A resonance type organic compound and its application

Abstract

The present invention relates to a resonance type organic compound and application thereof, belonging to the field of semiconductor technology. The present invention provides a compound having a structure represented by general formula (1) and general formula (2). The compound of the present invention has a narrow half-peak width, a high fluorescence quantum yield, a high glass transition temperature and molecular thermal stability, and suitable HOMO and LUMO energy levels. When the compound is used as a doping material in a light-emitting layer material of an OLED light-emitting device, the current efficiency of the device is significantly improved, and the purity of the light-emitting color and the life of the device are also greatly improved.

Description

Technical Field

[0001] The invention relates to the field of semiconductor technology, and in particular to a resonance type organic compound containing a carbazole-indole fused ring structure and application thereof. Background Art

[0002] Traditional fluorescent doped materials are limited by early technologies and can only use 25% of singlet excitons formed by electrical excitation to emit light. The internal quantum efficiency of the device is low (up to 25%), and the external quantum efficiency is generally less than 5%, which is far behind the efficiency of phosphorescent devices. Phosphorescent materials can effectively use singlet and triplet excitons formed by electrical excitation to emit light, due to the strong spin-orbit coupling of the heavy atom center, which enhances intersystem crossing, so that the internal quantum efficiency of the device can reach 100%.

[0003] With the advent of the 5G era, higher requirements are placed on color rendering standards. In addition to being efficient and stable, luminescent materials also require a narrower half-width to improve the purity of the device's luminescent color. Fluorescent doped materials can achieve high fluorescence quantum and narrow half-width through molecular engineering. Blue fluorescent doped materials have achieved a phased breakthrough, and the half-width of boron materials can be reduced to below 30nm. In the green light region, which is more sensitive to the human eye, research is mainly focused on phosphorescent doped materials, but their luminescent peak shape is difficult to narrow by simple methods. Therefore, in order to meet higher color rendering standards, it is of great significance to study efficient green fluorescent doped materials with narrow half-width.

[0004] In addition, TADF sensitized fluorescence technology (TSF) combines TADF materials with fluorescent doping materials, and uses TADF materials as exciton sensitization media to convert triplet excitons formed by electrical excitation into singlet excitons, and transfers energy to fluorescent doping materials through long-range energy transfer of singlet excitons. It can also achieve 100% device 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.

[0005] Boron compounds with a resonant structure are more likely to achieve narrow half-width luminescence. This type of material is used in TADF-sensitized fluorescence technology to achieve the preparation of devices with high efficiency and narrow half-width emission. For example, CN 107507921 A and CN110492006 A disclose a luminescent layer combination technology with a TADF material having a difference between the lowest singlet state and the lowest triplet state energy level of less than or equal to 0.2eV as the main body and a boron-containing material as the doping; CN 110492005A and CN 110492009 A disclose a luminescent layer combination scheme with an exciplex as the main body and a boron-containing material as the doping; both can achieve efficiency comparable to phosphorescence and a relatively narrow half-width. Therefore, the development of TADF-sensitized fluorescence 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

[0006] In view of the above problems existing in the prior art, the applicant of the present invention provides a resonance type organic compound and its application. The skeleton represented by the general formula (1) forms a resonance type organic compound after introducing the structure of carbazole indole fused ring, which has the effect of significantly adjusting light color, improving quantum yield and improving device life.

[0007] The technical solution of the present invention is as follows: a resonance type organic compound, the structure of the organic compound is shown in the general formula (1):

[0008]

[0009] In the general formula (1), A1-A3 represent substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C6-C 30 heteroaryl, substituted or unsubstituted C5-C 30 Cycloalkyl, substituted or unsubstituted C5-C 30 Cycloalkenyl;

[0010] Each occurrence of Z0 can be the same or different and is represented as C-R0;

[0011] X0 represents a single bond, -O-, -Si(R2)2-, -C(R3)2-, -N(R4-);

[0012] X1 represents a single bond, -O-, -S-, -Se-, -Si(R2)2-, -C(R3)2-, -N(R4-);

[0013] n can be 0 or 1;

[0014] Each occurrence of R0 is the same or different and is independently represented by H, deuterium atom, halogen atom, cyano group, C1-C 10alkyl or silyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0015] Each occurrence of R2, R3, and R4 is represented independently as C1-C 10 Alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted C5-C 30 Cycloalkyl, substituted or unsubstituted C5-C 30 Cycloalkenyl;

[0016] And R4 can also be connected to the A1 ring through a single bond to form a ring;

[0017] At least one of A1, A2, A3, and R4 is represented by the structure shown in general formula (2);

[0018] Each occurrence of Z can be the same or different and is represented by C-R1;

[0019] Each occurrence of R1 is the same or different and independently represents H, a deuterium atom, a halogen atom, a cyano group, a C1-C 10 alkyl or silyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0020] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C1-C 10 Alkyl, C5-C 10 Cycloalkyl, C5-C 10 Cycloalkenyl, C1-C 10 Alkoxy, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C3-C 30 One or more heteroaryl groups.

[0021] In a preferred embodiment, the structure of the organic compound is as shown in any one of the general formulas (1-1) to (1-2):

[0022]

[0023] In the general formula (1-1) to the general formula (1-2), A1 to A4 represent substituted or unsubstituted C6 to C 30 aryl, substituted or unsubstituted C6-C 30 heteroaryl, substituted or unsubstituted C5-C 30Cycloalkyl, substituted or unsubstituted C5-C 30 Cycloalkenyl;

[0024] Each occurrence of Z0 can be the same or different and is represented as C-R0;

[0025] X0 and X1 are independently single bonds, -O-, -Si(R2)2-, -C(R3)2-, -N(R4-);

[0026] n can be 0 or 1;

[0027] Each occurrence of R0 is the same or different and is independently represented by H, deuterium atom, halogen atom, cyano group, C1-C 10 alkyl or silyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0028] Each occurrence of R2, R3, and R4 is represented independently as C1-C 10 Alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted C5-C 30 Cycloalkyl, substituted or unsubstituted C5-C 30 Cycloalkenyl;

[0029] And R4 can also be connected to the A1 ring through a single bond to form a ring;

[0030] At least one of A1, A2, A3, and A4 is represented by the structure shown in general formula (2);

[0031] Each occurrence of Z can be the same or different and is represented by C-R1;

[0032] Each occurrence of R1 is the same or different and independently represents H, a deuterium atom, a halogen atom, a cyano group, a C1-C 10 alkyl or silyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0033] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C1-C 10 Alkyl, C5-C 10 Cycloalkyl, C5-C 10 Cycloalkenyl, C1-C 10 Alkoxy, C3-C 20 Cycloalkyl, C6-C 30Aryl, C3-C 30 One or more of heteroaryl and arylamine.

[0034] In a preferred embodiment, the structure of the organic compound is shown in any one of the general formulas (4) to (9):

[0035]

[0036] In general formula (4) to general formula (9), the definitions of Z0, Z, X0, X1, n, A1, A2, and A3 are the same as those defined above;

[0037] The dashed lines in the general formula represent connection via a single bond or no connection, and only two of the three dashed lines in each general formula represent connection via a single bond.

[0038] In a preferred embodiment, A1-A4 is represented by any one of the following ring structures:

[0039]

[0040] In a preferred embodiment, R0 and R1 are independently represented by the following structures:

[0041] Tert-butyl.

[0042] In a preferred embodiment, the structure of the organic compound is shown in any one of the general formulas (10) to (18):

[0043]

[0044]

[0045] In general formula (10) to general formula (18), the definitions of Z0, Z, X0, X1, n, A1, A2, and A3 are the same as those defined above.

[0046] In a preferred embodiment, the structure of the organic compound is shown in any one of the general formulas (19) to (22):

[0047]

[0048] In general formula (19) to general formula (22), the definitions of Z0 and Z are the same as those defined above;

[0049] The dashed lines in the general formula represent connection via a single bond or no connection, and only two of the three dashed lines in each general formula represent connection via a single bond.

[0050] In the above general formula, n is 0 or 1. When n is 0, it means that X1 does not exist, and A2 and A3 are not connected through X1.

[0051] In the general formula (2), the asterisk indicates a site that can be linked to other groups.

[0052] In a preferred embodiment, the structure of the organic compound is shown in any one of the general formulas (23) to (32):

[0053]

[0054] In general formulae (23) to (32), X0 represents a single bond, -O-, -Si(R2)2-, -C(R3)2-, -N(R4)-;

[0055] Each occurrence of R2, R3, and R4 is represented independently as C1-C 10 Alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl, substituted or unsubstituted C5-C 30 Cycloalkyl, substituted or unsubstituted C5-C 30 Cycloalkenyl;

[0056] Each occurrence of Z can be the same or different and is represented by C-R1;

[0057] Each occurrence of R1 is the same or different and independently represents H, a deuterium atom, a halogen atom, a cyano group, a C1-C 10 alkyl or silyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0058] R a1 -R a14 Each independently represents H, deuterium atom, halogen atom, cyano group, C1-C 10 alkyl or silyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 Heteroaryl and arylamine groups;

[0059] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C1-C 10 Alkyl, C5-C 10 Cycloalkyl, C5-C 10 Cycloalkenyl, C1-C 10 Alkoxy, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C3-C 30 One or more heteroaryl groups.

[0060] Preferably, the R a1 -R a14 and tert-butyl, deuterated tert-butyl, tritium-substituted tert-butyl, deuterated cyclopentyl, tritium-substituted cyclopentyl, cyclopentyl, phenyl, deuterated phenyl, tritium-substituted phenyl, biphenyl, deuterated biphenyl, tritium-substituted biphenyl 1,2-diphenyl terphenyl, ... The invention further comprises a deuterated methyl-substituted phenyl, a deuterated ethyl-substituted phenyl, a deuterated isopropyl-substituted phenyl, a deuterated tert-butyl-substituted phenyl, a deuterated methyl-substituted bisphenyl, a deuterated ethyl-substituted bisphenyl, a deuterated isopropyl-substituted bisphenyl, a deuterated tert-butyl-substituted phenyl, a deuterated methyl-substituted bisphenyl, a deuterated ethyl-substituted bisphenyl, a deuterated isopropyl-substituted bisphenyl, a deuterated tert-butyl-substituted bisphenyl, a tritiated methyl-substituted phenyl, a tritiated ethyl-substituted bisphenyl, a tritiated isopropyl-substituted phenyl, a tritiated tert-butyl-substituted phenyl, a tritiated methyl-substituted bisphenyl, a tritiated ethyl-substituted bisphenyl, a tritiated isopropyl-substituted bisphenyl or a tritiated tert-butyl-substituted bisphenyl.

[0061] Preferably, the R a1 -R a14 The independent representations are as follows:

[0062] Hydrogen atom, methyl, tert-butyl, phenyl, cyano,

[0063] Any one of.

[0064] In a preferred embodiment, R0 and R1 are independently hydrogen, deuterium, tritium, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated diphenyl biphenyl, tritiated biphenyl, deuterated terphenyl, tritiated terphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, pyridyl, quinolyl, furanyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted phenyl, isophthalic acid, tert-butyl phthalate ... Propyl-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, tritiated methyl-substituted phenyl, tritiated ethyl-substituted phenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, tritiated methyl-substituted biphenyl, tritiated ethyl-substituted biphenyl, tritiated isopropyl-substituted biphenyl or tritiated tert-butyl-substituted biphenyl;

[0065] R2, R3, and R4 are independently hydrogen, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl , tritiated biphenyl, deuterated terphenyl, tritiated terphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, pyridyl, quinolyl, furanyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 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, tritiated methyl substituted phenyl, tritiated ethyl substituted phenyl, tritiated isopropyl substituted phenyl, tritiated tert-butyl substituted phenyl, tritiated methyl substituted biphenyl, tritiated ethyl substituted biphenyl, tritiated isopropyl substituted biphenyl or tritiated tert-butyl substituted biphenyl;

[0066] A1-A4 are each independently a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a diphenyl ether group, a methyl-substituted diphenyl ether group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, a furanyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a phenyl-substituted amino group, a tert-butyl-substituted dibenzofuranyl group, a methyl-substituted phenyl group, an ethyl-substituted phenyl group, an isopropyl-substituted phenyl group, a tert-butyl-substituted phenyl group, a methyl-substituted biphenyl group, an ethyl-substituted biphenyl group, an isopropyl-substituted biphenyl group, a tert-butyl-substituted biphenyl group, or a xanthone group;

[0067] The substituents for the substituent group are optionally selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, -CF3, 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.

[0068] Preferably, the specific structural formula of the resonance type organic compound is any one of the following structures:

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096] An organic light-emitting device comprises a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode, and the functional layer of the organic light-emitting device comprises the resonance type organic compound.

[0097] In a preferred embodiment, the functional layer comprises a light-emitting layer, and the light-emitting layer comprises a host material and a doping material;

[0098] In a preferred embodiment, the doping material of the light-emitting layer is the resonance-type organic compound;

[0099] 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 a resonance-type organic compound.

[0100] Compared with the prior art, the beneficial technical effects of the present invention are:

[0101] (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 fluorescence under the action of an electric field and can be applied to OLED lighting or OLED display fields;

[0102] (2) The compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%;

[0103] (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 the luminous efficiency of the device;

[0104] (4) The structure represented by Formula 2 is connected to the skeleton represented by Formula 1 through a fused ring, which is beneficial to further enhance the resonance effect of the molecule and further narrow the emission spectrum of the material;

[0105] (5) The structure represented by Formula 2 combined with the skeleton represented by Formula 1 can further increase the degree of delocalization of the electron cloud, improve the oscillator strength of the excited state, and reduce the reorganization energy of the molecule, thereby reducing the Stokes shift and narrowing the half-peak width.

[0106] The compound of the present invention has a narrow half-peak width, a high fluorescence quantum yield, a low evaporation temperature, a high glass transition temperature and molecular thermal stability, and suitable HOMO and LUMO energy levels, and can be used as a doping material for the light-emitting layer of an organic electroluminescent device, thereby improving the luminescent color purity and life of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0107] 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;

[0108] 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.

[0109] Figure 2 Compound 1 in toluene solution (5×10 -5 M) in the spectrum;

[0110] Figure 3 Compound 381 in toluene solution (5×10 -5 M) in the spectrum;

[0111] Figure 4 Compound 720 in toluene solution (5×10 -5 M) in the spectrum;

[0112] Figure 5 is the solution of compound 1 in deuterated chloroform1 H NMR spectra;

[0113] Figure 6 is compound 381 in deuterated chloroform 1 H NMR spectra;

[0114] Figure 7 is compound 720 in deuterated chloroform 1 H NMR spectra. DETAILED DESCRIPTION

[0115] The present invention is described in detail below in conjunction with the accompanying drawings and embodiments.

[0116] In the present invention, unless otherwise specified, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule. In addition, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between energy levels is also a comparison of the magnitude of their absolute values. Those skilled in the art know that the greater the absolute value of an energy level, the lower the energy of the energy level.

[0117] In the accompanying drawings, the sizes of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, the layer or element may be directly on the other layer or substrate, or there may be intervening layers. In addition, it will be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or there may be one or more intervening layers. The same reference numerals throughout the text represent the same elements.

[0118] 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.

[0119] 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 plastic substrates; opaque substrates such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, its use direction is different. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.

[0120] 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 Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr or a metal mixture. The thickness of the first electrode layer depends on the material used, and is typically 50-500nm, preferably 70-300nm and more preferably 100-200nm.

[0121] 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.

[0122] Herein, 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.

[0123] 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 OLED devices.

[0124] Examples of the above materials include phthalocyanine derivatives, triazole derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, oxadiazole derivatives, hydrazone derivatives, stilbene derivatives, pyridoline derivatives, polysilane derivatives, imidazole derivatives, phenylenediamine derivatives, amino-substituted quilone derivatives, styryl anthracene derivatives, styrylamine derivatives and the like, fluorene derivatives, spirofluorene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, carbazole derivatives, polyarylalkane derivatives, polyphenylene vinyl and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole derivatives, thiophene oligomers and the like, conductive polymer oligomers, aromatic tertiary amine compounds, styrene amination compounds, compounds, triamines, tetraamines, benzidines, propargyl diamine derivatives, p-phenylenediamine derivatives, m-phenylenediamine derivatives, 1,1'-bis(4-diarylaminophenyl)cyclohexane, 4,4'-bis(diarylamino)biphenyls, bis[4-(diarylamino)phenyl]methanes, 4,4'-bis(diarylamino)terphenyls, 4,4'-bis(diarylamino)quaterphenyls, 4,4'-bis(diarylamino)diphenyl ethers, 4,4'-bis(diarylamino)diphenylsulfanes, bis[4-(diarylamino)phenyl]dimethylmethanes, bis[4-(diarylamino)phenyl]-bis(trifluoromethyl)methanes, or 2,2-diphenylethylene compounds.

[0125] Furthermore, according to the device matching requirements, the hole transport film layer between the hole transport auxiliary layer and the hole injection layer constituting the organic electroluminescent device can be a single film layer or a superposition structure of multiple hole transport materials. In this article, for the above-mentioned hole carrier conduction film layers with different functions, their film thickness is not particularly limited.

[0126] 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.

[0127] In view of the above empirical summary, for hole-type host 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.

[0128] Therefore, in one embodiment of the present invention, in order to better inject holes, the hole injection layer also includes a P-type doping 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.

[0129] 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.

[0130] 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.

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

[0132] The thickness of the electron blocking layer of the present invention may be 1-20 nm, preferably 5-10 nm, but the thickness is not limited to this range.

[0133] 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.

[0134] 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 resonance-type organic compound represented by the general formula (1) of the present invention.

[0135] The light-emitting layer may contain a single host material or a dual host material;

[0136] 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;

[0137] 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.

[0138] The light-emitting layer may include a host material, an exciton-sensitizing material, and a doping material;

[0139] 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 resonant 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.

[0140] 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.

[0141] 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 15-30 nm, but the thickness is not limited to this range.

[0142] 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.

[0143] The hole blocking layer is a layer that blocks the 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 efficiency 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 effects known in the prior art can be used, for example, phenanthroline derivatives such as bathocuproin (referred to as BCP), metal complexes of hydroxyquinoline derivatives such as aluminum (III) bis (2-methyl-8-quinoline) -4-phenylphenolate (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, 9,9'-(5-(6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)-1,3-phenylene)bis (9H-carbazole) (CAS No.: 1345338-69-3) and other pyrimidine derivatives. The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm, and more preferably 10-100 nm, but the thickness is not limited to this range.

[0144] 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. Preferably, the material has a high electron mobility. As the electron transport layer of the organic electroluminescent device of the present invention, the electron transport layer materials for organic electroluminescent devices known in the prior art can be used, for example, metal complexes of hydroxyquinoline derivatives represented by Alq3, BAlq and Liq, various rare earth metal complexes, triazole derivatives, 2,4-bis(9,9-dimethyl-9H-fluorene-2-yl)-6-(naphthalene-2-yl)-1,3,5-triazine (CAS No.: 1459162-51-6) and other triazine derivatives, 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201) and other imidazole derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, etc. 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.

[0145] The electron injection layer may be disposed above 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 known in the prior art can be used, for example, lithium; lithium salts such as 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide. 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.

[0146] 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, and is typically 10-50 nm, preferably 15-20 nm.

[0147] 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.

[0148] 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.

[0149] 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;

[0150] Preparation Example 1 Synthesis of Compound 1:

[0151]

[0152] Preparation of intermediate B1:

[0153] Add raw material A1 (50.0 mmol) and 500 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, add NBS (105 mmol) in batches, and stir at 0°C for 10 hours. Concentrate the reaction solution and purify it through a silica gel column using petroleum ether: ethyl acetate = 100:1 as a developing solvent to obtain intermediate B1. LC-MS: Measured value: 412.89 ([M+H] + ), theoretical value: 411.92.

[0154] Preparation of intermediate B2:

[0155] Add intermediate B1 (10mmol) and 50mL anhydrous DMF to a three-necked flask in sequence, and use nitrogen protection. Add NaH (net content 12mmol) wrapped in mineral oil (65%) in batches under ice-water bath conditions. Stir the mixture for 0.5 hours, and slowly drop the raw material A2 (10mmol) solution dissolved in 10mL anhydrous DMF. After the reaction is completed, add 100mL of water to quench the reaction, and filter the large amount of white precipitate precipitated. Collect the precipitate and use dichloromethane solution, dry it with anhydrous sodium sulfate, filter it, concentrate the reaction solution and purify it through a silica gel column using petroleum ether: ethyl acetate = 500: 1 as a developing agent to obtain intermediate B2. LC-MS: Measured value: 488.99 ([M+H] + ), theoretical value: 487.95.

[0156] Preparation of intermediate B3:

[0157] The intermediate B2 (10.0 mmol), tetra-n-butylammonium bromide (nBu4NBr) (1 mmol), triphenylphosphine (0.5 mmol), palladium acetate catalyst 0.2 mmol, potassium carbonate 20 mmol, DMAc 50 mL were added to the two-necked flask in sequence, and then nitrogen protection was applied, and the mixture was heated under reflux and stirred for 24 hours. After cooling, the organic phase was separated and collected, and the organic phase was dried over anhydrous sodium sulfate, and then filtered and concentrated. The compound was separated by a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain the intermediate B3. LC-MS: Measured value: 409.07 ([M+H] + ), theoretical value: 408.03.

[0158] Preparation of intermediate B4:

[0159] Add raw material A4 (10mmol) and 50mL anhydrous DMF to a three-necked flask in sequence, and use nitrogen protection. Add NaH (net content 12mmol) wrapped in mineral oil (65%) in batches under ice-water bath conditions. Stir the mixture at room temperature for 0.5 hours, and slowly drop the raw material A3 (10mmol) solution dissolved in 10mL anhydrous DMF. After the reaction is completed, add 100mL of water to quench the reaction, and filter the large amount of white precipitate precipitated. Collect the precipitate and use dichloromethane solution, dry it with anhydrous sodium sulfate, filter it, concentrate the reaction solution and purify it through a silica gel column using petroleum ether as a developing agent to obtain intermediate B4. LC-MS: Measured value: 374.25 ([M+H] + ), theoretical value: 373.22.

[0160] Preparation of intermediate B5:

[0161] Add intermediate B3 (10 mmol) and 100 mL of anhydrous DMF to a three-necked flask in sequence, and use nitrogen protection. Add NaH (net content 12 mmol) wrapped in mineral oil (65%) in batches under ice-water bath conditions. Stir the mixture for 0.5 hours, and slowly drop the intermediate B4 (10 mmol) solution dissolved in 20 mL of anhydrous DMF. After the reaction is completed, add 150 mL of water to quench the reaction, and filter the large amount of white precipitate. Collect the precipitate and use dichloromethane solution, dry it with anhydrous sodium sulfate, filter it, concentrate the reaction solution and purify it through a silica gel column using petroleum ether as a developing agent to obtain intermediate B5. LC-MS: Measured value: 762.33 ([M+H] + ), theoretical value: 761.24.

[0162] Preparation of compound 1:

[0163] In a low-temperature eggplant-shaped bottle, intermediate B5 (5.0 mmol) and tert-butylbenzene (50 mL) were added in sequence, the temperature was lowered to -78°C, and a n-hexane solution of n-butyl lithium (5.5 mmol) was slowly added, followed by nitrogen protection, stirring and warming to room temperature, and then n-hexane was removed under negative pressure at 60°C; after reacting for 2 hours, BBr3 (6.0 mmol) was added at -42°C, the temperature was kept stirring for 2 hours, and the temperature was slowly restored to room temperature. After stirring at room temperature for 10 hours, DIPEA (N, N-diisopropylethylamine) (10 mmol) was added in an ice-water bath and heated to 120°C and refluxed for 36 hours. The reaction was cooled to room temperature, the solution was filtered with diatomaceous earth, the organic phase was collected and the high-boiling solvent was removed by vacuum distillation, dissolved with dichloromethane, dried over anhydrous sodium sulfate, filtered, the organic phase was concentrated, and purified by a silica gel column, and toluene was used as a developing solvent to obtain compound 1. LC-MS: Measured value: 692.39 ([M+H] + ), theoretical value: 691.32. Compound 1 in toluene solution (5×10-5 M) is shown in the attached Figure 2 , compound 381 in deuterated chloroform 1 H NMR diagram is attached Figure 5 .

[0164] Preparation Example 2 Synthesis of Compound 84:

[0165]

[0166] Preparation of intermediate B6:

[0167] Add raw material A5 (10.0 mmol), NBS (20.0 mmol), and acetic acid 50 mL to a two-necked flask in sequence, then protect with nitrogen, avoid light, stir at 0°C for 10 hours, cool and wash with anhydrous sodium sulfite solution (3×50 mL), separate, collect the organic phase, and dry with anhydrous sodium sulfate, filter and concentrate the organic phase, separate the compound through a silica gel column with petroleum ether as the developing solvent, and obtain intermediate B6. LC-MS: Measured value: 440.99 ([M+H] + ), theoretical value: 439.95.

[0168] Preparation of intermediate B7:

[0169] The intermediate B6 (10.0 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) were added to the two-necked flask in sequence, and the mixture was stirred at room temperature for 0.5 hours. Then, the raw material A6 (10 mmol) dissolved in 10 mL of anhydrous DMF was added, and the mixture was stirred at room temperature for 5 hours. 100 mL of water was added to precipitate a large amount of white solid, which was filtered and dissolved in dichloromethane. The precipitate was dried and filtered using anhydrous sodium sulfate, and the organic phase was concentrated. The compound was separated by passing through a silica gel column using petroleum ether as a developing solvent to obtain the intermediate B7. LC-MS: Measured value: 531.03 ([M+H] + ), theoretical value: 530.00.

[0170] Preparation of intermediate B8:

[0171] Add intermediate B7 (5.0 mmol), N,N-dimethylformamide (DMAc) 50 mL, palladium acetate (0.5 mmol), potassium carbonate (25.0 mmol), tetra-n-butylammonium bromide (2.5 mmol) and triphenylphosphine (5 mmol) to a two-necked bottle in sequence, heat under reflux and stir for 24 hours, filter and concentrate the reaction solution, separate the compound through a silica gel column with petroleum ether as a developing solvent, and obtain intermediate B8. LC-MS: Measured value: 451.11 ([M+H] + ), theoretical value: 450.07.

[0172] Preparation of intermediate B9:

[0173] Add intermediate B8 (10.0 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) to a two-necked flask in sequence, stir at room temperature for 0.5 hours, then add intermediate B4 (10 mmol) dissolved in 10 mL anhydrous DMF, stir at room temperature for 5 hours, add 100 mL water, a large amount of white solid precipitates, filter, take the precipitate and dissolve it in dichloromethane, dry and filter it with anhydrous sodium sulfate, concentrate the organic phase, separate the compound through a silica gel column with petroleum ether: ethyl acetate = 10:1 as the developing solvent, and obtain intermediate B9. LC-MS: Measured value: 804.36 ([M+H] + ), theoretical value: 803.29.

[0174] Preparation of compound 84: Reference compound 1; LC-MS: Measured value: 734.32 ([M+H] + ), theoretical value: 733.36. 1 HNMR (400 MHz, deuterated chloroform) δ8.30 (d, 1H), 7.99–7.95 (m, 1H), 7.92 (q, 1H), 7.83 (d, 2H), 7.72 (dd, 2H), 7.68 (m, 1H), 7.55–7.49 (m, 1H), 7.47–7.36 (m, 4H), 7.31 (dd, 2H), 7.29 (d, 1H), 7.23 (m, 1H), 2.49 (d, 6H), 2.30 (s, 3H), 1.46 (s, 9H), 1.44 (s, 9H).

[0175] Preparation Example 3 Synthesis of Compound 8:

[0176]

[0177] Preparation of intermediate B10:

[0178] Raw material A7 (10.0 mmol), raw material A3 (10.0 mmol), cesium carbonate (22.0 mmol), and anhydrous NMP 50 mL were added to the two-necked flask in sequence, and then stirred and refluxed at 150° C. for 18 hours under nitrogen protection. The organic phase was concentrated and separated by passing through a silica gel column with petroleum ether as a developing solvent to obtain intermediate B10. LC-MS: Measured value: 189.14 ([M+H] + ), theoretical value: 188.06.

[0179] Preparation of intermediate B11:

[0180] Add intermediate B3 (10.0 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) to a two-necked flask in sequence, stir at room temperature for 0.5 hours, then add intermediate B10 (10 mmol) dissolved in 10 mL anhydrous DMF, stir at room temperature for 5 hours, add 100 mL water, a large amount of white solid precipitates, filter, take the precipitate and dissolve it in dichloromethane, dry and filter it with anhydrous sodium sulfate, concentrate the organic phase, separate the compound through a silica gel column with petroleum ether: ethyl acetate = 10:1 as the developing solvent, and obtain intermediate B11. LC-MS: Measured value: 577.04 ([M+H] + ), theoretical value: 576.08.

[0181] Preparation of compound 8:

[0182] In a low-temperature eggplant-shaped bottle, intermediate B11 (5.0 mmol) and tert-butylbenzene (50 mL) were added in sequence, the temperature was lowered to -78°C, and a n-hexane solution of n-butyl lithium (5.5 mmol) was slowly added, followed by stirring and warming to room temperature. At 60°C, n-hexane was removed under negative pressure; nitrogen protection was then connected, and BBr3 (6.0 mmol) was added at -42°C after reacting for 2 hours, the temperature was maintained and stirred for 2 hours, and the temperature was slowly restored to room temperature. After stirring at room temperature for 10 hours, DIPEA (N, N-diisopropylethylamine) (10 mmol) was added in an ice-water bath and heated to 120°C and refluxed for 36 hours. The reaction was cooled to room temperature, the solution was filtered with diatomaceous earth, the organic phase was collected and the high-boiling solvent was removed by distillation under reduced pressure, dissolved with dichloromethane, dried over anhydrous sodium sulfate, filtered, the organic phase was concentrated, and purified by a silica gel column, and toluene was used as a developing solvent to obtain compound 8. LC-MS: Measured value: 507.19 ([M+H] + ), theoretical value: 506.16. 1 H NMR (400 MHz, deuterated chloroform) δ8.18 (dd, 1H), 8.15 (dd, 1H), 8.11 (dd, 1H), 7.69–7.61 (m, 3H), 7.52 (dd, 1H), 7.49–7.20 (m, 9H), 7.11 (td, 1H), 7.09 (dd, 1H), 7.05 (dd, 1H).

[0183] Preparation Example 4 Synthesis of Compound 214:

[0184]

[0185] Preparation of intermediate B12:

[0186] Add raw material A1 (10.0 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) to a two-necked flask in sequence, stir at room temperature for 0.5 hours, then add raw material A8 (10 mmol) dissolved in 10 mL anhydrous DMF, stir at room temperature for 5 hours, add 100 mL of water, a large amount of white solid precipitates, filter, take the precipitate and dissolve it in dichloromethane, dry and filter it with anhydrous sodium sulfate, concentrate the organic phase, separate the compound through a silica gel column with petroleum ether: ethyl acetate = 50:1 as the developing solvent, and obtain intermediate B12. LC-MS: Measured value: 411.10 ([M+H] + ), theoretical value: 410.04.

[0187] Preparation of intermediate B13:

[0188] To a two-necked flask, add intermediate B12 (5.0 mmol), 50 mL of N,N-dimethylformamide (DMAc), palladium acetate (0.5 mmol), potassium carbonate (25.0 mmol), tetra-n-butylammonium bromide (2.5 mmol) and triphenylphosphine (5 mmol), heat under reflux and stir for 24 hours, filter and concentrate the reaction solution, separate the compound through a silica gel column with petroleum ether as a developing solvent, and obtain intermediate B13. LC-MS: Measured value: 331.15 ([M+H] + ), theoretical value: 330.12.

[0189] Preparation of intermediate B14:

[0190] Add raw material A4 (10.0 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) to a two-necked flask in sequence, stir at room temperature for 0.5 hours, then add raw material A9 (10 mmol) dissolved in 10 mL anhydrous DMF, stir at room temperature for 5 hours, add 100 mL water, a large amount of white solid precipitates, filter, take the precipitate and dissolve it in dichloromethane, dry and filter it with anhydrous sodium sulfate, concentrate the organic phase, separate the compound through a silica gel column with petroleum ether: ethyl acetate = 50:1 as the developing solvent, and obtain intermediate B14. LC-MS: Measured value: 452.11 ([M+H] + ), theoretical value: 451.13.

[0191] Preparation of intermediate B15:

[0192] Add intermediate B13 (10.0 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) to a two-necked flask in sequence, stir at room temperature for 0.5 hours, then add intermediate B14 (10 mmol) dissolved in 10 mL anhydrous DMF, stir at room temperature for 5 hours, add 100 mL of water, a large amount of white solid precipitates, filter, take the precipitate and dissolve it in dichloromethane, dry and filter it with anhydrous sodium sulfate, concentrate the organic phase, separate the compound through a silica gel column with petroleum ether: ethyl acetate = 10:1 as the developing solvent, and obtain intermediate B15. LC-MS: Measured value: 762.22 ([M+H] + ), theoretical value: 761.24.

[0193] Preparation of compound 214:

[0194] Into a cryogenic eggplant-shaped flask, intermediate B15 (5.0 mmol) and tert-butylbenzene (50 mL) were added in sequence, and the temperature was lowered to -78°C. A solution of n-butyllithium (5.5 mmol) in n-hexane was slowly added, followed by stirring and warming to room temperature. The n-hexane was then removed under negative pressure at 60°C. Nitrogen protection was then applied, and BBr3 (6.0 mmol) was added at -42°C after reacting for 2 hours. The temperature was maintained and stirred for 2 hours, and the temperature was slowly restored to room temperature. After stirring at room temperature for 10 hours, DIPEA (N,N-diisopropylethylamine) (10 mmol) was added in an ice-water bath and heated to 120°C and refluxed for 36 hours. The reaction was cooled to room temperature, the solution was filtered with diatomaceous earth, the organic phase was collected and the high-boiling solvent was removed by distillation under reduced pressure, dissolved with dichloromethane, dried over anhydrous sodium sulfate, filtered, the organic phase was concentrated, and purified by a silica gel column. Toluene was used as a developing agent to obtain compound 214. Since the target site has a higher reactivity, the B connection site will be selectively connected at the site shown in 214. LC-MS: Found: 692.35 ([M+H] + ), theoretical value: 691.32. 1 H NMR (400 MHz, deuterated chloroform) δ8.37 (d, 1H), 8.14–8.09 (m, 1H), 8.04 (dd, 1H), 8.01–7.93 (m, 1H), 7.90–7.84 (m, 1H), 7.71 (dd, 1H), 7.68–7.60 (m, 2H), 7.55–7.51 (m, 2H), 7.45–7.39 (m, 3H), 7.30–7.22 (m, 6H), 7.15 (d, 1H), 1.33 (s, 9H), 1.27 (s, 9H).

[0195] Preparation Example 5 Synthesis of Compound 206:

[0196]

[0197] Preparation of intermediate B16:

[0198] Raw material A9 (10.0 mmol), raw material A7 (10.0 mmol), cesium carbonate (22 mmol), and anhydrous NMP 50 mL were added to the two-necked flask in sequence, and then stirred and refluxed at 150° C. for 6 hours under nitrogen protection. The organic phase was concentrated and separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate B16. LC-MS: Measured value: 266.99 ([M+H] + ), theoretical value: 265.97.

[0199] Preparation of intermediate B17:

[0200] The intermediate B13 (10 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) were added to the two-necked flask in sequence, and the mixture was stirred at room temperature for 0.5 hours. Then, the raw material B16 (10 mmol) dissolved in 10 mL of anhydrous DMF was added, and the mixture was stirred at room temperature for 5 hours. 100 mL of water was added to precipitate a large amount of white solid, which was filtered. The precipitate was dissolved in dichloromethane, dried and filtered using anhydrous sodium sulfate, and the organic phase was concentrated. The compound was separated by a silica gel column using petroleum ether: ethyl acetate = 20:1 as the developing solvent to obtain the intermediate B17. LC-MS: Measured value: 577.10 ([M+H] + ), theoretical value: 576.08.

[0201] Preparation of compound 206:

[0202] In a low-temperature eggplant-shaped bottle, intermediate B17 (5.0 mmol) and tert-butylbenzene (50 mL) were added in sequence, the temperature was lowered to -78°C, and a n-hexane solution of n-butyl lithium (5.5 mmol) was slowly added, followed by stirring and warming to room temperature, and then n-hexane was removed under negative pressure at 60°C; nitrogen protection was then connected, and BBr3 (6.0 mmol) was added at -42°C after reacting for 2 hours, the temperature was maintained and stirred for 2 hours, and the temperature was slowly restored to room temperature. After stirring at room temperature for 10 hours, DIPEA (N, N-diisopropylethylamine) (10 mmol) was added in an ice-water bath and heated to 120°C and refluxed for 36 hours. The reaction was cooled to room temperature, the solution was filtered with diatomaceous earth, the organic phase was collected and the high-boiling solvent was removed by distillation under reduced pressure, dissolved with dichloromethane, dried over anhydrous sodium sulfate, filtered, the organic phase was concentrated, and purified by a silica gel column, and toluene was used as a developing solvent to obtain compound 206. LC-MS: Measured value: 507.31 ([M+H] + ), theoretical value: 506.16. 1H NMR (400 MHz, deuterated chloroform) δ 8.20–8.12 (m, 1H), 8.10–8.03 (m, 2H), 7.91 (dd, 1H), 7.78–7.66 (m, 2H), 7.59 (dd, 1H), 7.53–7.30 (m, 8H), 7.21 (dd, 1H), 7.06 (m, 1H), 6.95 (dd, 1H), 6.88 (dd, 1H).

[0203] Preparation Example 6 Synthesis of Compound 218:

[0204]

[0205] Preparation of intermediate B18:

[0206] Compound 214 (10.0 mmol), raw material A10 (15 mmol), [Ir(COD)(OCH3)]2 (0.06 mmol), and 50 mL of tetrahydrofuran were added to a single-mouth bottle in sequence, and the reaction was carried out at room temperature for 10 hours, and nitrogen was protected. The reaction was then filtered, the organic phase was concentrated, and the compound was separated by a silica gel column with petroleum ether: ethyl acetate = 1:1 as the developing solvent to obtain intermediate B18. The reaction has relatively good selectivity (reference DOI: 10.31635 / ccschem.021.202101033), and the boric ester at the para position of B has higher activity and selectivity. LC-MS: Measured value: 818.38 ([M+H] + ), theoretical value: 817.40.

[0207] Preparation of compound 218:

[0208] The intermediate B18 (10.0 mmol), the raw material A11 (10.0 mmol), the Pd(PPh3)4 catalyst 0.1 mmol, 50 mL of tetrahydrofuran: water = 10:1 mixed solution, potassium carbonate (20 mmol) were added to the two-necked flask in sequence, and then nitrogen was protected and stirred at 80°C for 6 hours. After cooling, the liquid was separated and the organic phase was collected, dried over anhydrous sodium sulfate, filtered and concentrated, and the compound was separated by silica gel column with petroleum ether: ethyl acetate = 5:1 as the developing solvent to obtain compound 218. LC-MS: Measured value: 923.35 ([M+H] + ), theoretical value: 922.40. 1H NMR (400 MHz, deuterated chloroform) δ8.71–8.62 (m, 1H), 8.59–8.51 (m, 4H), 8.35–8.33 (m, 2H), 8.30 (d, 1H), 8.23 ​​(dd, 1H), 8.16 (dd, 1H), 8.11 (dd, 1H), 7.76 (dd, 1H), 7.70 (d, 1H), 7.60 (m, 2H), 7.55–7.43 (m, 6H), 7.39–7.28 (m, 5H), 7.22 (td, 2H), 7.15 (d, 1H), 1.44 (s, 9H), 1.37 (s, 9H).

[0209] Preparation Example 7 Synthesis of Compound 221:

[0210]

[0211] Preparation of intermediate B19:

[0212] Compound 206 (10.0 mmol), raw material A10 (15 mmol), [Ir(COD)(OCH3)]2 (0.06 mmol), and 50 mL of tetrahydrofuran were added to a single-mouth bottle in sequence, and reacted at room temperature for 10 hours, and protected by nitrogen. The reaction was then filtered, the organic phase was concentrated, and the compound was separated by a silica gel column with petroleum ether: ethyl acetate = 1:1 as the developing solvent to obtain intermediate B19. LC-MS: Measured value: 633.30 ([M+H] + ), theoretical value: 632.24.

[0213] Preparation of compound 221:

[0214] The intermediate B19 (10.0 mmol), the raw material A11 (10.0 mmol), the Pd(PPh3)4 catalyst 0.1 mmol, 50 mL of tetrahydrofuran: water = 10: 1 mixed solution, potassium carbonate (20 mmol) were added to the two-necked flask in sequence, and then nitrogen was protected and stirred at 80°C for 6 hours. After cooling, the liquid was separated and the organic phase was collected, dried over anhydrous sodium sulfate, filtered and concentrated, and the compound was separated by silica gel column with petroleum ether: ethyl acetate = 5: 1 as the developing solvent to obtain compound 221. LC-MS: Measured value: 738.28 ([M+H] + ), theoretical value: 737.24. 1H NMR (400 MHz, deuterated chloroform) δ 8.52–8.39 (m, 4H), 8.24–8.19 (m, 1H), 8.16–8.02 (m, 3H), 7.75 (dd, 1H), 7.68–7.59 (m, 2H), 7.57–7.49 (m, 6H), 7.43–7.20 (m, 8H), 7.15 (td, 1H), 7.09 (dd, 1H), 7.02 (d, 1H).

[0215] Preparation Example 8 Synthesis of Compound 232:

[0216]

[0217]

[0218] Preparation of intermediate B20:

[0219] Add raw material A12 (5.0 mmol), N,N-dimethylformamide (DMAc) 50 mL, palladium acetate (0.5 mmol), potassium carbonate (25.0 mmol), tetra-n-butylammonium bromide (2.5 mmol) and triphenylphosphine (5 mmol) to a two-necked bottle in sequence, heat and reflux with stirring for 24 hours, filter and concentrate the reaction solution, separate the compound by silica gel column with petroleum ether as the developing solvent, and obtain intermediate B20. LC-MS: Measured value: 242.11 ([M+H] + ), theoretical value: 241.09.

[0220] Preparation of intermediate B21:

[0221] The intermediate B20 (10.0 mmol), NBS (20.0 mmol), and anhydrous DMF 7 mL were added to the two-necked flask in sequence, and then nitrogen was protected, and refluxed and stirred at 0°C for 10 hours. After cooling, it was washed with anhydrous sodium sulfite solution (3×50 mL), separated, and the organic phase was collected and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated, and the compound was separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate B21. LC-MS: Measured value: 320.10 ([M+H] + ), theoretical value: 319.00.

[0222] Preparation of intermediate B22:

[0223] The intermediate B21 (10.0 mmol), the raw material A13 (10.0 mmol), the Pd2(dba)3 catalyst 0.1 mmol, potassium tert-butyl alcohol (20 mmol), tri-tert-butylphosphine (0.3 mmol), and toluene 50 mL were added to the two-necked flask in sequence, and then nitrogen was protected, refluxed and stirred at 110°C for 6 hours, and the organic phase was filtered and concentrated after cooling, and the compound was separated by silica gel column with petroleum ether: ethyl acetate = 10:1 as the developing solvent to obtain the intermediate B22. LC-MS: Measured value: 401.10 ([M+H] + ), theoretical value: 400.05.

[0224] Preparation of intermediate B23:

[0225] To a two-necked flask, add intermediate B22 (5.0 mmol), 50 mL of N,N-dimethylformamide (DMAc), palladium acetate (0.5 mmol), potassium carbonate (25.0 mmol), tetra-n-butylammonium bromide (2.5 mmol) and triphenylphosphine (5 mmol), heat under reflux and stir for 24 hours, filter and concentrate the reaction solution, separate the compound through a silica gel column with petroleum ether as a developing solvent, and obtain intermediate B23. LC-MS: Measured value: 365.18 ([M+H] + ), theoretical value: 364.08.

[0226] Preparation of intermediate B24:

[0227] The intermediate B23 (10.0 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) were added to the two-necked flask in sequence, and the mixture was stirred at room temperature for 0.5 hours. Then, the raw material B4 (10 mmol) dissolved in 10 mL of anhydrous DMF was added, and the mixture was stirred at room temperature for 5 hours. 100 mL of water was added to precipitate a large amount of white solid, which was filtered. The precipitate was dissolved in dichloromethane, dried and filtered using anhydrous sodium sulfate, and the organic phase was concentrated. The compound was separated by a silica gel column using petroleum ether: ethyl acetate = 10:1 as the developing solvent to obtain the intermediate B24. LC-MS: Measured value: 718.33 ([M+H] + ), theoretical value: 717.29.

[0228] Preparation of compound 232:

[0229] In a low-temperature eggplant-shaped bottle, intermediate B24 (5.0 mmol) and tert-butylbenzene (50 mL) were added in sequence, the temperature was lowered to -78°C, and a n-hexane solution of tert-butyl lithium (6.0 mmol) was slowly added, followed by stirring and warming to room temperature, and then the n-hexane was removed under negative pressure at 60°C; nitrogen protection was then connected, and BBr3 (6.5 mmol) was added at -42°C after reacting for 2 hours, the temperature was kept stirring for 2 hours, and the temperature was slowly restored to room temperature. After stirring at room temperature for 10 hours, DIPEA (N, N-diisopropylethylamine) (1 mmol) was added in an ice-water bath and heated to 120°C and refluxed for 36 hours. The reaction was cooled to room temperature, the solution was filtered with diatomaceous earth, the organic phase was collected and the high-boiling solvent was removed by distillation under reduced pressure, dissolved with dichloromethane, dried over anhydrous sodium sulfate, filtered, the organic phase was concentrated, and purified by a silica gel column, and toluene was used as a developing solvent to obtain compound 232. LC-MS: Measured value: 692.49 ([M+H] + ), theoretical value: 691.32. 1 H NMR (400 MHz, deuterated chloroform) δ8.19 (d, 1H), 8.15 (dd, 1H), 8.01 (dd, 1H), 7.92–7.88 (m, 2H), 7.70–7.63 (m, 4H), 7.42 (s, 1H), 7.39–7.11 (m, 10H), 1.47 (s, 9H), 1.34 (s, 9H).

[0230] Preparation Example 9 Synthesis of Compound 239:

[0231]

[0232] Preparation of intermediate B25:

[0233] The intermediate B23 (10.0 mmol), anhydrous DMF 40 mL and NaH (11.0 mmol) were added to the two-necked flask in sequence, and stirred at room temperature for 0.5 hours. Then, the raw material B10 (10 mmol) dissolved in 10 mL of anhydrous DMF was added, and stirred at room temperature for 5 hours. 100 mL of water was added to precipitate a large amount of white solid, which was filtered. The precipitate was dissolved in dichloromethane, dried and filtered using anhydrous sodium sulfate, and the organic phase was concentrated. The compound was separated by a silica gel column with petroleum ether: ethyl acetate = 15:1 as the developing solvent to obtain the intermediate B25. LC-MS: Measured value: 533.20 ([M+H] + ), theoretical value: 532.13.

[0234] Preparation of compound 239:

[0235] In a low-temperature eggplant-shaped bottle, intermediate B25 (5.0 mmol) and tert-butylbenzene (50 mL) were added in sequence, the temperature was lowered to -78°C, and a n-hexane solution of tert-butyl lithium (6.0 mmol) was slowly added, followed by stirring and warming to room temperature, and then the n-hexane was removed under negative pressure at 60°C; nitrogen protection was then connected, and BBr3 (6.5 mmol) was added at -42°C after reacting for 2 hours, the temperature was maintained and stirred for 2 hours, and the temperature was slowly restored to room temperature. After stirring at room temperature for 10 hours, DIPEA (N, N-diisopropylethylamine) (12 mmol) was added in an ice-water bath and heated to 120°C and refluxed for 36 hours. The reaction was cooled to room temperature, the solution was filtered with diatomaceous earth, the organic phase was collected and the high-boiling solvent was removed by distillation under reduced pressure, dissolved with dichloromethane, dried over anhydrous sodium sulfate, filtered, the organic phase was concentrated, and purified by a silica gel column, and toluene was used as a developing solvent to obtain compound 239. LC-MS: Measured value: 507.19 ([M+H] + ), theoretical value: 506.16. 1 H NMR (400 MHz, deuterated chloroform) δ8.19 (dd, 1H), 8.01 (dd, 1H), 7.95 (dd, 1H), 7.73 (dd, 1H), 7.61 (m, 2H), 7.55–7.43 (m, 2H), 7.40–7.30 (m, 7H), 7.19 (t, 1H), 7.01 (m, 1H), 6.92 (dd, 1H), 6.88 (dd, 1H).

[0236] Preparation Example 10 Synthesis of Compound 280:

[0237]

[0238] The synthesis of intermediate B26 was based on intermediate B18. LC-MS: Measured value: 818.35 ([M+H] + ), theoretical value 817.40.

[0239] The preparation of compound 280 was based on compound 218. LC-MS: Measured value: 923.45 ([M+H] + ), theoretical value 922.40. 1H NMR (400 MHz, deuterated chloroform) δ8.63–8.59 (m, 1H), 8.55–8.51 (m, 4H), 8.42 (d, 1H), 8.39 (dd, 2H), 8.19–8.15 (m, 1H), 8.12–8.01 (m, 1H), 7.87 (dd, 1H), 7.69–7.55 (m, 3H), 7.48–7.42 (m, 7H), 7.37–7.30 (m, 5H), 7.23 (t, 1H), 7.11 (dd, 2H), 1.46 (s, 9H), 1.38 (s, 9H).

[0240] Preparation Example 11 Synthesis of Compound 300:

[0241]

[0242]

[0243] The preparation of intermediate B27 was based on intermediate B12. LC-MS: Measured value: 439.10 ([M+H] + ), theoretical value 438.07. Preparation of intermediate B28 refers to intermediate 13. LC-MS: Measured value: 359.17 ([M+H] + ), theoretical value 358.15. Preparation of intermediate B29 refers to intermediate 15. LC-MS: Measured value: 790.16 ([M+H] + ), theoretical value 789.27. Synthesis of compound 300 Reference compound 214. LC-MS: Measured value: 720.49 ([M+H] + ), theoretical value 719.35. Preparation Example 12 Synthesis of Compound 293:

[0244]

[0245] The preparation of intermediate B36 was based on intermediate B17. LC-MS: Measured value: 605.15 ([M+H] + ), theoretical value 604.12. Preparation of compound 293 Reference compound 206. LC-MS: Measured value: 535.33 ([M+H] + ), theoretical value 534.19. Preparation Example 13 Synthesis of Compound 309:

[0246]

[0247] The synthesis of intermediate B30 was based on intermediate B18. LC-MS: Measured value: 846.51 ([M+H] + ), theoretical value 845.43.

[0248] The preparation of compound 309 was based on compound 218. LC-MS: Measured value: 951.41 ([M+H] + ), theoretical value 950.43.

[0249] Preparation Example 14 Synthesis of Compound 312:

[0250]

[0251] The preparation of intermediate B31 was based on intermediate B19. LC-MS: Measured value: 661.22 ([M+H] + ), theoretical value 660.28.

[0252] The preparation of compound 312 was based on compound 221. LC-MS: Measured value: 766.13 ([M+H] + ), theoretical value 765.27.

[0253] Preparation Example 15 Synthesis of Compound 348:

[0254]

[0255] Synthesis of intermediate B32:

[0256] The raw material A12 (10.0 mmol), the raw material A13 (10.0 mmol), the Pd(PPh3)4 catalyst 0.1 mmol, 50 mL of tetrahydrofuran: water = 10:1 mixed solution, potassium carbonate (20 mmol) were added to the two-necked flask in sequence, and then nitrogen was protected and stirred at 80°C for 6 hours. After cooling, the liquid was separated and the organic phase was collected, dried over anhydrous sodium sulfate, filtered and concentrated, and the compound was separated by silica gel column with petroleum ether: ethyl acetate = 5:1 as the developing solvent to obtain intermediate B32. LC-MS: Measured value: 377.23 ([M+H] + ), theoretical value: 376.12.

[0257] Synthesis of intermediate B33:

[0258] The intermediate B32 (10.0 mmol) and triethylphosphine oxide (20.0 mmol) were added to the two-necked flask in sequence, and then the mixture was stirred and refluxed for 24 hours under nitrogen protection. After cooling, the reaction solution was concentrated and separated by passing through a silica gel column with petroleum ether: ethyl acetate = 100:1 as the developing solvent to obtain the intermediate B33. LC-MS: Measured value: 345.22 ([M+H] + ), theoretical value: 344.13.

[0259] The preparation of intermediate B34 was based on intermediate B15. LC-MS: Measured value: 776.41 ([M+H] +), theoretical value 775.26.

[0260] The preparation of compound 348 was based on compound 214. LC-MS: Measured value: 706.51 ([M+H] + ), theoretical value 705.33.

[0261] Preparation Example 16 Synthesis of Compound 350:

[0262]

[0263] The synthesis of intermediate B35 was based on intermediate B17. LC-MS: Measured value: 591.22 ([M+H] + ), theoretical value 590.10.

[0264] The preparation of compound 350 was based on compound 206. LC-MS: Found: 521.30 ([M+H] + ), theoretical value 520.17.

[0265] Preparation Example 17 Synthesis of Compound 381:

[0266]

[0267] Raw material A3 (10.0 mmol), raw material A14 (10.0 mmol), cesium carbonate (22 mmol), and anhydrous NMP 50 mL were added to the two-necked flask in sequence, and then the mixture was stirred and refluxed at 150° C. for 24 hours under nitrogen protection. The organic phase was concentrated and the compound was separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate B36. LC-MS: 245.17 ([M+H] + ), theoretical value 244.13.

[0268] Under nitrogen, 10 mmol of intermediate B36, 10 mmol of intermediate B3 and 11 mmol of NaH were added to 100 mL of anhydrous DMF and heated to 150°C for 36 hours. After the reaction was cooled to room temperature, 200 mL of water was added, filtered and the precipitate was collected. The precipitate was dissolved with 50 mL of dichloromethane, dried with anhydrous sodium sulfate and filtered, concentrated and separated by column chromatography to obtain intermediate B37. LC-MS: 633.22 ([M+H] + ), theoretical value 632.15.

[0269] Under nitrogen, 30 mL of tert-butylbenzene and 2 mmol of intermediate B37 were added to a sealed pressure-resistant tube, and 3.2 mL of 2.5 M n-butyl lithium (n-hexane) solution was slowly added at 0 ° C. The reaction was heated to 80 degrees Celsius and reacted for 12 hours. 8.0 mmol of boron tribromide was added dropwise at -40 ° C, and the reaction continued at room temperature for 2 hours. Then 12 mmol of N, N-diisopropylethylamine (DIPEA) was added to the system at 0 ° C, heated to 150 ° C and continued to react for 48 hours. The reaction solution was cooled to room temperature, the solvent was removed under negative pressure, and then dissolved with 50 mL of dichloromethane, the organic phase was collected by filtration and concentrated, and the compound 381 was obtained by column chromatography. LC-MS: Measured value: 563.23 ([M+H] + ), theoretical value 562.22. Compound 381 was dissolved in toluene solution (5×10 -5 M) is shown in the attached Figure 3 , compound 381 in deuterated chloroform 1 HNMR diagram is attached Figure 6 .

[0270] Preparation Example 18 Synthesis of Compound 720:

[0271]

[0272] Raw material A15 (10.0 mmol), raw material A16 (10.0 mmol), cesium carbonate (22 mmol), and anhydrous NMP 50 mL were added to the two-necked flask in sequence, and then the mixture was stirred and refluxed at 150° C. for 13 hours under nitrogen protection. The organic phase was concentrated and the compound was separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate B38. LC-MS: 544.33 ([M+H] + ), theoretical value 543.29.

[0273] Under nitrogen, 10 mmol of intermediate B38, 10 mmol of intermediate B3 and 11 mmol of NaH were added to 100 mL of anhydrous DMF and heated to 150°C for 36 hours. After the reaction was cooled to room temperature, 200 mL of water was added, filtered and the precipitate was collected. The precipitate was dissolved with 50 mL of dichloromethane, dried with anhydrous sodium sulfate and filtered, concentrated and separated by column chromatography to obtain intermediate B39. LC-MS: 932.41 ([M+H] + ), theoretical value 931.31.

[0274] Under nitrogen, 30 mL of tert-butylbenzene and 2 mmol of intermediate B39 were added to a sealed pressure-resistant tube, and 3.2 mL of 2.5 M n-butyllithium (n-hexane) solution was slowly added at 0 ° C. The reaction was heated to 80 degrees Celsius and reacted for 12 hours. 8.0 mmol of boron tribromide was added dropwise at -40 ° C, and the reaction continued at room temperature for 2 hours. Then 12 mmol of N, N-diisopropylethylamine was added to the system at 0 ° C, heated to 150 ° C and continued to react for 48 hours. The reaction solution was cooled to room temperature, the solvent was removed under negative pressure, and then dissolved with 50 mL of dichloromethane, the organic phase was collected by filtration and concentrated, and the compound 720 was obtained by column chromatography. LC-MS: Measured value: 862.42 ([M+H] + ), theoretical value 861.39. Compound 720 was dissolved in toluene solution (5×10 -5 M) is shown in the attached Figure 4 , compound 720 in deuterated chloroform 1 H NMR diagram is attached Figure 7 .

[0275] The structural characteristics of the compounds obtained in each preparation example are shown in Table 1

[0276] Table 1

[0277]

[0278] The compounds of the present invention are used in light-emitting devices and can be used as doping materials for light-emitting layers. The physical and chemical properties of the compounds prepared in the above embodiments of the present invention were tested, and the test results are as follows:

[0279] The fluorescence quantum yields of compounds 1, 8, 84, 214, 206, 218, 221, 232, 239, 280, 300, 293, 309, 312, 348, 350, 381, and 720 were 86.1%, 89.8%, 91.1%, 94.2%, 91.3%, 98.9%, 93.2%, 92.1%, 89.4%, 85.5%, 89.2%, 91.6%, 90.0%, 85.0%, 87.5%, 89.2%, 95.32%, 99.80%, respectively.

[0280] The half-widths of compounds 1, 8, 84, 214, 206, 218, 221, 232, 239, 280, 300, 293, 309, 312, 348, 350, 381, and 720 are 23 nm, 26 nm, 21 nm, 30 nm, 27 nm, 28 nm, 26 nm, 25 nm, 27 nm, 29 nm, 26 nm, 30 nm, 31 nm, 33 nm, 32 nm, 29 nm, 18 nm, and 17 nm, respectively.

[0281] Note: PLQY (fluorescence quantum yield) and FWHM (half-maximum width) are measured in thin film state by Horiba's Fluorolog-3 series fluorescence spectrometer.

[0282] It can be seen from the above data that the compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%; at the same time, the spectral FWHM of the material is narrow, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device.

[0283] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device embodiments 1-18 and device comparative examples 1-2. The device manufacturing process of device embodiments 2-18 and device comparative 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 light-emitting layer material in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 2 and Table 3 respectively.

[0284] Device Example 1

[0285] like Figure 1 As 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, washed with a cleaning agent (Semiclean M-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 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 CBP as the main material and compound 1 as the doping material. The mass ratio of CBP and compound 1 is 97:3, and the film 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.

[0286] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device examples 19-36 and device comparative examples 3-4. The device manufacturing process of device examples 20-36 and device comparative examples 3-4 of the present invention is exactly the same as that of device example 19, 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 light-emitting layer material in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 2 and Table 3 respectively.

[0287] Device Example 19

[0288] 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 (Semiclean M-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 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 CBP and DMAC-BP as dual host materials, compound 1 as a doping material, CBP, DMAC-BP and compound 1. The mass ratio is 67:30:3, and the film 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.

[0289] The molecular structure formula of the relevant materials is shown below:

[0290]

[0291] 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, external quantum efficiency and life of the device are measured. The device examples and comparative examples prepared by the same method are shown in Table 2; the test results of the current efficiency, external quantum efficiency and life of the obtained device are shown in Table 3.

[0292] Table 2

[0293]

[0294]

[0295]

[0296] Table 3

[0297]

[0298] Note: Voltage, current efficiency, and luminous peak are measured using IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.); the 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.

[0299] It can be seen from the device data results in Table 3 that, compared with device comparison examples 1-2, the current efficiency, external quantum efficiency and device life of the organic light-emitting device embodiments 1-18 of the present invention are greatly improved relative to OLED devices of known materials.

[0300] By comparing Examples 19-36 with Comparative Examples 3-4, it can be seen that the current efficiency, external quantum efficiency and device life of the organic light-emitting devices of Examples 19-36 of the present invention are greatly improved compared with OLED devices made of known materials.

[0301] 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 resonance type organic compound, characterized in that: The structure of the organic compound is shown in general formula (1-2): In the general formula (1-2), A1-A3 represents phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, benzofuranyl, dibenzofuranyl, dibenzothiophenyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 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 or the structure represented by the general formula (2); Each occurrence of Z0 can be the same or different and is represented as C-R0; X0 represents -O-, -N(R4)-; R0 is the same or different each time it appears and is independently represented by H, a deuterium atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated cyclopentyl group, a cyclopentyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a deuterated terphenyl group, a terphenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a spirofluorenyl group, a 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 or deuterated tert-butyl-substituted biphenyl; R4 represents phenyl, deuterated phenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, tert-butyl substituted phenyl, deuterated methyl substituted phenyl, deuterated ethyl substituted phenyl, deuterated isopropyl substituted phenyl or deuterated tert-butyl substituted phenyl; and R4 and A1 ring are connected to form a ring via a single bond; One of A1, A2, and A3 has a structure represented by general formula (2); Each occurrence of Z can be the same or different and is represented by C-R1; R1 is the same or different each time it appears and is independently H, a deuterium atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated cyclopentyl group, a cyclopentyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a deuterated terphenyl group, a terphenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a spirofluorenyl group, a 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 or deuterated tert-butyl substituted biphenyl.

2. The resonance type organic compound according to claim 1, characterized in that The A1 and A3 are represented by any of the following ring structures:

3. A resonance type organic compound, characterized in that: The structure of the organic compound is shown in any one of the general formulas (7) to (9): In general formulas (7) to (9), A1 is phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, benzofuranyl, dibenzofuranyl, dibenzothiophenyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 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; Each occurrence of Z0 can be the same or different and is represented as C-R0; X0 represents -O-, -N(R4)-; R0 is the same or different each time it appears and is independently represented by H, a deuterium atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated cyclopentyl group, a cyclopentyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a deuterated terphenyl group, a terphenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a spirofluorenyl group, a 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 or deuterated tert-butyl-substituted biphenyl; R4 represents phenyl, deuterated phenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, tert-butyl substituted phenyl, deuterated methyl substituted phenyl, deuterated ethyl substituted phenyl, deuterated isopropyl substituted phenyl or deuterated tert-butyl substituted phenyl; and R4 and A1 ring are connected to form a ring via a single bond; Each occurrence of Z can be the same or different and is represented by C-R1; R1 is the same or different each time it appears and is independently H, a deuterium atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated cyclopentyl group, a cyclopentyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a deuterated terphenyl group, a terphenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a spirofluorenyl group, a 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 or deuterated tert-butyl-substituted biphenyl; The dashed lines in the general formula represent connection via a single bond or no connection, and only two of the three dashed lines in each general formula represent connection via a single bond.

4. A resonance type organic compound, characterized in that: The structure of the organic compound is shown in any one of the general formulas (12) to (14), (16) and (18): In the general formulas (12) to (14), (16) and (18), A1 is phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, benzofuranyl, dibenzofuranyl, dibenzothiophenyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 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 and tert-butyl-substituted biphenyl; Each occurrence of Z0 can be the same or different and is represented as C-R0; X0 represents -O-, -N(R4)-; R0 is the same or different each time it appears and is independently represented by H, a deuterium atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated cyclopentyl group, a cyclopentyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a deuterated terphenyl group, a terphenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a spirofluorenyl group, a 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 or deuterated tert-butyl-substituted biphenyl; R4 represents phenyl, deuterated phenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, tert-butyl substituted phenyl, deuterated methyl substituted phenyl, deuterated ethyl substituted phenyl, deuterated isopropyl substituted phenyl or deuterated tert-butyl substituted phenyl; and R4 and A1 ring are connected to form a ring via a single bond; Each occurrence of Z can be the same or different and is represented by C-R1; R1 is the same or different each time it appears and is independently H, a deuterium atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a deuterated cyclopentyl group, a cyclopentyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a deuterated terphenyl group, a terphenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a spirofluorenyl group, a 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 or deuterated tert-butyl substituted biphenyl.

5. A resonance type organic compound, characterized in that: The specific structural formula of the resonance type organic compound is any one of the following structures:

6. An organic light-emitting device comprising a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode, characterized in that: The functional layer of the organic light-emitting device comprises the resonance-type organic compound according to any one of claims 1 to 5.

7. The organic light-emitting device according to claim 6, wherein the functional layer comprises a light-emitting layer, characterized in that: The doping material of the light-emitting layer is the resonance-type organic compound according to any one of claims 1 to 5.

8. The organic light-emitting device according to claim 6, wherein the functional layer comprises a light-emitting layer, characterized in that: 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 resonance-type organic compound according to any one of claims 1 to 5.

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