. Use of the boron nitrogen compound according to any one of claims 1 to 9 in the preparation of electronic devices.

11. The use according to claim 10, 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.

12. 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 9.

13. 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 9.

14. A composition, characterized in that The composition comprises the boron nitrogen compound according to any one of claims 1 to 9.

15. A preparation, characterized in that The preparation comprises the boron nitrogen compound according to any one of claims 1 to 9 and at least one solvent.

16. A display or lighting device, characterized in that: The device comprises one or more of the organic electroluminescent device according to claim 12 or the organic photoelectric device according to claim 13.

Images