Boron-nitrogen compound and organic electroluminescent device containing the same

Abstract

The present invention relates to the technical field of preparation of organic photoelectric materials, and specifically to a boron nitrogen compound and an organic electroluminescent device containing the same. The boron nitrogen compound of the present invention has good electron and hole receiving capabilities, and by introducing a spirocyclic group with large steric hindrance, the interaction between luminescent molecules can be effectively suppressed. The large conjugated spirocyclic structural unit can improve the energy transfer performance between the host and the guest or sensitizer. Specifically, the organic electroluminescent device using the boron nitrogen compound of the present invention as a functional layer, especially as a light-emitting layer, has improved current efficiency, reduced lighting voltage, and greatly improved device life. This shows that after most electrons and holes recombine, the energy is effectively transferred to the boron nitrogen compound, thereby achieving high luminous efficiency.

Description

Technical Field

[0001] The present 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 increasing demand for information technology, the performance requirements for panel displays are becoming increasingly stringent. OLEDs, with their advantages such as autonomous illumination, low-voltage DC drive, full curing, wide viewing angle, and rich colors, have attracted widespread attention for their potential applications in next-generation display and lighting technologies, and their application prospects are very broad. Organic electroluminescent devices are spontaneously emitting light. The luminescence mechanism of OLEDs is that under the action of an applied electric field, electrons and holes are injected from the positive and negative electrodes, respectively, and then migrate, recombine, and decay within the organic material to produce light. The typical structure of an OLED includes one or more functional layers: a cathode layer, an anode layer, an electron injection layer, an electron transport layer, a hole blocking layer, a hole transport layer, a hole injection layer, and a light-emitting layer. Despite rapid progress in organic electroluminescence research, many challenges remain to be addressed. For example, the development of high-efficiency, long-life, narrow-emission green light materials has been a pressing challenge for those skilled in the art. Summary of the Invention

[0003] The present invention addresses the shortcomings of existing technologies by providing a boron-nitrogen compound and an organic electroluminescent device containing the same. By introducing a large spirocyclic steric group, the present invention effectively suppresses interactions between luminescent molecules. By introducing a large conjugated spirocyclic structure, the electron- and hole-accepting capacity of the boron-nitrogen compound is optimized, enhancing energy transfer between the host and guest and reducing the concentration of high-energy excitons in the light-emitting layer, thereby achieving a highly efficient, long-lived, 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:

[0005] According to one or more embodiments, the present invention provides a boron nitrogen compound having the general structure shown in the following formula I:

[0006] ;

[0007] 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 groups, substituted or unsubstituted C3-C24 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C5-C30 heteroaryl groups; R4 and R5 can be selectively linked 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 groups, C3-C24 cycloalkyl groups, C6-C30 aryl groups, and C5-C30 heteroaryl groups.

[0008] 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, dibenzothiophenyl, dimethylfluorenyl, N-phenyl-carbazolyl, spirocyclopentanefluorenyl, and 2,4,6-triphenyltriazinyl; and at least one of Ring A or Ring B is selected from substituted phenyl.

[0009] More preferably, in Formula I, Ring A and Ring B are not simultaneously selected from naphthyl or quinoxalinyl.

[0010] Preferably, in Formula I, R1-R3 are each the same or different and are selected from C1-C10 alkyl groups.

[0011] More preferably, in Formula I, R1-R3 are each identically selected from C1-C5 alkyl groups.

[0012] 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.

[0013] Preferably, R4 and R5 in Formula I are connected to form a ring to form a general structure shown in Formula I-1:

[0014] ;

[0015] In Formula I-1, the substitution of Ring A, Ring B, R1-R3, and R6 is 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 linked to form a ring.

[0016] 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.

[0017] 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.

[0018] Preferably, R6 and R7 in Formula I-1 are connected to form a ring to form the following structure, where * indicates the connection mode:

[0019] .

[0020] Preferably, one or more hydrogen atoms in Formula I or Formula I-1 may be deuterated.

[0021] Preferably, Formula I or Formula I-1 has a bilaterally symmetrical substitution structure.

[0022] 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:

[0023] .

[0024] In one aspect, the present invention further provides the use of a boron-nitrogen compound having a general structure as shown in Formula I or Formula I-1 above in the preparation of electronic devices.

[0025] 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).

[0026] In another aspect, the present invention further provides an organic electroluminescent device comprising a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises a boron-nitrogen compound having the general structure shown in Formula I or Formula I-1 above.

[0027] 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, wherein the mass percentage of the boron-nitrogen compound is 0.1%-50%.

[0028] In another aspect, the present invention further provides an organic optoelectronic 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 the general structure shown in Formula I or Formula I-1. For example, the boron-nitrogen compound can be included in the light-emitting material layer as a dopant.

[0029] The present invention also provides a composition comprising a boron-nitrogen compound having the general structure shown in Formula I or Formula I-1.

[0030] The present invention also provides a preparation comprising a boron nitrogen compound having the general structure shown in Formula I or Formula I-1 above or the composition as described above and at least one solvent. The solvent is not particularly limited and can be any solvent known to those skilled in the art, such as an unsaturated hydrocarbon solvent, a halogenated saturated hydrocarbon solvent, a halogenated unsaturated hydrocarbon solvent, an ether solvent, or an ester solvent; 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; and the ester solvent is an alkyl benzoate.

[0031] 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.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention provides a boron-nitrogen compound with excellent electron- and hole-accepting capacity. By introducing a large sterically hindered spirocyclic ring and a monosubstituted spirocyclic group, interactions between luminescent molecules can be effectively suppressed. The large conjugated spirocyclic structure and monosubstituted units such as dibenzofuran, dibenzothiophene, biphenyl, and fluorene enhance the energy transfer between the host and guest (or sensitizer) in the compound. Specifically, organic electroluminescent devices fabricated using the boron-nitrogen compound as a functional layer, particularly as a light-emitting layer, exhibit significantly improved current efficiency and device life. This suggests that after the majority of electrons and holes recombine, the energy is effectively transferred to the boron-nitrogen compound, resulting in high luminous efficiency. DETAILED DESCRIPTION

[0034] 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, as 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 this practice or test, example methods and materials are now described.

[0035] As used herein, "alkyl" refers to a monovalent alkyl group having 1 to 24 carbon atoms, preferably 1 to 14 carbon atoms, and more preferably 1 to 6 carbon atoms. Examples of this term include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, and the like.

[0036] The term "cycloalkyl" as used herein 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 may be substituted with 1 to 3 alkyl groups. 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.

[0037] As used herein, "aryl" refers to an unsaturated aromatic carbocyclic ring having 6-30 carbon atoms and having a monocyclic ring (e.g., phenyl) or polycyclic condensation (e.g., naphthyl or anthracenyl), preferably 6-18 carbon atoms, more preferably 1-12 carbon atoms. Preferred aryl groups include phenyl, biphenyl, naphthyl, phenanthrenyl, terphenyl, and the like. Unless otherwise specified for an individual substituent, such an aryl group may be optionally substituted with 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, and the like. Preferred substituents include, but are not limited to, alkyl, alkoxy, halogen, cyano, nitro, trihalomethyl, and thioalkoxy.

[0038] The "heteroaryl" mentioned in the present invention refers to a general term for groups having 5 to 30 carbon atoms and in which one or more aromatic carbon atoms in an aromatic group are replaced by a heteroatom, preferably 5 to 18 carbon atoms, wherein the heteroatom includes but is not limited to oxygen (O), sulfur (S) or nitrogen (N), silicon (Si) or germanium (Ge) atoms. The heteroaryl group may be a monocyclic heteroaryl group or a condensed-ring heteroaryl group. Examples may include pyridyl, pyrrolyl, pyridyl, thienyl, furyl, indolyl, quinolyl, isoquinolyl, quinoxalinyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc., but are not limited thereto.

[0039] The substitution in the present invention may be by a single bond or fusion. The "connection to form a ring" in the present invention may include a monocyclic ring, a polycyclic ring, and a fused ring, and the ring may be unsubstituted or substituted by one or more identical or different groups.

[0040] 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.

[0041] Unless otherwise stated, all commercial reagents involved in the following experiments were used directly after purchase.

[0042] In a preferred embodiment of the present invention, the OLED device of the present invention comprises a hole transport layer. The hole transport material may be preferably selected from known or unknown materials, and is particularly preferably selected from the following structures, but this does not mean that the present invention is limited to the following structures (Ph is phenyl):

[0043]

[0044] In a preferred embodiment of the present invention, the hole injection layer contained in the OLED device of the present invention has the following structure, but it does not mean that the present invention is limited to the following structure:

[0045]

[0046] In a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of the following compounds, but this does not mean that the present invention is limited to the following structures:

[0047]

[0048] The following examples explain in detail the preparation method of the boron nitrogen compound, i.e., the guest compound, and the luminescent properties of the device. The molecular structure of the relevant material is shown below:

[0049]

[0050] Example 1: Synthesis of Compound 1

[0051] ;

[0052] (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 of 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 °C 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 over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was separated and purified by silica gel chromatography with dichloromethane: petroleum ether = 1:7 as the eluent to obtain product 1-3 (212 mg, yield 49%). Mass spectrum m / z, theoretical value 437.31; found value M+H: 438.33;

[0053] (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 of 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 over sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography with a 1:8 ratio of dichloromethane to petroleum ether as the eluent to obtain product 1-6 (523 mg, yield 88%). Mass spectrum m / z, theoretical value 592.99; found value M+H: 594.01;

[0054] (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 resulting 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 resulting crude product was separated and purified by silica gel chromatography using a 1:1 ratio of dichloromethane to petroleum ether as the eluent to afford product 1-8 (457 mg, 55% yield). Mass spectrum: m / z: theoretical: 821.24; found: M+H: 822.26.

[0055] (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 of 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 over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was separated and purified by silica gel chromatography with dichloromethane: petroleum ether = 1:2 as the eluent to obtain product 1-9 (387 mg, yield 33%). Mass spectrum m / z, theoretical value 1178.62; found value M+H: 1179.65;

[0056] (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). The system was reacted at 60°C for 4 hours, then cooled to -50°C, and 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 resulting crude product was purified by silica gel chromatography using a 1:3 ratio of dichloromethane to petroleum ether as the eluent to afford product 1 (236 mg, 20% yield). Mass spectrum: m / z: theoretical: 1152.65; found: M+H: 1153.68.

[0057] Example 2: Synthesis of Compound 57

[0058] ;

[0059] (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 of toluene solution. Under nitrogen atmosphere, 10 mL of 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 over sodium sulfate. The solvent was removed by distillation under reduced pressure, 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; found value M+H: 381.11;

[0060] (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 of DMF solution, and potassium carbonate (691 mg, 5 mmoL) was added. The reaction system was heated at 140 °C 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 over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was separated and purified by silica gel chromatography with dichloromethane: petroleum ether = 1:9 as the eluent to obtain product 57-5 (712 mg, yield 79%). Mass spectrum m / z, theoretical value 898.48; found value M+H: 899.50;

[0061] (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 resulting 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 resulting crude product was separated and purified by silica gel chromatography using a 1:3 ratio of dichloromethane to petroleum ether as the eluent to afford product 57-7 (487 mg, 40% yield). Mass spectrum: m / z: theoretical: 1224.73; found: M+H: 1225.75.

[0062] (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, followed by the slow addition of NBS (178 mg, 1 mmol) 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 over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was separated and purified by silica gel chromatography using dichloromethane:petroleum ether = 1:4 as the eluent to obtain product 57-8 (465 mg, yield 36%). Mass spectrum m / z, theoretical value 1302.64; found value M+H: 1303.66;

[0063] (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 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 resulting crude product was purified by silica gel chromatography using a 1:5 ratio of dichloromethane to petroleum ether as the eluent to afford product 57 (248 mg, 20% yield). Mass spectrum: m / z: calcd. 1232.71; found: M+H: 1233.73.

[0064] Example 3: Synthesis of Compound 99

[0065] ;

[0066] 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, compound 99-2 (230 mg, 1 mmol) was slowly added. The mixture was slowly warmed to room temperature and allowed to react overnight, followed by the addition of 1 mL of ice water. 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 resulting residue was dissolved in acetic acid (100 mL), followed by the dropwise addition of concentrated hydrochloric acid (10 mL). 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 resulting crude product was separated and purified by silica gel chromatography using a 1:5 ratio of dichloromethane to petroleum ether as the eluent to afford product 99-3 (423 mg, 46% yield). Mass spectrum: m / z: theoretical: 922.39; found: M+H: 923.42.

[0067] 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, compound 99-4 (422 mg, 1 mmol) was slowly added. The mixture was slowly warmed to room temperature and allowed to react overnight, followed by the addition of 1 mL of ice water. 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 resulting residue was dissolved in acetic acid (100 mL), followed by the dropwise addition of concentrated hydrochloric acid (10 mL). 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 resulting crude product was separated and purified by silica gel chromatography using a 1:6 ratio of dichloromethane to petroleum ether as the eluent to afford product 99-5 (504 mg, 42% yield). Mass spectrum: m / z: theoretical: 1198.62; found: M+H: 1199.64.

[0068] Synthesis of compound 99-6: Compound 99-5 (1198 mg, 1 mmol) was slowly added to 100 mL of glacial acetic acid at 0°C in the dark. NBS (178 mg, 1 mmol) was then 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 over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was purified by silica gel chromatography using a 1:4 ratio of dichloromethane to petroleum ether as the eluent to afford product 99-6 (562 mg, 44% yield). Mass spectrum: m / z: theoretical: 1276.53; found: M+H: 1277.56.

[0069] Synthesis of Compound 99: Under a nitrogen atmosphere at zero degrees Celsius, tert-butyllithium (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). The reaction was continued at 60°C for 4 hours, then cooled to -50°C, followed by the addition of BBr₃ (494 mg, 2 mmol). After 1 hour of reaction at room temperature, N,N-diisopropylethylamine (259 mg, 2 mmol) was added. The reaction was then heated to 120°C for 12 hours. After cooling to room temperature, 5 mL of 1 M aqueous sodium acetate solution 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 resulting crude product was purified by silica gel chromatography using a 1:6 ratio of dichloromethane to petroleum ether as the eluent to afford product 99 (278 mg, 23% yield). Mass spectrum: m / z: theoretical: 1206.60; found: M+H: 1207.63.

[0070] Example 4: Synthesis of Compound 3

[0071] Compound 3 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 24%. Mass spectrum m / z: theoretical value: 1126.60; found value: M+H: 1127.62.

[0072] Example 5: Synthesis of Compound 5

[0073] Compound 5 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 24%. Mass spectrum m / z: theoretical value: 1142.57; found value: M+H: 1143.59.

[0074] Example 6: Synthesis of Compound 10

[0075] Compound 10 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 21%. Mass spectrum m / z: theoretical value: 1188.65; found value: M+H: 1189.67.

[0076] Example 7: Synthesis of Compound 11

[0077] Compound 11 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 24%. Mass spectrum m / z: theoretical value: 1267.67; found value: M+H: 1268.69.

[0078] Example 8: Synthesis of Compound 14

[0079] Compound 14 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 25%. Mass spectrum m / z: theoretical value: 1251.66; found value: M+H: 1252.68.

[0080] Example 9: Synthesis of Compound 17

[0081] Compound 17 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 27%. Mass spectrum m / z: theoretical value: 1202.67; found value: M+H: 1203.69.

[0082] Example 10: Synthesis of Compound 22

[0083] Compound 22 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 25%. Mass spectrum m / z: theoretical value: 1176.61; found value: M+H: 1177.63.

[0084] Example 11: Synthesis of Compound 26

[0085] Compound 26 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 20%. Mass spectrum m / z: theoretical value: 1317.68; found value: M+H: 1318.71.

[0086] Example 12: Synthesis of Compound 32

[0087] Compound 32 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 26%. Mass spectrum m / z: theoretical value: 1164.62; found value: M+H: 1165.65.

[0088] Example 13: Synthesis of Compound 39

[0089] Compound 39 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 26%. Mass spectrum m / z: theoretical value: 1182.70; found value: M+H: 1183.72.

[0090] Example 14: Synthesis of Compound 44

[0091] Compound 44 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 23%. Mass spectrum m / z: theoretical value: 1194.61; found value: M+H: 1195.63.

[0092] Example 15: Synthesis of Compound 52

[0093] Compound 52 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 21%. Mass spectrum m / z: theoretical value: 1126.63; found value: M+H: 1127.65.

[0094] Example 16: Synthesis of Compound 60

[0095] Compound 60 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 21%. Mass spectrum m / z: theoretical value: 1206.66; found value: M+H: 1207.68.

[0096] Example 17: Synthesis of Compound 67

[0097] Compound 67 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 26%. Mass spectrum m / z: theoretical value: 1166.57; found value: M+H: 1167.59.

[0098] Example 18: Synthesis of Compound 76

[0099] Compound 76 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 22%. Mass spectrum m / z: theoretical value: 1178.64; found value: M+H: 1179.67.

[0100] Example 19: Synthesis of Compound 86

[0101] Compound 86 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 24%. Mass spectrum m / z: theoretical value: 1214.67; found value: M+H: 1215.69.

[0102] Example 20: Synthesis of Compound 92

[0103] Compound 92 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 20%. Mass spectrum m / z: theoretical value: 1141.64; found value: M+H: 1142.66.

[0104] Example 21: Synthesis of Compound 104

[0105] Compound 104 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 29%. Mass spectrum m / z: theoretical value: 1338.70; found value: M+H: 1339.72.

[0106] Example 22: Synthesis of Compound 107

[0107] Compound 107 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 23%. Mass spectrum m / z: theoretical value: 1166.57; found value: M+H: 1167.69.

[0108] Example 23: Synthesis of Compound 108

[0109] Compound 108 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 25%. Mass spectrum m / z: theoretical value: 1168.56; found value: M+H: 1169.58.

[0110] Example 24: Synthesis of Compound 109

[0111] Compound 109 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 23%. Mass spectrum m / z: theoretical value: 1216.59; found value: M+H: 1217.61.

[0112] Example 25: Synthesis of Compound 115

[0113] Compound 115 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 26%. Mass spectrum m / z: theoretical value: 1186.60; found value: M+H: 1187.62.

[0114] Example 26: Synthesis of Compound 116

[0115] Compound 116 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 25%. Mass spectrum m / z: theoretical value: 1278.70; found value: M+H: 1279.72.

[0116] Example 27: Synthesis of Compound 119

[0117] Compound 119 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 23%. Mass spectrum m / z: theoretical value: 1180.55; found value: M+H: 1181.58.

[0118] Example 28: Synthesis of Compound 129

[0119] Compound 129 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 22%. Mass spectrum m / z: theoretical value: 1146.51; found value: M+H: 1147.53.

[0120] Example 29: Synthesis of Compound 133

[0121] Compound 133 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 26%. Mass spectrum m / z: theoretical value: 1146.51; found value: M+H: 1147.53.

[0122] Example 30: Synthesis of Compound 141

[0123] Compound 141 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 23%. Mass spectrum m / z: theoretical value: 1218.58; found value: M+H: 1219.61.

[0124] Example 31: Synthesis of Compound 149

[0125] Compound 149 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 24%. Mass spectrum m / z: theoretical value: 1117.55; found value: M+H: 1118.57.

[0126] Example 32: Synthesis of Compound 152

[0127] Compound 152 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 29%. Mass spectrum m / z: theoretical value: 1168.56; found value: M+H: 1169.58.

[0128] Example 33: Synthesis of Compound 153

[0129] Compound 153 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 27%. Mass spectrum m / z: theoretical value: 1278.66; found value: M+H: 1279.68.

[0130] Example 34: Synthesis of Compound 157

[0131] Compound 157 was prepared by referring to the preparation schemes of Examples 1 to 3. The yield of the final product was 22%. Mass spectrum m / z: theoretical value: 1072.57; found value: M+H: 1073.59.

[0132] Fabrication of OLED devices:

[0133] As a reference preparation method for a device embodiment, the present invention evaporates a p-doped material on the surface of ITO glass or the anode with a light-emitting area of ​​2 mm×2 mm, 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, then co-evaporates a host material (GH-1 and GH-2), GD-Ir, and the boron nitrogen compound prepared by the present invention (guest material) at a mass ratio of 63:33:3:1 on the hole transport layer 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 Al cathode to manufacture an organic electroluminescent diode.

[0134] In a preferred embodiment, the structure of the bottom-emitting OLED device provided by the present invention is as follows: glass containing ITO is used as the anode, and the HIL is HT-4:P-3 (mass ratio 97:3) with a thickness of 10 nm; the HTL is HT-4 with a thickness of 60 nm; the EBL is HT-15 with a thickness of 20 nm; the EML is a host 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; the ETL is ET-5:LiQ (mass ratio 50:50) with a thickness of 35 nm; the EIL is a 1 nm LiF layer; and then the cathode Al is evaporated to 70 nm to prepare an organic electroluminescent diode, which is recorded as Application Example 1.

[0135] Referring to the device structure provided in Application Example 1, the boron-nitrogen compounds listed in Table 1 were selected as the implementation targets in place of Compound 1 to prepare organic electroluminescent diodes, designated as Application Examples 2 through 26 and Comparative Examples 1-3. The devices prepared in these Application Examples and Comparative Examples were tested using standard methods for characteristics such as current efficiency and lifetime. The device luminescence characteristics are shown in Table 1.

[0136] Table 1. Device luminescence characteristics data table

[0137]

[0138] As can be seen from Table 1, electronic devices prepared using the compounds of the present invention as light-emitting layer materials exhibit higher current efficiency and lifespan. Compared to Comparative Examples 1-3, Application Examples 1 to 26 all demonstrate good device performance in terms of current efficiency and lifespan. These improvements in device performance are attributed to the enhanced electron transport capabilities of the boron nitrogen compound materials of the present invention. This demonstrates that the boron nitrogen compounds provided by the present invention have considerable commercial application value.

[0139] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A boron-nitrogen compound, characterized in that: The boron-nitrogen compound is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

2. Use of the boron nitrogen compound according to claim 1 as a light-emitting layer doping material in the preparation of electronic devices.

3. The use according to claim 2, characterized in that The electronic device is an organic electroluminescent device.

4. 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 comprises a light-emitting layer, and the light-emitting layer comprises the boron nitrogen compound according to claim 1.

5. 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 disposed between the first electrode and the second electrode; the light-emitting material layer contains the boron nitrogen compound as claimed in claim 1.

6. A composition, characterized in that The composition comprises the boron nitrogen compound as claimed in claim 1.

7. A preparation, characterized in that The preparation comprises the boron nitrogen compound according to claim 1 and at least one solvent.

8. A display or lighting device, characterized in that: The device comprises one or more of the organic electroluminescent device according to claim 4 and / or the organic photoelectric device according to claim 5.

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