Boron-containing organic compound and organic electroluminescent device containing same

Abstract

The invention discloses a boron-containing organic compound and an organic electroluminescent device containing the same, and belongs to the technical field of semiconductors. The structure of the organic compound is shown as a general formula (1), # imgabs0. When the compound is used as a doping material in a light-emitting layer material of an OLED light-emitting device, the compound can be used as a light-emitting layer green light doping material of the organic light-emitting device, so that the light-emitting efficiency of the device is improved, and the service life of the device is prolonged.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor technology, and in particular to a boron-containing organic compound and an organic electroluminescent device containing the same. Background Art

[0002] Compared with liquid crystal display (LCD), organic light-emitting diode (OLED) has technical advantages such as lighter and thinner, high color contrast, low power consumption, fast response, high clarity, and flexibility, and is believed to dominate future display terminal products. With the advent of the 5G era, the new information display industry is in urgent need of iterative development. The early lower color gamut standards (BT.709 and DCIP3) can no longer meet the high-quality technical development needs of display products. In order to achieve the performance requirements of ultra-high definition and higher picture quality of display products, the new generation of display standards (BT.2020) drives OLED luminescent materials to develop towards high color purity, which requires the core luminescent materials to have a narrower emission spectrum. Among the three commercialized OLED red, green and blue color rendering technologies, blue light uses traditional fluorescent triplet-triplet conversion (TTF) technology, which has low efficiency but high color purity and basically meets the BT.2020 display indicators; green and red light use phosphorescence technology, which has high efficiency. Red light is close to the BT.2020 display indicators, while green light is limited by the wider emission spectrum of phosphorescence, which is quite different from the requirements of high-definition display indicators. Therefore, it is very critical to develop high-color-purity green light OLED materials.

[0003] Since 2020, green light materials with narrow half-width (half-width <30nm) based on boron-nitrogen resonance structures have been reported one after another: DOI:10.1002 / adom.201902142, DOI:10.1002 / anie.202008264, DOI:10.1021 / jacs.0c10081, DOI:10.1038 / s41467-022-32607-3, DOI:10.1002 / anie.202202380, etc., showing the extremely high color purity and efficiency of this type of material, becoming the development trend of high color purity green light OLEDs. However, there are still many technical difficulties in the development of green light ultra-high color purity materials containing boron and nitrogen structures. The existing materials also have the defects that their efficiency and lifespan cannot meet the needs of mass production. The development of narrow half-width green light materials based on boron and nitrogen resonance structures that can meet practical applications is a key technical point for the next generation of high color purity, high color gamut coverage, high efficiency and high immersion display devices.

[0004] In addition, the sensitization technology combines triplet exciton-sensitizing materials (including but not limited to TADF materials and phosphorescent materials) with fluorescent doping materials, utilizes triplet exciton-sensitizing materials as exciton-sensitizing media, fully utilizes triplet excitons, and transfers energy to fluorescent doping materials through energy transfer, which can also achieve 100% device internal quantum efficiency. This technology can make up for the shortcomings of insufficient exciton utilization of fluorescent doping materials, and effectively give play to the characteristics of high fluorescence quantum yield, high device stability, high color purity and low price of fluorescent doping materials, and has broad prospects in OLEDs applications. For example, CN107507921A and CN110492006A disclose a luminescent layer combination technology with TADF materials with a difference of the lowest singlet and triplet energy levels of less than or equal to 0.2eV as the main body and boron-containing materials as doping; CN110492005A and CN110492009A disclose a luminescent layer combination scheme with an exciplex as the main body and boron-containing materials as doping; both can achieve efficiency comparable to phosphorescence and a relatively narrow half-width. Therefore, the development of sensitization technology based on narrow half-width boron-based luminescent materials has unique advantages and strong potential in terms of BT.2020 display indicators. Summary of the invention

[0005] In view of the above problems existing in the prior art, the present invention provides a boron-containing organic compound and an organic electroluminescent device containing the same. The compound of the present invention is used as a doping material of the light-emitting layer of the organic electroluminescent device to emit green fluorescence.

[0006] The technical solution of the present invention is as follows: a boron-containing organic compound, the structure of which is shown in general formula (1):

[0007]

[0008] R1 and R2, which are the same or different each time, represent a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0009] R1 and R2 can be connected to form a C6-C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring;

[0010] Z1, Z2, Z3, Z4, Z5, and Z6 are independently represented by N, CH, or C-R0;

[0011] R0, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0012] Each occurrence of M1, M2, M3, M4, and M5 that is the same or different indicates that C6 to C6 is substituted or unsubstituted by one or more R. 30 An aromatic ring, a 5-30 membered heteroaromatic ring substituted or unsubstituted by one or more R;

[0013] R, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0014] Each occurrence of X, whether the same or different, is represented by one of C and Si;

[0015] The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl;

[0016] The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B.

[0017] In a preferred embodiment, the structure of the boron-containing organic compound is shown in the general formula (1-1):

[0018]

[0019] In the general formula (1-1), R1-R 12 Each occurrence of the same or different atoms represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0020] R1-R 12 Any two adjacent groups can be connected to form a C6~C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring;

[0021] Z1, Z2, Z3, Z4, Z5, and Z6 are independently represented by N, CH, or C-R0;

[0022] R0, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0023] Each occurrence of M1 and M5 being the same or different indicates that C6 to C6 is substituted or unsubstituted by one or more R. 30 An aromatic ring, a 5-30 membered heteroaromatic ring substituted or unsubstituted by one or more R;

[0024] R, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0025] Each occurrence of X, whether the same or different, is represented by one of C and Si;

[0026] The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl;

[0027] The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B.

[0028] Preferably, the structure of the boron-containing organic compound is as shown in general formula (2-1):

[0029]

[0030] In the general formula (2-1), R1-R 19Each occurrence of the same or different atoms represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0031] R1-R 19 Any two adjacent groups can be connected to form a C6~C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring;

[0032] Z1, Z2, Z3, Z4, Z5, and Z6 are independently represented by N, CH, or C-R0;

[0033] R0, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0034] M1 appears the same or different C6~C each time 30 One of an aromatic ring and a 5-30 membered heteroaromatic ring;

[0035] Each occurrence of X, whether the same or different, is represented by one of C and Si;

[0036] The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl;

[0037] The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B.

[0038] Preferably, the structure of the boron-containing organic compound is as shown in general formula (3-1):

[0039]

[0040] In the general formula (3-1), Z1-Z6, R1-R 19 , the definition of X is the same as that in the general formula (2-1).

[0041] Preferably, the structure of the boron-containing organic compound is as shown in general formula (4-1):

[0042]

[0043] In the general formula (4-1), R1-R 19 Each occurrence of the same or different atoms represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0044] R1-R 19 Any two adjacent groups can be connected to form a C6~C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring;

[0045] Z1, Z2, Z3, Z4, Z5, and Z6 are independently represented by N, CH, or C-R0;

[0046] R0, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0047] M1 appears the same or different C6~C each time 30 One of an aromatic ring and a 5-30 membered heteroaromatic ring;

[0048] Each occurrence of X, whether the same or different, is represented by one of C and Si;

[0049] Each occurrence of Y that is the same or different is represented by C(R a )(R b )、Si(R c )(R d ), NR e , O, S;

[0050] R a , R b , R c , R d , R e Each independently represents C1 to C2 substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 Aryloxy, substituted or unsubstituted C6~C 30 aryl, or a 5-30 membered heteroaryl group which may be substituted by a substituent; and R a With R b , R c With R d Can be connected to form a five-membered ring or a six-membered ring;

[0051] The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl;

[0052] The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B.

[0053] Preferably, the structure of the boron-containing organic compound is as shown in general formula (5-1):

[0054]

[0055] In the general formula (5-1), Z1-Z6, R1-R 19 , the definitions of X and Y are the same as those in the general formula (4-1).

[0056] In a preferred embodiment, the structure of the boron-containing organic compound is as shown in any one of the general formulas (4-1) to (4-8):

[0057]

[0058]

[0059] In the general formula (4-2) to the general formula (4-8), Z1-Z6, R1-R 19 , R e , the definition of X is the same as that in general formula (4-1);

[0060] R 21 -R 32 Each occurrence of the same or different atoms represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent;

[0061] R1-R 32 Any two adjacent groups can be connected to form a C6~C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring;

[0062] The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl;

[0063] The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B.

[0064] Preferably, the R1-R 32and tert-butyl, deuterated tert-butyl, deuterated tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, deuterated cyclopentyl, methyl substituted cyclopentyl, cyclohexyl, phenyl, deuterated tert-butyl, cyclopentyl substituted ...pentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclohexyl, phenyl, deuterated tert-butyl, cyclopentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclopentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclohexyl, phenyl, deuterated tert-butyl, cyclopentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclopentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclopentyl substituted Phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9- One of dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazine, phenyl-substituted boryl, methoxy, tert-butoxy, and diphenylamine;

[0065] The R a , R b , R c , R d , R eEach of the following independently represents adamantyl, methyl, deuterated methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9, 9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy;

[0066] Said R and R0 are independently represented by a deuterium atom, a tritium atom, a halogen atom, a cyano group, an adamantyl group, a methyl group, a deuterated methyl group, a deuterated methyl group, a trifluoromethyl group, an ethyl group, a deuterated ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a deuterated cyclopentyl group, a methyl-substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated substituted phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9 - one of dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy, and diphenylamine;

[0067] The M1, M2, M3, M4, and M5 are represented by phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, phenyl-substituted amino, tert-butyl-substituted dibenzofuranyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, and xanthone;

[0068] The substituent for the substituent group is optionally selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, an adamantyl group, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a methoxy group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a pyridazinyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a quinolyl group, an isoquinolyl group, a furanyl group, a thienyl group, an indolyl group, a pyrrolyl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a carbazolinyl group, an azaphenanthryl group, and a diphenylamine group.

[0069] Preferably, the M5 is represented by one of the structures shown below:

[0070] The M1 is represented by the following structure: The M2 is represented by the following structure:

[0071] The M3 is represented by the following structure: The M4 is represented by the following structure:

[0072] The R1-R 32 Each independently represents the following structure: hydrogen atom, cyano group, deuterium atom, methyl group, ethyl group, isopropyl group, tert-butyl group,

[0073]

[0074] Any one of.

[0075] The R and R0 are independently represented by the following structures:

[0076] Deuterium atom, methyl, ethyl, isopropyl, tert-butyl, cyano, trifluoromethyl,

[0077] Any of;

[0078] The R e It is represented by the following structure:

[0079]

[0080] Any one of.

[0081] In a preferred embodiment, the specific structure of the boron-containing organic compound is any one of the following structures:

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] The present invention also provides an organic electroluminescent device, comprising a substrate, a first electrode, an organic light-emitting functional layer and a second electrode in sequence, wherein the organic light-emitting functional layer is located between the first electrode and the second electrode, and the organic light-emitting functional layer comprises a light-emitting layer, wherein the light-emitting layer contains the boron-containing organic compound of the present invention;

[0094] In a preferred embodiment, the light-emitting layer comprises a main material and a doping material, and the doping material comprises the boron-containing organic compound described in the present invention;

[0095] In a preferred embodiment, the light-emitting layer comprises a first main material, a second main material and a doping material, at least one of the first main material and the second main material is a TADF material, and the doping material is the boron-containing organic compound described in the present invention.

[0096] In a preferred embodiment, the functional layer comprises a light-emitting layer, the light-emitting layer comprises a main material, an exciton-sensitizing material and a doping material, the exciton-sensitizing material is a complex containing a metal element, and the doping material is the boron-containing organic compound described in the present invention.

[0097] Compared with the prior art, the beneficial technical effects of the present invention are:

[0098] (1) The compounds of the present invention are applied to OLED devices and can be used as doping materials for light-emitting layer materials. They can emit green fluorescence under the action of an electric field and can be applied to OLED lighting or OLED display fields;

[0099] (2) The compound of the present invention is used as a doping material and introduced into a phosphorescent sensitizer, which can effectively improve the efficiency and life of the device;

[0100] (3) The spectral FWHM of the compound of the present invention is relatively narrow, which can effectively improve the color gamut of the device and enhance the luminous efficiency of the device;

[0101] (4) The compound of the present invention is used as a doping material, and the TADF sensitizer is introduced as a second host, which can effectively improve the device efficiency;

[0102] The compound of the invention has a narrow half-peak width characteristic and can be used as a green light doping material of a light-emitting layer of an organic electroluminescent device, thereby improving the efficiency and life of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0103] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in the present invention are applied;

[0104] Among them, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer; DETAILED DESCRIPTION

[0105] The present invention is described in detail below in conjunction with the accompanying drawings and embodiments.

[0106] In the present invention, when describing electrodes and organic electroluminescent devices, as well as other structures, the words "upper", "lower", "top" and "bottom" used to indicate orientation only indicate the orientation in a certain state, and do not mean that the related structure can only exist in the orientation described; on the contrary, if the structure can change its position, such as inverted, the orientation of the structure will be changed accordingly. Specifically, in the present invention, the "bottom" or "lower" side of the electrode refers to the side of the electrode close to the substrate during the preparation process, and the opposite side away from the substrate is the "top" or "upper" side.

[0107] In the present invention, the substituted or unsubstituted aromatic amine group described in the present invention refers to Wherein Q1 and Q2 represent substituted or unsubstituted aromatic groups, and Q1 and Q2 preferably represent substituted or unsubstituted C6-C 30 aryl or substituted or unsubstituted 5-30 membered heteroaryl.

[0108] In the present invention, the substituted or unsubstituted C6-C 30Aryl refers to substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted The invention also includes, but is not limited to, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a combination thereof, or a condensed ring of a combination of the foregoing groups.

[0109] In the present invention, the substituted or unsubstituted 5-30 membered heteroaryl group refers to a substituted or unsubstituted furyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothienyl, a substituted or unsubstituted benzo imidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof, or condensed rings of combinations of the foregoing groups, but are not limited thereto.

[0110] The C1-C 10 Alkyl (including straight-chain alkyl and branched alkyl) refers to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl and the like, but is not limited thereto.

[0111] The C3-C 10Cycloalkyl refers to a monovalent monocyclic saturated hydrocarbon group including 3 to 10 carbon atoms as ring atoms. In this article, C4-C9 cycloalkyl is preferably used, C5-C8 cycloalkyl is more preferably used, and C5-C7 cycloalkyl is particularly preferably used. Non-limiting examples thereof may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl and cycloheptyl, but are not limited thereto.

[0112] The halogen atom mentioned in the present invention refers to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0113] The C1-C 10 The alkoxy group refers to a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group or the like, but is not limited thereto.

[0114] The C2-C 10 Alkenyl refers to vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1,1-dimethylallyl, 1-methylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl and 3-phenyl-1-butenyl, etc., but is not limited thereto.

[0115] The substituent for the substituent group is optionally selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, a trifluoromethyl group, an adamantyl group, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a methoxy group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a pyridazinyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a quinolyl group, an isoquinolyl group, a furanyl group, a thienyl group, an indolyl group, a pyrrolyl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a carbazolinyl group, and an azaphenanthryl group.

[0116] As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent PI film substrates; opaque substrates such as silicon substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, its use direction is different. In the present invention, a transparent PI film substrate is preferably used. The thickness of the substrate is not particularly limited.

[0117] A first electrode is formed on a substrate, and the first electrode and the second electrode may be opposite to each other. The first electrode may be an anode. The first electrode may be a transmissive electrode, a semi-transmissive electrode or a reflective electrode. When the first electrode is a transmissive electrode, it may be formed using a transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO) or indium tin zinc oxide (ITZO). When the first electrode is a semi-transmissive electrode or a reflective electrode, it may include metals such as Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir or Cr, or an alloy of several metals, or a combination of metals, metal oxides and metal alloys. The thickness of the first electrode layer depends on the material used, and is typically 50-500 nm, preferably 70-300 nm and more preferably 100-200 nm.

[0118] The organic functional material layer disposed between the first electrode and the second electrode includes, from bottom to top, a hole transport region, a light emitting layer and an electron transport region.

[0119] In the present invention, the hole transport region constituting the organic electroluminescent device can be exemplified by a hole injection layer, a hole transport layer, an electron blocking layer, and the like.

[0120] As the material for the hole injection layer, the hole transport layer, and the electron blocking layer, any material can be selected from known related materials used for organic electroluminescent devices.

[0121] The hole injection layer contains a main organic material that can conduct holes, and also contains a P-type dopant material with a deep HOMO energy level (the corresponding LUMO energy level will also be very deep). Based on empirical summary, in order to achieve smooth injection of holes from the anode to the organic film layer, the HOMO energy level of the main organic material that conducts holes used in the anode interface buffer layer must have certain characteristics with the P-doped material, so that the charge transfer state between the main material and the dopant material can be realized, the ohmic contact between the buffer layer and the anode can be achieved, and the efficient injection from the electrode to the hole injection conduction can be achieved.

[0122] In view of the above empirical summary, for hole-type host organic materials with different HOMO energy levels, different P-doped materials need to be selected to match them in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0123] Preferably, the main organic material of the hole injection layer of the present invention can be selected from the compounds disclosed in the following prior arts: JP1996048656A, JP1996048656A, CN1702065A, CN101535256A, CN103108859A, US20120112176A1, JP1989142657A, CN105439999A or CN103108859A.

[0124] Preferably, the P-type doping material is selected from the compounds with charge conductivity disclosed in the prior art, and the P-type dopant can be selected from the compounds disclosed in any one of the following documents: WO2011073149A, EP1968131A1, EP2276085A1, EP2213662A1, EP1722602A1, EP2045848A1, DE10200703122 0A1, US20100181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A and WO2012095143A1, but are not limited thereto.

[0125] In one embodiment of the present invention, the hole injection layer comprises a P-type dopant material with charge conductivity selected from the following: quinone derivatives, such as tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); or hexaazatriphenylene derivatives, such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN); or cyclopropane derivatives, such as 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyanoformyl))tris(2,3,5,6-tetrafluorobenzyl); or metal oxides, such as tungsten oxide and molybdenum oxide, but not limited to these.

[0126] In the hole injection layer of the present invention, the ratio of the hole transport material to the P-type doping material used is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0127] The thickness of the hole injection layer of the present invention may be 5-100 nm, preferably 5-50 nm, and more preferably 5-20 nm, but the thickness is not limited to this range.

[0128] Preferably, the hole transport layer material of the present invention may be selected from the following compounds disclosed in the prior art:

[0129]

[0130] Preferably, the hole transport layer material and the host organic material in the hole injection layer of the present invention are selected from the same compound.

[0131] The thickness of the hole transport layer of the present invention may be 5-200 nm, preferably 10-150 nm, and more preferably 20-100 nm, but the thickness is not limited to this range.

[0132] In one embodiment of the present invention, the electron blocking layer material of the present invention may be selected from the following compounds disclosed in the prior art:

[0133]

[0134] The thickness of the electron blocking layer of the present invention may be 1-50 nm, preferably 5-40 nm, but the thickness is not limited to this range.

[0135] After forming the hole injection layer, the hole transport layer and the electron blocking layer, a corresponding light emitting layer is formed on the electron blocking layer.

[0136] The light-emitting layer may include a host material and a dopant material. The host material may be a common green light host material in the art, and the dopant material may be a boron-containing organic compound represented by the general formula (1) of the present invention.

[0137] The light-emitting layer may contain a single host material or a dual host material;

[0138] The dual-host material comprises a first host material and a second host material, and preferably at least one of the first host material and the second host material is a TADF material;

[0139] TADF materials refer to materials with thermally activated delayed fluorescence properties, characterized by a small energy level difference between the first excited singlet state and the first excited triplet state, so that the singlet excitons and triplet excitons generated can be used simultaneously in the device, making the utilization rate of the excitons generated by the device as close to 100% as possible. Compared with traditional fluorescent materials, TADF materials have a higher exciton utilization rate.

[0140] The light-emitting layer may include a host material, an exciton-sensitizing material, and a doping material;

[0141] Exciton sensitizing materials refer to materials that can make the luminescent material in the luminescent layer fully utilize the electroexcitons, so that the luminescent layer finally produces the emission spectrum of the sensitized material. Exciton sensitizers may undertake functions such as exciton capture, exciton conversion, and exciton transfer in electroluminescent devices. The boron-containing organic compound represented by the general formula (1) of the present invention and the exciton sensitizing material are used in combination, which has a significant improvement effect on the problems of device efficiency improvement, exciton annihilation in the device, and efficiency reduction.

[0142] In the light-emitting layer of the present invention, the ratio of the host material to the doping material used is 99:1-70:30, preferably 99:1-85:15 and more preferably 97:3-87:13, based on mass.

[0143] The thickness of the light-emitting layer can be adjusted to optimize the light-emitting efficiency and the driving voltage. The preferred thickness range is 5 nm to 50 nm, more preferably 10-50 nm, and more preferably 15-40 nm, but the thickness is not limited to this range.

[0144] In the present invention, the electron transport region may include, from bottom to top, a hole blocking layer, an electron transport layer, and an electron injection layer disposed on the light emitting layer, but is not limited thereto.

[0145] The hole blocking layer is a layer that blocks holes injected from the anode from passing through the light-emitting layer and entering the cathode, thereby extending the life of the device and improving the performance of the device. The hole blocking layer of the present invention can be arranged on the light-emitting layer. As the hole blocking layer material of the organic electroluminescent device of the present invention, compounds with hole blocking function known in the prior art can be used, for example:

[0146]

[0147] The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm, more preferably 5-50 nm, but the thickness is not limited to this range.

[0148] The electron transport layer may be disposed on the light-emitting layer or (if present) the hole blocking layer. The electron transport layer material is a material that easily receives electrons from the cathode and transfers the received electrons to the light-emitting layer. A material having a high electron mobility is preferred. As the electron transport layer of the organic electroluminescent device of the present invention, the electron transport layer materials for organic electroluminescent devices disclosed in the prior art can be used, for example:

[0149]

[0150]

[0151] In a preferred embodiment of the present invention, the electron transport layer further comprises other compounds conventionally used in electron transport layers, for example, Alq3, LiQ, preferably LiQ.

[0152] The thickness of the electron transport layer of the present invention may be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm, but the thickness is not limited to this range.

[0153] The electron injection layer may be disposed on the electron transport layer. The electron injection layer material is generally preferably a material having a low work function so that electrons are easily injected into the organic functional material layer. As the electron injection layer material of the organic electroluminescent device of the present invention, the electron injection layer material for organic electroluminescent devices disclosed in the prior art can be used, for example: LiF, Cs2CO3, CsF, Csq, NaF, MgF2, CaF2, Al2O3, Yb, etc.

[0154] The thickness of the electron injection layer of the present invention may be 0.1-5 nm, preferably 0.5-3 nm, and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0155] The second electrode may be disposed above the electron transport region. The second electrode may be a cathode. The second electrode may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the second electrode is a transmissive electrode, the second electrode may include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag, or a compound or mixture thereof; when the second electrode is a semi-transmissive electrode or a reflective electrode, the second electrode may include Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or a compound or mixture thereof, but is not limited thereto. The thickness of the cathode depends on the material used.

[0156] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.

[0157] The method for preparing the organic electroluminescent device of the present invention comprises laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode successively on a substrate, and optionally a covering layer. In this regard, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI methods can be used, but are not limited thereto. In the present invention, it is preferred to use a vacuum evaporation method to form the various layers. Those skilled in the art can conventionally select various process conditions in the vacuum evaporation method according to actual needs.

[0158] Synthesis Example

[0159] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art;

[0160] Example 1 Synthesis of Compound 7:

[0161]

[0162] Preparation of intermediate M1:

[0163] Under nitrogen protection, raw material A1 (18 mmol, 3.47 g) and cesium carbonate (54 mmol, 17.59 g) were added to a three-necked flask, and 120 mL of anhydrous DMF was added. The mixture was stirred at room temperature for 25 minutes, and raw material B1 (39.6 mmol, 11.07 g) was continued to be added to the reaction mixture. The mixture was stirred and refluxed for 20 hours, cooled, filtered, washed with water, dried, and purified by silica gel column chromatography to obtain intermediate M1.

[0164] Preparation of intermediate N1:

[0165] The intermediate M1 (5.2mmol, 3.70g) was dissolved in 50mL of tetrahydrofuran (THF) solution, and 2.5mL of n-butyl lithium (2.5M, 5.7mmol) in n-hexane solution was slowly added at -78°C under nitrogen gas flow; after stirring at -78°C for 2 hours, 20mL of tetrahydrofuran solution of raw material C1 (5.4mmol, 1.24g) was slowly added. The reaction mixture was then slowly heated to room temperature and stirred overnight. 25mL of dilute hydrochloric acid (1M) solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted three times with ethyl acetate. The combined organic layer was dried over sodium sulfate and filtered. After the solvent was removed under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. The water layer was then separated and extracted with dichloromethane. Dry over sodium sulfate, filter, and evaporate by rotary concentrator and column to give intermediate N1.

[0166] Preparation of intermediate K1:

[0167] Add intermediate N1 (24 mmol, 20.28 g) and 220 mL of glacial acetic acid to a three-necked flask in sequence, and use nitrogen protection, cool to 0°C using a low-temperature tank and strictly avoid light, add NBS (25 mmol, 4.45 g) in batches, and stir at 0°C for 12 hours. Concentrate the reaction solution and purify it through a silica gel column to obtain intermediate K1.

[0168] Preparation of compound 7:

[0169] In a sealed pressure tube, under nitrogen protection, intermediate K1 (15mmol, 13.86g) and 110mL o-dichlorobenzene were added. 2.5M n-butyl lithium in n-hexane solution (12mmol, 30mL) was added at -78°C, the system was heated to 60°C and reacted for 2 hours, then boron tribromide (15mmol, 1.5mL) was added at 0°C, the reaction was continued at room temperature for 6 hours, then N,N-diisopropylethylamine (20mmol, 3.5mL) was added to the system at 0°C, heated to 200°C and reacted for 12 hours. After the reaction, the organic layer was decompressed and concentrated, and then purified by silica gel column chromatography to obtain compound 7. In toluene solution (1×10 -5 The half-peak width is 25 nm. 1 HNMR(400MHz,Chloroform-d)δ8.84–8.58(m,2H),8.39–8.16(m,3H),8.14–7.98(m,1H),7.90–7.77(m,2H),7.68(dd ,1H),7.60(t,1H),7.53(d,1H),7.48–7.41(m,4H),7.38–7.26(m,3H),7.20(t,3H),1.41(s,9H),1.36–1.24(m,27H).

[0170] Example 2 Synthesis of Compound 30:

[0171]

[0172] Preparation of intermediate M1:

[0173] Under nitrogen protection, raw material A1 (18 mmol, 3.47 g) and cesium carbonate (54 mmol, 17.59 g) were added to a three-necked flask, and 120 mL of anhydrous DMF was added. The mixture was stirred at room temperature for 25 minutes, and raw material B1 (39.6 mmol, 11.07 g) was continued to be added to the reaction mixture. The mixture was stirred and refluxed for 20 hours, cooled, filtered, washed with water, dried, and purified by silica gel column chromatography to obtain intermediate M1.

[0174] Preparation of intermediate N2:

[0175] The intermediate M1 (5.2mmol, 3.70g) was dissolved in 50mL of tetrahydrofuran (THF) solution, and 2.5mL of n-butyl lithium (2.5M, 5.7mmol) in n-hexane solution was slowly added at -78°C under nitrogen gas flow; after stirring at -78°C for 2 hours, 20mL of tetrahydrofuran solution of raw material C2 (5.4mmol, 1.32g) was slowly added. The reaction mixture was then slowly heated to room temperature and stirred overnight. 25mL of dilute hydrochloric acid (1M) solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted three times with ethyl acetate. The combined organic layer was dried over sodium sulfate and filtered. After the solvent was removed under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. The water layer was then separated and extracted with dichloromethane. Dry over sodium sulfate, filter, and evaporate by rotary concentrator and column to obtain intermediate N2.

[0176] Preparation of intermediate K2:

[0177] Add intermediate N2 (24 mmol, 20.62 g) and 220 mL of glacial acetic acid to a three-necked flask in sequence, and use nitrogen protection, cool to 0°C using a low-temperature tank and strictly avoid light, add NBS (25 mmol, 4.45 g) in batches, and stir at 0°C for 12 hours. Concentrate the reaction solution and purify it through a silica gel column to obtain intermediate K2.

[0178] Preparation of compound 30:

[0179] In a sealed pressure tube, under nitrogen protection, intermediate K2 (15mmol, 14.07g) and 110mL o-dichlorobenzene were added. 2.5M n-butyl lithium in n-hexane solution (12mmol, 30mL) was added at -78°C, the system was heated to 60°C and reacted for 2 hours, then boron tribromide (15mmol, 1.5mL) was added at 0°C, the reaction was continued at room temperature for 6 hours, then N,N-diisopropylethylamine (20mmol, 3.5mL) was added to the system at 0°C, heated to 200°C and reacted for 12 hours. After the reaction, the organic layer was decompressed and concentrated, and then purified by silica gel column chromatography to obtain compound 30. In toluene solution (1×10 -5 The half-peak width is 26 nm. 1HNMR(400MHz,Chloroform-d)δ8.78–8.64(m,2H),8.36–8.22(m,3H),7.90–7.76(m,2H),7.68(dd,1H), 7.60(t,1H),7.56–7.41(m,5H),7.38–7.29(m,2H),7.24–7.12(m,4H),2.38(d,3H),1.59–0.91(m,36H).

[0180] Example 3 Synthesis of Compound 53:

[0181]

[0182] Preparation of intermediate M2:

[0183] Add raw material E1 (1.22 g, 5 mmol) and cesium carbonate (4.07 g, 12.5 mmol) into a two-necked flask, add 50 mL of anhydrous DMF under nitrogen protection, stir at room temperature for 30 min, add raw material D1 (1.86 g, 5.2 mmol) under nitrogen protection, stir at 140 ° C for 12 h under nitrogen protection, filter, wash with water, dry, and pass through a column with PE:EA = 20:1 to obtain intermediate M2.

[0184] Preparation of intermediate J1:

[0185] The intermediate M2 (4.19 g, 7.2 mmol) was dissolved in 30 mL of anhydrous ether, and 10 mL of a hexane solution of n-butyl lithium (1.6 M) was added dropwise under a N2 atmosphere at 0°C with stirring; the mixture was stirred at 0°C for 1 hour, and then 10 mL of an anhydrous toluene solution of the raw material F1 (2.41 g, 8 mmol) was added dropwise; the reaction mixture was stirred at 35°C for 2 hours, and then cooled to room temperature; after adding water, the product was extracted with ethyl acetate. The combined organic layer was washed with brine and dried over anhydrous Na2SO4; after filtration and evaporation, it was passed through a column to obtain the intermediate J1.

[0186] Preparation of intermediate K3:

[0187] Intermediate J1 (3.20 g, 4.9 mmol) was dissolved in 50 mL of toluene solution, and raw material B1 (1.40 g, 5 mmol), tri-tert-butylphosphine (0.05 g, 0.25 mmol), sodium tert-butoxide (1.25 g, 13 mmol) and palladium acetate (0.02 g, 0.08 mmol) were added and stirred vigorously. The resulting mixture was refluxed at 105 ° C for 9 hours and then allowed to reach room temperature. Ethyl acetate (100 mL) was then added. The mixture was washed 3 times with deionized water (100 mL). After drying over anhydrous magnesium sulfate overnight, ethyl acetate was evaporated under reduced pressure. The remaining mixture was poured into 100 mL of petroleum ether under stirring and filtered to obtain intermediate K3.

[0188] Preparation of compound 53:

[0189] The intermediate K3 (10.75 g, 12 mmol) was dissolved in 150 mL of tert-butylbenzene. Under a nitrogen atmosphere at 0°C, 9 mL of a n-pentane solution of tert-butyl lithium (1.6 M) was slowly added, stirred at 60°C for 2 hours, and after adding boron tribromide (1.5 mL, 15 mmol) at 0°C, the reaction mixture was stirred at room temperature for 1 hour. N, N-diisopropylethylamine (DIPEA) (3.2 mL, 18 mmol) was added at 0°C, and the reaction mixture was allowed to reach room temperature. After stirring at 130°C for 6 hours, the reaction mixture was cooled to room temperature. Methanol was added to the reaction mixture to remove residual BBr3. The mixture was separated and extracted with water and dichloromethane. The combined organic layer was condensed in a vacuum and passed through a column to obtain compound 53. In a toluene solution (1×10 -5 The half-peak width is 27 nm. 1 HNMR(400MHz,Chloroform-d)δ8.81(d,1H),8.42(d,1H),8.34–8.29(m,1H),8.09(d,1H),7.98–7.88(m,2H),7.85–7.79(m,1H),7.76–

[0190] 7.55(m,8H),7.51–7.40(m,3H),7.34(dd,1H),7.20(d,2H),1.41(s,9H),1.34–1.29(m,27H).

[0191] Example 4 Synthesis of Compound 78:

[0192]

[0193] Preparation of intermediate L1:

[0194] In a three-necked flask, raw material G1 (0.36 g, 2 mmol), raw material H1 (0.58 g, 2 mmol), 50 mL toluene, 16 mL ethanol, 8 ml water, potassium carbonate (0.83 g, 6 mmol), Pd (PPh3) 4 (0.12 g, 0.1 mmol) were added, nitrogen was passed through, and the reaction was refluxed for 8 h. After the reaction was completed, it was cooled to room temperature, and water was added to quench the reaction. The organic phases were extracted three times with ethyl acetate, and then dried with anhydrous sodium sulfate, filtered and concentrated to obtain a crude product. The intermediate L1 was purified by recrystallization (EA / PE).

[0195] Preparation of intermediate Q1:

[0196] Intermediate L1 (8.63 g, 25 mmol) was dissolved in 100 mL of toluene solution, and raw material B2 (5.16 g, 25 mmol), tri-tert-butylphosphine (0.3 g, 1.5 mmol), sodium tert-butoxide (6.25 g, 65 mmol) and palladium acetate (0.09 g, 0.4 mmol) were added and stirred vigorously. The resulting mixture was refluxed at 105 ° C for 10 hours and then allowed to reach room temperature. Ethyl acetate (100 mL) was then added. The mixture was washed 3 times with deionized water (100 mL). After drying over anhydrous magnesium sulfate overnight, ethyl acetate was evaporated under reduced pressure. The remaining mixture was poured into 100 mL of petroleum ether under stirring. Intermediate Q1 was obtained after filtration.

[0197] Preparation of intermediate M3:

[0198] Add raw material A2 (1.68 g, 5 mmol) and cesium carbonate (4.07 g, 12.5 mmol) into a two-necked flask, add 50 mL of anhydrous DMF under nitrogen protection, stir at room temperature for 30 min, add raw material B1 (1.4 g, 5 mmol) under nitrogen protection, stir at 140 ° C for 12 h under nitrogen protection, filter, wash with water, dry, and pass through a column with PE:EA = 20:1 to obtain intermediate M3.

[0199] Preparation of intermediate N3:

[0200] The intermediate M3 (2.97 g, 5 mmol) was dissolved in 50 mL of tetrahydrofuran (THF) solution. Under the condition of nitrogen passing at 0°C, 3.8 mL of n-butyl lithium (1.6 M) n-hexane solution was slowly added; after stirring at 0°C for 2 hours, 10 mL of tetrahydrofuran solution of raw material C1 (1.27 g, 5.5 mmol) was slowly added. Then the reaction mixture was slowly heated to room temperature and stirred overnight. Dilute hydrochloric acid solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted with ethyl acetate three times. The combined organic layer was dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. Then the water layer was separated and extracted with dichloromethane. Drying with sodium sulfate, filtering, and evaporation by rotary concentration and column were performed to obtain intermediate N3.

[0201] Preparation of intermediate K4:

[0202] Intermediate N3 (1.70 g, 2.5 mmol) was dissolved in 50 mL of toluene solution, and intermediate Q1 (1.18 g, 2.5 mmol), tri-tert-butylphosphine (0.03 g, 0.125 mmol), sodium tert-butoxide (0.62 g, 6.5 mmol) and palladium acetate (0.01 g, 0.04 mmol) were added and stirred vigorously. The resulting mixture was refluxed at 105 ° C for 10 hours and then allowed to reach room temperature. Ethyl acetate (100 mL) was then added. The mixture was washed 3 times with deionized water (100 mL). After drying over anhydrous magnesium sulfate overnight, the ethyl acetate was evaporated under reduced pressure. The remaining mixture was poured into 100 mL of petroleum ether under stirring and filtered to obtain intermediate K4.

[0203] Preparation of compound 78:

[0204] The intermediate K4 (13.39 g, 12.5 mmol) was dissolved in 150 mL of tert-butylbenzene solution. Under a nitrogen atmosphere at 0°C, 10 mL of tert-butyl lithium (1.6 M) in n-pentane was slowly added and stirred at 60°C for 2 hours. After adding boron tribromide (1.5 mL, 15 mmol) at 0°C, the reaction mixture was stirred at room temperature for 1 hour. N, N-diisopropylethylamine (DIPEA) (3.2 mL, 18 mmol) was added at 0°C and the reaction mixture was allowed to reach room temperature. After stirring at 130°C for 6 hours, the reaction mixture was cooled to room temperature. Methanol was added to the reaction mixture to remove residual BBr3. The mixture was separated and extracted with water and dichloromethane. The combined organic layers were condensed in a vacuum and passed through a column to obtain compound 78. In toluene solution (1×10 -5 The half-peak width is 29 nm. 1HNMR(400MHz,Chloroform-d)δ8.79–8.72(m,1H),8.32–8.22(m,2H),8.09–8.02(m,1H),7.99–7.91(m,2H),7.88–7.75(m,2H),7.65–

[0205] 7.37(m,14H),7.34–7.17(m,8H),1.34(dd,36H).

[0206] Example 5 Synthesis of Compound 81:

[0207]

[0208] Preparation of intermediate P1:

[0209] Raw material A3 (12mmol, 3.26g), raw material S1 (10mmol, 2.04g) were added to a three-necked flask, dissolved with a mixed solvent (70mL toluene, 35mL ethanol), and then Pd (PPh3) 4 (0.10mmol, 0.12g), 15mL of 3mol / L K2CO3 aqueous solution were added, and the reaction was heated to reflux for 12 hours under nitrogen protection. The sampling point plate was taken to confirm that the reaction was complete. After cooling to room temperature, the reaction mixture was filtered through a diatomaceous earth pad, rinsed with chloroform, and the resulting filtrate was evaporated in vacuo. The obtained residue was purified by column chromatography on silica gel using hexane / toluene as eluent to obtain intermediate P1.

[0210] Preparation of intermediate M4:

[0211] Under nitrogen protection, intermediate P1 (18 mmol, 4.84 g) and cesium carbonate (54 mmol, 17.59 g) were added to a three-necked flask, and 120 mL of anhydrous DMF was added. The mixture was stirred at room temperature for 25 minutes, and raw material B1 (39.6 mmol, 11.07 g) was continued to be added to the reaction mixture. The mixture was stirred and refluxed for 20 hours, cooled, filtered, washed with water, dried, and purified by silica gel column chromatography to obtain intermediate M4.

[0212] Preparation of intermediate N4:

[0213] The intermediate M4 (5.2mmol, 4.10g) was dissolved in 50mL of tetrahydrofuran (THF) solution, and 2.5mL of n-butyl lithium (2.5M, 5.7mmol) in n-hexane solution was slowly added at -78°C under nitrogen gas flow; after stirring at -78°C for 2 hours, 20mL of tetrahydrofuran solution of raw material C1 (5.4mmol, 1.24g) was slowly added. The reaction mixture was then slowly heated to room temperature and stirred overnight. 25mL of dilute hydrochloric acid (1M) solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted three times with ethyl acetate. The combined organic layer was dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. The water layer was then separated and extracted with dichloromethane. Dry over sodium sulfate, filter, and evaporate by rotary concentrator and column to give intermediate N4.

[0214] Preparation of intermediate K5:

[0215] Add intermediate N4 (24 mmol, 22.11 g) and 220 mL of glacial acetic acid to a three-necked flask in sequence, and use nitrogen protection, cool to 0°C using a low-temperature tank and strictly avoid light, add NBS (25 mmol, 4.45 g) in batches, and stir at 0°C for 12 hours. Concentrate the reaction solution and purify it through a silica gel column to obtain intermediate K5.

[0216] Preparation of compound 81:

[0217] In a sealed pressure tube, under nitrogen protection, intermediate K5 (16mmol, 16.00g) and 150mL o-dichlorobenzene were added. 2.5M n-butyl lithium in n-hexane solution (12mmol, 30mL) was added at -78°C, the system was heated to 60°C and reacted for 2 hours, then boron tribromide (15mmol, 1.5mL) was added at 0°C, the reaction was continued at room temperature for 6 hours, then N,N-diisopropylethylamine (20mmol, 3.5mL) was added to the system at 0°C, heated to 200°C and reacted for 12 hours. After the reaction was completed, the organic layer was decompressed and concentrated, and then purified by silica gel column chromatography to obtain compound 81. In toluene solution (1×10 -5 The half-peak width is 28 nm. 1 HNMR(400MHz,Chloroform-d)δ8.79–8.65(m,2H),8.37–8.22(m,3H),8.10–8.03(m,1H),7 .89–7.77(m,2H),7.72–7.56(m,3H),7.52–7.15(m,14H),1.41(s,9H),1.36–1.27(m,27H).

[0218] Example 6 Synthesis of Compound 89:

[0219]

[0220] Preparation of intermediate P2:

[0221] Raw material A3 (12mmol, 3.26g), raw material S2 (10mmol, 3.30g) were added to a three-necked flask, dissolved with a mixed solvent (70mL toluene, 35mL ethanol), and then Pd (PPh3) 4 (0.10mmol, 0.12g), 15mL of 3mol / L K2CO3 aqueous solution were added, and the reaction was heated to reflux for 12 hours under nitrogen protection. The sampling point plate was taken to confirm that the reaction was complete. After cooling to room temperature, the reaction mixture was filtered through a diatomaceous earth pad, rinsed with chloroform, and the resulting filtrate was evaporated in vacuo. The obtained residue was purified by column chromatography on silica gel using hexane / toluene as eluent to obtain intermediate P2.

[0222] Preparation of intermediate M5:

[0223] Under nitrogen protection, intermediate P2 (18 mmol, 7.11 g) and cesium carbonate (54 mmol, 17.59 g) were added to a three-necked flask, and 120 mL of anhydrous DMF was added. The mixture was stirred at room temperature for 25 minutes, and raw material B1 (39.6 mmol, 11.07 g) was continued to be added to the reaction mixture. The mixture was stirred and refluxed for 20 hours, cooled, filtered, washed with water, dried, and purified by silica gel column chromatography to obtain intermediate M5.

[0224] Preparation of intermediate N5:

[0225] The intermediate M5 (5.2mmol, 4.75g) was dissolved in 50mL of tetrahydrofuran (THF) solution, and 2.5mL of n-butyl lithium (2.5M, 5.7mmol) in n-hexane solution was slowly added at -78°C under nitrogen gas flow; after stirring at -78°C for 2 hours, 20mL of tetrahydrofuran solution of raw material C1 (5.4mmol, 1.24g) was slowly added. The reaction mixture was then slowly heated to room temperature and stirred overnight. 25mL of dilute hydrochloric acid (1M) solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted three times with ethyl acetate. The combined organic layer was dried over sodium sulfate and filtered. After the solvent was removed under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. The water layer was then separated and extracted with dichloromethane. Dry over sodium sulfate, filter, and evaporate by rotary concentrator and column to give intermediate N5.

[0226] Preparation of intermediate K6:

[0227] Add intermediate N5 (24 mmol, 25.14 g) and 220 mL of glacial acetic acid to a three-necked flask in sequence, and use nitrogen protection, cool to 0°C using a low-temperature tank and strictly avoid light, add NBS (25 mmol, 4.45 g) in batches, and stir at 0°C for 12 hours. Concentrate the reaction solution and purify it through a silica gel column to obtain intermediate K6.

[0228] Preparation of compound 89:

[0229] In a sealed pressure tube, under nitrogen protection, intermediate K6 (16mmol, 18.02g) and 180mL o-dichlorobenzene were added. 2.5M n-butyl lithium in n-hexane solution (12mmol, 30mL) was added at -78°C, the system was heated to 60°C and reacted for 2 hours, then boron tribromide (18mmol, 1.8mL) was added at 0°C, the reaction was continued at room temperature for 6 hours, then N,N-diisopropylethylamine (20mmol, 3.5mL) was added to the system at 0°C, heated to 200°C and reacted for 12 hours. After the reaction was completed, the organic layer was decompressed and concentrated, and then purified by silica gel column chromatography to obtain compound 89. In toluene solution (1×10 -5 The half-peak width is 25 nm. 1 H NMR(400MHz,Chloroform-d)δ8.78–8.66(m,2H),8.38–8.20(m,3H),8.11–7.95(m,3H),7. 88–7.76(m,2H),7.75–7.53(m,7H),7.52–7.17(m,14H),1.41(s,9H),1.36–1.28(m,27H).

[0230] Example 7 Synthesis of Compound 94:

[0231]

[0232]

[0233] Preparation of intermediate P3:

[0234] Raw material A3 (12mmol, 3.26g), raw material S3 (10mmol, 3.14g) were added to a three-necked flask, dissolved with a mixed solvent (70mL toluene, 35mL ethanol), and then Pd (PPh3) 4 (0.10mmol, 0.12g), 15mL of 3mol / L K2CO3 aqueous solution were added, and the reaction was heated to reflux for 12 hours under nitrogen protection. The sampling point plate was taken to confirm that the reaction was complete. After cooling to room temperature, the reaction mixture was filtered through a diatomaceous earth pad, rinsed with chloroform, and the resulting filtrate was evaporated in vacuo. The obtained residue was purified by column chromatography on silica gel using hexane / toluene as eluent to obtain intermediate P3.

[0235] Preparation of intermediate M6:

[0236] Under nitrogen protection, intermediate P3 (18 mmol, 6.83 g) and cesium carbonate (54 mmol, 17.59 g) were added to a three-necked flask, and 120 mL of anhydrous DMF was added. The mixture was stirred at room temperature for 25 minutes, and raw material B1 (40 mmol, 11.18 g) was continued to be added to the reaction mixture. The mixture was stirred and refluxed for 20 hours, cooled, filtered, washed with water, dried, and purified by silica gel column chromatography to obtain intermediate M6.

[0237] Preparation of intermediate N6:

[0238] The intermediate M6 (5.2mmol, 4.67g) was dissolved in 50mL of tetrahydrofuran (THF) solution, and 2.5mL of n-butyl lithium (2.5M, 5.7mmol) in n-hexane solution was slowly added at -78°C under nitrogen gas flow; after stirring at -78°C for 2 hours, 20mL of tetrahydrofuran solution of raw material C1 (5.4mmol, 1.24g) was slowly added. The reaction mixture was then slowly heated to room temperature and stirred overnight. 25mL of dilute hydrochloric acid (1M) solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted three times with ethyl acetate. The combined organic layer was dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. The water layer was then separated and extracted with dichloromethane. Dry over sodium sulfate, filter, and evaporate by rotary concentrator and column to give intermediate N6.

[0239] Preparation of intermediate K7:

[0240] Add intermediate N6 (24 mmol, 24.76 g) and 220 mL of glacial acetic acid to a three-necked flask in sequence, and use nitrogen protection, cool to 0°C using a low-temperature tank and strictly avoid light, add NBS (25 mmol, 4.45 g) in batches, and stir at 0°C for 12 hours. Concentrate the reaction solution and purify it through a silica gel column to obtain intermediate K7.

[0241] Preparation of compound 94:

[0242] In a sealed pressure tube, under nitrogen protection, intermediate K7 (10mmol, 11.10g) and 110mL o-dichlorobenzene were added. 2.5M n-butyl lithium in n-hexane solution (12mmol, 30mL) was added at -78°C, the system was heated to 60°C and reacted for 2 hours, then boron tribromide (15mmol, 1.5mL) was added at 0°C, the reaction was continued at room temperature for 6 hours, then N,N-diisopropylethylamine (20mmol, 3.5mL) was added to the system at 0°C, heated to 200°C and reacted for 12 hours. After the reaction was completed, the organic layer was decompressed and concentrated, and then purified by silica gel column chromatography to obtain compound 94. In toluene solution (1×10 -5 The half-peak width is 27 nm. 1 HNMR(400MHz,Chloroform-d)δ8.78–8.64(m,2H),8.39–8.18(m,3H),8.12–8.02(m,1H),7.88–7.76(m,2H ),7.73–7.55(m,3H),7.48–7.40(m,3H),7.39–7.07(m,9H),1.74(t,4H),1.41(s,9H),1.36–1.22(m,39H).

[0243] Example 8 Synthesis of Compound 246:

[0244]

[0245] Preparation of intermediate X1:

[0246] In a three-necked flask, under nitrogen, (5.16 g, 25 mmol) of raw material B2, (7.36 g, 25 mmol) of raw material T1, (6.01 g, 60 mmol) of calcium carbonate and (0.02 g, 0.25 mmol) of Cu powder catalyst were added in sequence, and 200 mL of anhydrous DMF was added. The obtained suspension was heated to 130 ° C with silicone oil, stirred for 12 hours, extracted with ethyl acetate three times, and the organic phases were combined, then dried with anhydrous sodium sulfate, filtered and concentrated to obtain a crude product. The intermediate X1 was purified by recrystallization (ethyl acetate / petroleum ether).

[0247] Preparation of intermediate Y1:

[0248] In a three-necked flask, under nitrogen, (9.32 g, 25 mmol) of intermediate X1, (0.42 g, 1.5 mmol) of tricyclohexylphosphine, (19.55 g, 60 mmol) of cesium carbonate, (0.06 g, 0.25 mmol) of palladium acetate were added in sequence, and 200 mL of DMA was added. The resulting suspension was heated to 160 ° C with silicone oil, stirred for 9 hours, extracted three times with ethyl acetate, and the organic phases were combined, then dried with anhydrous sodium sulfate, filtered and concentrated to obtain a crude product. Intermediate Y1 was obtained by purification through recrystallization (ethyl acetate / petroleum ether).

[0249] Preparation of intermediate M3:

[0250] Add raw material A2 (1.68 g, 5 mmol) and cesium carbonate (4.07 g, 12.5 mmol) into a two-necked flask, add 50 mL of anhydrous DMF under nitrogen protection, stir at room temperature for 30 min, add raw material B1 (1.4 g, 5 mmol) under nitrogen protection, stir at 140 ° C for 12 h under nitrogen protection, filter, wash with water, dry, and pass through a column with PE:EA = 20:1 to obtain intermediate M3.

[0251] Preparation of intermediate N3:

[0252] The intermediate M3 (2.97 g, 5 mmol) was dissolved in 50 mL of tetrahydrofuran (THF) solution. Under the condition of nitrogen passing at 0°C, 3.8 mL of n-butyl lithium (1.6 M) n-hexane solution was slowly added; after stirring at 0°C for 2 hours, 10 mL of tetrahydrofuran solution of raw material C1 (1.27 g, 5.5 mmol) was slowly added. Then the reaction mixture was slowly heated to room temperature and stirred overnight. Dilute hydrochloric acid solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted with ethyl acetate three times. The combined organic layer was dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. Then the water layer was separated and extracted with dichloromethane. Drying with sodium sulfate, filtering, and evaporation by rotary concentration and column were performed to obtain intermediate N3.

[0253] Preparation of intermediate K8:

[0254] The intermediate N3 (1.70 g, 2.5 mmol) was dissolved in 50 mL of toluene solution, and the intermediate Y1 (0.84 g, 2.5 mmol), tri-tert-butylphosphine (0.03 g, 0.125 mmol), sodium tert-butoxide (0.62 g, 6.5 mmol) and palladium acetate (0.01 g, 0.04 mmol) were added and stirred vigorously. The resulting mixture was refluxed at 105 ° C for 10 hours and then allowed to reach room temperature. Ethyl acetate (100 mL) was then added. The mixture was washed 3 times with deionized water (100 mL). After drying over anhydrous magnesium sulfate overnight, the ethyl acetate was evaporated under reduced pressure. The remaining mixture was poured into 100 mL of petroleum ether under stirring and filtered to obtain intermediate K8.

[0255] Preparation of compound 246:

[0256] The intermediate K8 (11.71 g, 12.5 mmol) was dissolved in 150 mL of tert-butylbenzene solution. Under a nitrogen atmosphere at 0°C, 10 mL of tert-butyl lithium (1.6 M) in n-pentane was slowly added and stirred at 60°C for 2 hours. After adding boron tribromide (1.5 mL, 15 mmol) at 0°C, the reaction mixture was stirred at room temperature for 1 hour. N, N-diisopropylethylamine (DIPEA) (3.5 mL, 20 mmol) was added at 0°C and the reaction mixture was allowed to reach room temperature. After stirring at 130°C for 6 hours, the reaction mixture was cooled to room temperature. Methanol was added to the reaction mixture to remove residual BBr3. The mixture was separated and extracted with water and dichloromethane. The combined organic layers were condensed in a vacuum and passed through a column to obtain compound 246. In toluene solution (1×10 -5 The half-peak width is 26 nm. 1 HNMR(400MHz,Chloroform-d)δ8.81–8.69(m,1H),8.45–8.21(m,4H),8.16–8.02(m,2H ),7.95–7.75(m,3H),7.67–7.39(m,9H),7.38–7.15(m,6H),1.41(s,9H),1.32(d,18H).

[0257] Example 9 Synthesis of Compound 254:

[0258]

[0259] Preparation of intermediate W1:

[0260] Under nitrogen protection, raw material D2 (0.54 g, 2 mmol) and (Boc)2O (0.55 g, 2.5 mmol) were dissolved in 50 mL of tetrahydrofuran, DMAP (0.06 g, 0.5 mmol) was added and stirred at room temperature for 2 hours. The suspension was filtered, and the solid was washed with 20 mL of tetrahydrofuran and 40 mL of ethyl acetate to obtain intermediate W1.

[0261] Preparation of intermediate V1:

[0262] The intermediate W1 (1.90 g, 5.1 mmol) was dissolved in 50 mL of tetrahydrofuran (THF) solution. Under the condition of nitrogen passing at 0°C, 3.8 mL of n-butyl lithium (1.6 M) n-hexane solution was slowly added; after stirring at 0°C for 2 hours, 10 mL of tetrahydrofuran solution of raw material C2 (0.99 g, 5.5 mmol) was slowly added. Then the reaction mixture was slowly heated to room temperature and stirred overnight. Dilute hydrochloric acid solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted with ethyl acetate three times. The combined organic layer was dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. Then the water layer was separated and extracted with dichloromethane. It was dried over sodium sulfate, filtered, and evaporated by rotary concentration and passed through a column to obtain intermediate V1.

[0263] Preparation of intermediate Y2:

[0264] In a three-necked flask, under nitrogen protection, the intermediate V1 (0.46 g, 1 mmol) was dissolved in 20 mL of dichloromethane, followed by the addition of 10 mL of trifluoroacetic acid and stirred at room temperature for 23 hours. The reaction was then quenched with a saturated sodium bicarbonate solution, washed with dichloromethane, separated and collected organic phases, dried over anhydrous sodium sulfate, and concentrated. Purification was performed by a silica gel column (ethyl acetate: petroleum ether = 1:10) to obtain the intermediate Y2.

[0265] Preparation of intermediate M3:

[0266] Add raw material A2 (1.68 g, 5 mmol) and cesium carbonate (4.07 g, 12.5 mmol) into a two-necked flask, add 50 mL of anhydrous DMF under nitrogen protection, stir at room temperature for 30 min, add raw material B1 (1.4 g, 5 mmol) under nitrogen protection, stir at 140 ° C for 12 h under nitrogen protection, filter, wash with water, dry, and pass through a column with PE:EA = 20:1 to obtain intermediate M3.

[0267] Preparation of intermediate N3:

[0268] The intermediate M3 (2.97 g, 5 mmol) was dissolved in 50 mL of tetrahydrofuran (THF) solution. Under the condition of nitrogen passing at 0°C, 3.8 mL of n-butyl lithium (1.6 M) n-hexane solution was slowly added; after stirring at 0°C for 2 hours, 10 mL of tetrahydrofuran solution of raw material C1 (1.27 g, 5.5 mmol) was slowly added. Then the reaction mixture was slowly heated to room temperature and stirred overnight. Dilute hydrochloric acid solution, distilled water and ethyl acetate were added to the reaction mixture, the water layer was separated, and extracted with ethyl acetate three times. The combined organic layer was dried over sodium sulfate and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane, and then 47% boron trifluoride-diethyl ether was slowly added. The reaction mixture was stirred overnight and slowly quenched with NaHCO3 aqueous solution. Then the water layer was separated and extracted with dichloromethane. Drying with sodium sulfate, filtering, and evaporation by rotary concentration and column were performed to obtain intermediate N3.

[0269] Preparation of intermediate K9:

[0270] The intermediate N3 (1.70 g, 2.5 mmol) was dissolved in 50 mL of toluene solution, and the intermediate Y2 (0.89 g, 2.5 mmol), tri-tert-butylphosphine (0.03 g, 0.125 mmol), sodium tert-butoxide (0.62 g, 6.5 mmol) and palladium acetate (0.01 g, 0.04 mmol) were added and stirred vigorously. The resulting mixture was refluxed at 105 ° C for 10 hours and then allowed to reach room temperature. Ethyl acetate (100 mL) was then added. The mixture was washed 3 times with deionized water (100 mL). After drying over anhydrous magnesium sulfate overnight, the ethyl acetate was evaporated under reduced pressure. The remaining mixture was poured into 100 mL of petroleum ether under stirring and filtered to obtain intermediate K9.

[0271] Preparation of compound 254:

[0272] The intermediate K9 (11.95 g, 12.5 mmol) was dissolved in 150 mL of tert-butylbenzene solution. Under a nitrogen atmosphere at 0°C, 10 mL of tert-butyl lithium (1.6 M) in n-pentane was slowly added and stirred at 60°C for 2 hours. After adding boron tribromide (1.5 mL, 15 mmol) at 0°C, the reaction mixture was stirred at room temperature for 1 hour. N, N-diisopropylethylamine (DIPEA) (3.5 mL, 20 mmol) was added at 0°C and the reaction mixture was allowed to reach room temperature. After stirring at 130°C for 6 hours, the reaction mixture was cooled to room temperature. Methanol was added to the reaction mixture to remove residual BBr3. The mixture was separated and extracted with water and dichloromethane. The combined organic layers were condensed in a vacuum and passed through a column to obtain compound 254. In toluene solution (1×10 -5 The half-peak width is 25 nm. 1HNMR(400MHz,Chloroform-d)δ8.81–8.71(m,1H),8.33–8.21(m,2H),8.17–8.01 (m,2H),7.91–7.74(m,4H),7.66–7.14(m,19H),7.06–6.89(m,3H),1.32(d,18H).

[0273] Note: The half-peak width (FWHM) is obtained by testing the Fluorolog-3 series fluorescence spectrometer of Horiba.

[0274] The structural characteristics of the compounds obtained in each example are shown in Table 1

[0275] Table 1

[0276]

[0277] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device embodiments 1-9 and device comparison examples 1-2. The device manufacturing process of device embodiments 2-9 and device comparison examples 1-2 of the present invention is exactly the same as that of device embodiment 1, and the same substrate material and electrode material are used. The film thickness of the electrode material is also the same. The difference is that the doping material of the light-emitting layer in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 2-1 and Table 3 respectively:

[0278] Device Example 1

[0279] like Figure 1As shown, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washing with a cleaning agent (SemicleanM-L20), washing with pure water, drying, and then ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as a hole injection layer 3, and the mass ratio of HT-1 and HI-1 is 97:3. Then evaporate HT-1 with a thickness of 60nm as a hole transport layer 4. Then evaporate EB-1 with a thickness of 30nm as an electron blocking layer 5. After the above electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is made, using GH-1 and GH-2 as the main materials, compound 7 as the doping material, the mass ratio of GH-1, GH-2 and compound 7 is 69:30:1, and the thickness of the light-emitting layer is 30nm. After the above-mentioned light-emitting layer 6, HB-1 was vacuum-deposited to a thickness of 5 nm, which was the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq were vacuum-deposited to a thickness of 30 nm, with a mass ratio of ET-1 to Liq of 1:1. On the electron transport layer 8, a LiF layer with a thickness of 1 nm was made by vacuum evaporation, which was the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a thickness of 80 nm was made by vacuum evaporation, with a mass ratio of Mg to Ag of 1:9, which was used as the cathode layer 10.

[0280] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device embodiments 10-18 and device comparative examples 3-4. The device manufacturing process of device embodiments 11-18 of the present invention and device comparative examples 3-4 is exactly the same as that of device embodiment 10, and the same substrate material and electrode material are used. The film thickness of the electrode material is also consistent. The difference is that the doping material of the light-emitting layer in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 2-2 and Table 3, respectively.

[0281] Device Example 10

[0282] The transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washed with a cleaning agent (SemicleanM-L20), washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as the hole injection layer 3, and the mass ratio of HT-1 to HI-1 is 97:3. Then, HT-1 with a thickness of 60nm is evaporated as the hole transport layer 4. Then, EB-1 with a thickness of 30nm is evaporated as the electron blocking layer 5. After the above-mentioned electron blocking material is deposited, the light-emitting layer 6 of the OLED light-emitting device is prepared, using GH-1 and GH-2 as the main materials, GD-1 as the first doping material, and compound 7 as the second doping material. The mass ratio of GH-1, GH-2, GD-1 and compound 7 is 66.5:30:3:0.5, and the thickness of the light-emitting layer is 30nm. After the above-mentioned light-emitting layer 6, HB-1 is vacuum-deposited with a film thickness of 5nm. This layer is the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq are vacuum-deposited. The mass ratio of ET-1 and Liq is 1:1, and the film thickness is 30nm. This layer is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1nm is prepared by a vacuum evaporation device. This layer is the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a film thickness of 80nm is prepared by a vacuum evaporation device. The mass ratio of Mg and Ag is 1:9. This layer is used as the cathode layer 10.

[0283] The molecular structure formula of the relevant materials is shown below:

[0284]

[0285] After the OLED light-emitting device is completed as described above, the anode and cathode are connected by a known driving circuit, and the current efficiency and life of the device are measured. The device examples and comparative examples prepared by the same method are shown in Table 2-1 and Table 2-2; the test results of the current efficiency and life of the obtained device are shown in Table 3.

[0286] Table 2-1

[0287]

[0288] Table 2-2

[0289]

[0290]

[0291] Table 3

[0292]

[0293] Note: Current efficiency and luminescence peak are tested using IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.); life test system is EAS-62C OLED device life tester from Japan System Technology Co., Ltd.; LT95 refers to the time it takes for the device brightness to decay to 95%; all data are at 10mA / cm 2 Next test.

[0294] It can be seen from the device data results in Table 3 that, compared with the comparative compounds ref-1 and ref-2, the boron-containing compound of the present invention can well achieve the effect of green light emission, and the organic light-emitting device of the present invention, whether in a single-doping system or a double-doping system, has a greatly improved current efficiency and lifespan compared with OLED devices of known materials; when an exciton-sensitizing material is used as the first doping, the device efficiency is significantly improved compared with a single-doping system.

[0295] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A boron-containing organic compound, characterized in that The structure of the boron-containing organic compound is shown in general formula (1): R1 and R2, which are the same or different each time, represent a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; R1 and R2 can be connected to form a C6-C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring; Z1, Z2, Z3, Z4, Z5, and Z6 are independently represented by N, CH, or C-R0; R0, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; Each occurrence of M1, M2, M3, M4, and M5 that is the same or different indicates that C6 to C6 is substituted or unsubstituted by one or more R. 30 An aromatic ring, a 5-30 membered heteroaromatic ring substituted or unsubstituted by one or more R; R, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; Each occurrence of X, whether the same or different, is represented by one of C and Si; The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl; The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B.

2. The boron-containing organic compound according to claim 1, characterized in that The structure of the boron-containing organic compound is shown in general formula (1-1): In the general formula (1-1), R1-R 12 Each occurrence of the same or different atoms represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; R1-R 12 Any two adjacent groups can be connected to form a C6~C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring; Z1, Z2, Z3, Z4, Z5, and Z6 are independently represented by N, CH, or C-R0; R0, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; Each occurrence of M1 and M5 being the same or different indicates that C6 to C6 is substituted or unsubstituted by one or more R. 30 An aromatic ring, a 5-30 membered heteroaromatic ring substituted or unsubstituted by one or more R; R, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C2~C 10 Alkenyl, substituted or unsubstituted C2~C 10 Alkynyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; Each occurrence of X, whether the same or different, is represented by one of C and Si; The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl; The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B.

3. The boron-containing organic compound according to claim 1, characterized in that The structure of the boron-containing organic compound is shown in general formula (2-1): In the general formula (2-1), R1-R 19 Each occurrence of the same or different atoms represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; R1-R 19 Any two adjacent groups can be connected to form a C6~C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring; Z1, Z2, Z3, Z4, Z5, and Z6 are independently represented by N, CH, or C-R0; R0, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; M1 appears the same or different C6~C each time 30 One of an aromatic ring and a 5-30 membered heteroaromatic ring; Each occurrence of X, whether the same or different, is represented by one of C and Si; The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl; The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B. Preferably, the structure of the boron-containing organic compound is as shown in general formula (3-1): In the general formula (3-1), Z1-Z6, R1-R 19 , the definition of X is the same as that in the general formula (2-1).

4. The boron-containing organic compound according to claim 1, characterized in that The structure of the boron-containing organic compound is shown in general formula (4-1): In the general formula (4-1), R1-R 19 Each occurrence of the same or different atoms represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; R1-R 19 Any two adjacent groups can be connected to form a C6~C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring; Z1, Z2, Z3, Z4, Z5, and Z6 are independently represented by N, CH, or C-R0; R0, which is the same or different each time, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; M1 appears the same or different C6~C each time 30 One of an aromatic ring and a 5-30 membered heteroaromatic ring; Each occurrence of X, whether the same or different, is represented by one of C and Si; Each occurrence of Y that is the same or different is represented by C(R a )(R b )、Si(R c )(R d ), NR e , O, S; R a , R b , R c , R d , R e Each independently represents C1 to C2 substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 Aryloxy, substituted or unsubstituted C6~C 30 aryl, or a 5-30 membered heteroaryl group which may be substituted by a substituent; and R a With R b , R c With R d Can be connected to form a five-membered ring or a six-membered ring; The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl; The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B. Preferably, the structure of the boron-containing organic compound is as shown in general formula (5-1): In the general formula (5-1), Z1-Z6, R1-R 19 , the definitions of X and Y are the same as those in the general formula (4-1).

5. The boron-containing organic compound according to claim 4, characterized in that The structure of the boron-containing organic compound is shown in any one of the general formulas (4-1) to (4-8): In the general formula (4-2) to the general formula (4-8), Z1-Z6, R1-R 19 , R e , the definition of X is the same as that in general formula (4-1); R 21 -R 32 Each occurrence of the same or different atoms represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a C1-C2 group substituted or unsubstituted by a substituent. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C5~C 10 aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 One of aryl, 5-30 membered heteroaryl which may be substituted by a substituent; R1-R 32 Any two adjacent groups can be connected to form a C6~C 30 Aromatic ring, 5-30 membered heteroaromatic ring substituted or unsubstituted by substituents, C5-C 30 aliphatic ring; The substituents are selected from deuterium, tritium, halogen atoms, cyano groups, C1-C 10 Alkyl, deuterium or tritium substituted C1~C 10 Alkyl, C6~C 30 Aryl, deuterium or tritium substituted C6~C 30 Any one or more of aryl, 5-30 membered heteroaryl, deuterium or tritium substituted 5-30 membered heteroaryl; The heteroatom in the heteroaryl group is selected from one of O, S, N, Si and B.

6. The boron-containing organic compound according to any one of claims 1 to 5, characterized in that The R1-R 32 and tert-butyl, deuterated tert-butyl, deuterated tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, deuterated cyclopentyl, methyl substituted cyclopentyl, cyclohexyl, phenyl, deuterated tert-butyl, cyclopentyl substituted ...pentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclohexyl, phenyl, deuterated tert-butyl, cyclopentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclopentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclohexyl, phenyl, deuterated tert-butyl, cyclopentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclopentyl substituted cyclopentyl, methyl substituted cyclopentyl, cyclopentyl substituted Phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9- One of dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazine, phenyl-substituted boryl, methoxy, tert-butoxy, and diphenylamine; The R a , R b , R c , R d , R e Each of the following independently represents adamantyl, methyl, deuterated methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9, 9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy; Said R and R0 are independently represented by a deuterium atom, a tritium atom, a halogen atom, a cyano group, an adamantyl group, a methyl group, a deuterated methyl group, a deuterated methyl group, a trifluoromethyl group, an ethyl group, a deuterated ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a deuterated cyclopentyl group, a methyl-substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated substituted phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9 - one of dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy, and diphenylamine; The M1, M2, M3, M4, and M5 are represented by phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, phenyl-substituted amino, tert-butyl-substituted dibenzofuranyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, and xanthone; The substituent for the substituent group is optionally selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, an adamantyl group, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a methoxy group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a pyridazinyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a quinolyl group, an isoquinolyl group, a furanyl group, a thienyl group, an indolyl group, a pyrrolyl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a carbazolinyl group, an azaphenanthryl group, and a diphenylamine group.

7. The boron-containing organic compound according to any one of claims 1 to 5, characterized in that The M5 is represented by one of the structures shown below; The M1 is represented by the following structure: The M2 is represented by the following structure: The M3 is represented by the following structure: The M4 is represented by the following structure: The R1-R 32 Each independently represents the following structure: hydrogen atom, cyano group, deuterium atom, methyl group, ethyl group, isopropyl group, tert-butyl group, Any one of. The R and R0 are independently represented by the following structures: Deuterium atom, methyl, ethyl, isopropyl, tert-butyl, cyano, trifluoromethyl, Any of; The R e It is represented by the following structure: Any one of.

8. The boron-containing organic compound according to claim 1, characterized in that The specific structure of the boron-containing organic compound is any one of the following structures:

9. An organic electroluminescent device, comprising a substrate, a first electrode, an organic light-emitting functional layer and a second electrode in sequence, wherein the organic light-emitting functional layer is located between the first electrode and the second electrode, and the organic light-emitting functional layer includes a light-emitting layer, characterized in that: The light-emitting layer contains the boron-containing organic compound according to any one of claims 1 to 8; Preferably, the light-emitting layer comprises a host material and a doping material, and the doping material comprises the boron-containing organic compound according to any one of claims 1 to 8; Preferably, the light-emitting layer comprises a first host material, a second host material and a doping material, at least one of the first host material and the second host material is a TADF material, and the doping material is the boron-containing organic compound according to any one of claims 1-8.

10. The organic light-emitting device according to claim 9, wherein the functional layer comprises a light-emitting layer, and the light-emitting layer comprises a host material, an exciton-sensitizing material and a doping material, wherein the exciton-sensitizing material is a complex containing a metal element, and the doping material is a boron-containing organic compound according to any one of claims 1 to 8.

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