Stable multi-resonance thermal activation delayed fluorescence material as well as preparation and application thereof

Abstract

The invention discloses a stable multi-resonance thermally activated delayed fluorescent material as well as preparation and application thereof. The multi-resonance thermal activation delayed fluorescent material has a structure as shown in a formula (I), a formula (II) or a formula (III): # imgabs0 # R1, R2, R5, R6, R7, R10, R11, R12 and R13 respectively and independently represent hydrogen, tert-butyl, phenyl, adamantyl or 3, 5-diphenyl triazinyl, and R < 2 >, R < 5 >, R < 6 >, R < 7 >, R < 10 >, R < 11 >, R < 12 > and R < 13 > independently represent hydrogen, tert-butyl, phenyl, adamantyl or 3, 5-diphenyl triazinyl; r < 3 >, R < 4 >, R < 8 >, R < 9 >, R < 14 > and R < 15 > respectively represent monosubstituents to maximum allowable substituents, and are independently selected from one of hydrogen, C1-C12 chain alkyl, C5-C6 cycloalkyl, C1-C10 alkoxy, halogen, nitryl, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; x1, X2 and X3 are respectively and independently selected from oxygen, sulfur or selenium; and X4, X5 and X6 are independently selected from a single bond, dimethyl, diphenyl, fluorene ring substituted carbon, fluorene ring substituted silicon or fluorene ring substituted germanium.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, in particular to a stable multiple resonance thermally activated delayed fluorescence material and its preparation and application. Background Art

[0002] Organic Light-Emitting Diode (OLED), also known as organic electrolaser display or organic light-emitting semiconductor, is a current-type organic light-emitting device that produces light through the injection and recombination of carriers. Compared with traditional liquid crystal displays (LCD), OLED has high luminous efficiency. Its light-emitting mechanism enables OLED screens to independently control brightness and color at the individual pixel level, achieving deep grayscale and high-contrast displays. Therefore, the overall brightness and color performance of OLED screens are superior to traditional LCDs. In addition, the fast response characteristics of OLED make OLED screens more suitable for dynamic image displays, such as dynamic videos and sports games. Flexible screens can be used in scenarios such as foldable phones, wearable devices, and smart watches, greatly improving the user experience. The development of OLED luminescent materials has gone through three generations of innovation. The first generation of traditional fluorescent materials (such as aluminum chelates) only utilizes the radiative transition of singlet excitons. Although they are low-cost and have high color purity, they have a significant efficiency bottleneck. The second generation of phosphorescent materials (such as Ir and Pt complexes) enhances spin-orbit coupling through heavy metal atoms to achieve effective utilization of singlet and triplet excitons. The internal quantum efficiency can reach 100%. However, for blue light materials, poor stability, high cost and efficiency roll-off have hindered its development. The emergence of Multi-Resonance Thermally Activated Delayed Fluorescence (MR-TADF) materials combines the advantages of the first two generations of luminescent materials. It achieves a narrow emission spectrum with a full width at half maximum (FWHM) of less than 30nm through intramolecular multi-resonance electronic structures (such as rigid B / N skeletons). At the same time, the singlet-triplet energy gap (ΔE ST ) is small, ensuring 100% exciton utilization. Compared to traditional TADF materials that rely on intermolecular charge transfer to broaden the spectrum, MR-TADF materials significantly improve color purity while maintaining high external quantum efficiency (EQE). This combination of high color gamut and low power consumption makes it an ideal choice for ultra-high-definition displays and miniaturized AR / VR devices, driving OLED technology towards higher performance and wider application scenarios.

[0003] At present, the lifespan of devices is still one of the obstacles restricting the development of OLEDs. One of the reasons that limit the lifespan of devices is exciton annihilation, such as triplet-triplet annihilation and triplet-polaron interaction. When the driving current increases, the exciton generation rate exceeds the exciton recombination rate, resulting in an increase in the concentration of triplet excitons. The high-energy triplet excitons interact to form a higher-energy exciton and a ground-state molecule or degrade themselves, thereby quenching the efficiency and lifespan of OLED devices. For the most critical pure organic light-emitting molecules in OLEDs, their intrinsic stability has a decisive influence on the lifespan of the device. Therefore, it is very necessary to develop chemically stable MR-TADF materials to improve the lifespan of OLED devices.

[0004] It should be noted that the information disclosed in the above background technology section is only used to understand the background of this application, and therefore may include information that does not constitute prior art known to ordinary technicians in this field. Summary of the Invention

[0005] In order to make up for the deficiencies of the prior art, the present invention provides a stable multi-resonance thermally activated delayed fluorescence material and its preparation and application.

[0006] The present invention adopts the following technical solutions:

[0007] In a first aspect, a stable multi-resonance thermally activated delayed fluorescent material is provided, which has a structure shown in formula (I), formula (II) or formula (III):

[0008]

[0009] In formula (I), (II), and (III), R1, R2, R5, R6, R7, R 10 ,R 11 ,R 12 ,R 13 Each independently represents hydrogen, tert-butyl, phenyl, adamantyl or 3,5-diphenyltriazinyl; R3, R4, R8, R9, R 14 ,R 15 Each represents a single substituent to the maximum permissible substituent, and is independently selected from one of hydrogen, C1-C12 chain alkyl, C5-C6 cycloalkyl, C1-C10 alkoxy, halogen, nitro, hydroxy, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; X1, X2, X3 are each independently selected from oxygen, sulfur or selenium; X4, X5, X6 are each independently selected from a single bond, dimethyl, diphenyl, fluorene ring-substituted carbon, fluorene ring-substituted silicon, or fluorene ring-substituted germanium.

[0010] In a second aspect, a method for preparing the multi-resonance thermally activated delayed fluorescent material according to the first aspect is provided, comprising the following steps:

[0011] (1) For compound No. 1 represented by formula (I), its synthesis route is as follows:

[0012]

[0013] (1.1) Synthesis of intermediate B: 2,5-dibromo-1,3-difluorobenzene, precursor A, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate B was obtained by post-treatment.

[0014] (1.2) Synthesis of intermediate D: The intermediate B, precursor C, and cesium carbonate are dissolved in ultra-dry N,N-dimethylformamide, reacted under nitrogen protection, and post-processed to obtain intermediate D;

[0015] (1.3) Synthesis of Intermediate E: Under nitrogen protection, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate D dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate E is obtained by post-treatment.

[0016] (1.4) Synthesis of intermediate F: Intermediate E, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate F was obtained by post-treatment.

[0017] (1.5) Synthesis of Compound No. 1 of Formula (I): Intermediate F, precursor G, tetrakis(triphenylphosphine)palladium, and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol, and deionized water, and reacted under nitrogen. After the reaction, the compound No. 1 of Formula (I) is obtained by post-treatment.

[0018] (2) For compound No. 2 represented by formula (II), its synthesis route is as follows:

[0019]

[0020] (2.1) Synthesis of intermediate I: 2,5-dibromo-1,3-difluorobenzene, precursor H, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen. After the reaction, intermediate I was obtained by post-treatment.

[0021] (2.2) Synthesis of intermediate K: Intermediate I, precursor J, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate I was obtained by post-treatment.

[0022] (2.3) Synthesis of Intermediate L: Under nitrogen protection, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate K dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate L is obtained by post-treatment.

[0023] (2.4) Synthesis of intermediate M: Intermediate L, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate M was obtained by post-treatment.

[0024] (2.5) Synthesis of Compound No. 2 of Formula (II): Intermediate M, precursor N, tetrakis(triphenylphosphine)palladium, and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol, and deionized water, and reacted under nitrogen. After the reaction, compound No. 2 of Formula (II) is obtained by post-treatment.

[0025] (3) For compound No. 3 represented by formula (III), its synthesis route is as follows:

[0026]

[0027] (3.1) Synthesis of intermediate P: 2,5-dibromo-1,3-difluorobenzene, precursor O, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen. After the reaction, intermediate P was obtained by post-treatment.

[0028] (3.2) Synthesis of intermediate R: Intermediate I, precursor J, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate R was obtained by post-treatment.

[0029] (3.3) Synthesis of Intermediate S: Under nitrogen, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate R dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate S is obtained by post-treatment.

[0030] (3.4) Synthesis of intermediate T: Intermediate S, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate T was obtained by post-treatment.

[0031] (3.5) Synthesis of compound No. 3 represented by formula (III): The intermediate T, precursor U, tetrakis(triphenylphosphine)palladium and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol and deionized water, and reacted under nitrogen protection. After the reaction, compound No. 3 represented by formula (III) is obtained by post-treatment.

[0032] In a third aspect, a use of the multi-resonance thermally activated delayed fluorescent material described in the first aspect is provided, wherein the multi-resonance thermally activated delayed fluorescent material is used as a functional material for an organic electronic device.

[0033] In a fourth aspect, an organic electroluminescent device is provided, comprising an anode layer, a cathode layer, and one or more organic functional layers inserted between the anode layer and the cathode layer, wherein the organic functional layer comprises the multi-resonance thermally activated delayed fluorescent material according to any one of claims 1 to 2.

[0034] The present invention has the following beneficial effects: the multiple resonance thermally activated delayed fluorescence material of the present invention is based on the covalent connection of the MR-TADF skeleton and the triazine structural unit, and the triazine structural group is optimized at the substitution connection site and the peripheral substituents to regulate the performance of the material. The material of the present invention has high thermal stability (thermal decomposition temperature T d The present invention offers advantages such as a temperature range of >400°C, a narrow emission spectrum (FWHM <40nm), and high exciton utilization (photoluminescence quantum yield PLQY >90%). The synthetic route of the present invention enables gram-scale production with high yields. By manipulating the MR-TADF backbone and the types of substituents, the luminescence color of the molecules synthesized via this route can cover the entire visible light range. The application of the present invention's multi-resonant thermally activated delayed fluorescence material in organic electroluminescent devices can improve device stability and lifespan, providing a solution with high commercial potential for next-generation OLED display technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the hydrogen spectrum of intermediate B in Example 1 of the present invention;

[0036] Figure 2 This is the hydrogen spectrum of the intermediate D in Example 1 of the present invention;

[0037] Figure 3 This is the hydrogen spectrum of the intermediate E in Example 1 of the present invention;

[0038] Figure 4 is the hydrogen spectrum of intermediate F in Example 1 of the present invention;

[0039] Figure 5 is the hydrogen spectrum of compound No. 1 in Example 1 of the present invention;

[0040] Figure 6 is the mass spectrum of Compound No. 1 in Example 1 of the present invention;

[0041] Figure 7 is the hydrogen spectrum of intermediate 1 in Example 2 of the present invention;

[0042] Figure 8 This is the hydrogen spectrum of the intermediate K in Example 2 of the present invention;

[0043] Figure 9 This is the hydrogen spectrum of the intermediate L in Example 2 of the present invention;

[0044] Figure 10 This is the hydrogen spectrum of the intermediate M in Example 2 of the present invention;

[0045] Figure 11 This is the hydrogen spectrum of compound No. 2 in Example 2 of the present invention;

[0046] Figure 12 is the mass spectrum of Compound No. 2 in Example 2 of the present invention;

[0047] Figure 13 is the mass spectrum of intermediate R in Example 3 of the present invention;

[0048] Figure 14 is the mass spectrum of the intermediate S in Example 3 of the present invention;

[0049] Figure 15 This is the mass spectrum of the intermediate T in Example 3 of the present invention;

[0050] Figure 16 This is the hydrogen spectrum of compound No. 3 in Example 3 of the present invention;

[0051] Figure 17 is the mass spectrum of Compound No. 3 in Example 3 of the present invention;

[0052] Figure 18 is a thermogravimetric analysis chart of Compound No. 1, Compound No. 2, and Compound No. 3 in Examples 1-3 of the present invention;

[0053] Figure 19 Compound No. 1, Compound No. 2 and Compound No. 3 in Examples 1-3 of the present invention are 2×10 -5 M emission spectrum in toluene solution;

[0054] Figure 20 The devices A1, A2, and A3 in Example 4 of the present invention are at 1000 cd / m 2 Operational life graph at brightness. DETAILED DESCRIPTION

[0055] The following is a detailed description of the embodiments of the present invention. It should be emphasized that the following description is merely illustrative and is not intended to limit the scope and application of the present invention. In the absence of conflict, the embodiments and features in the embodiments of this application can be combined with each other.

[0056] A specific embodiment of the present invention provides a stable multi-resonance thermally activated delayed fluorescent material having a structure shown in formula (I), formula (II) or formula (III):

[0057]

[0058] In formula (I), (II), and (III),

[0059] R1,R2,R5,R6,R7,R 10 ,R 11 ,R 12 ,R 13 each independently represents hydrogen, tert-butyl, phenyl, adamantyl or 3,5-diphenyltriazinyl;

[0060] R3,R4,R8,R9,R 14 ,R 15 Each represents a single substituent to the maximum permissible substituent, and is independently selected from one of hydrogen, C1-C12 chain alkyl, C5-C6 cycloalkyl, C1-C10 alkoxy, halogen, nitro, hydroxy, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0061] X1, X2, X3 are each independently selected from oxygen, sulfur or selenium;

[0062] X4, X5, and X6 are each independently selected from a single bond, dimethyl, diphenyl, fluorene ring-substituted carbon, fluorene ring-substituted silicon, or fluorene ring-substituted germanium.

[0063] In some embodiments, the multiple resonance thermally activated delayed fluorescent material is selected from one of the following compounds Z-1 to Z-657:

[0064]

[0065]

[0066]

[0067]

[0068]

[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]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] The present invention also provides a method for preparing the multi-resonance thermally activated delayed fluorescent material. In this context, "slowly heating" refers to a heating rate of 3-5°C / min, and "room temperature" refers to a temperature of 20-30°C. The preparation method comprises the following steps:

[0103] (1) For compound No. 1 represented by formula (I), its synthesis route is as follows:

[0104]

[0105] (1.1) Synthesis of intermediate B: 2,5-dibromo-1,3-difluorobenzene, precursor A, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate B was obtained by post-treatment.

[0106] Preferably, the synthesis of intermediate B is as follows: 2,5-dibromo-1,3-difluorobenzene (1.0 eq., "eq." represents molar equivalent), precursor A (1.0-1.1 eq.) and cesium carbonate (2.0-3.0 eq.) are dissolved in ultra-dry N,N-dimethylformamide, and the mixture is stirred at 160 ° C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture is diluted with dichloromethane and washed three times with deionized water. The organic layer is collected and dried over anhydrous magnesium sulfate. After filtration, the solvent is removed by rotary evaporation under reduced pressure. The crude product is purified by column chromatography to obtain intermediate B.

[0107] (1.2) Synthesis of intermediate D: The intermediate B, precursor C, and cesium carbonate are dissolved in ultra-dry N,N-dimethylformamide, reacted under nitrogen protection, and post-processed to obtain intermediate D;

[0108] Preferably, the synthesis of intermediate D: intermediate B (1.0 eq.), precursor C (1.0-1.1 eq.) and cesium carbonate (2.0-3.0 eq.) are dissolved in ultra-dry N,N-dimethylformamide, and the mixture is stirred at 160 ° C for 12 hours under a nitrogen environment. After cooling to room temperature, the mixture is diluted with dichloromethane and washed three times with deionized water. The organic layer is collected and dried over anhydrous magnesium sulfate. After filtering, the solvent is removed by vacuum rotary evaporation, and the crude product is purified by column chromatography to obtain intermediate D.

[0109] (1.3) Synthesis of Intermediate E: Under nitrogen protection, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate D dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate E is obtained by post-treatment.

[0110] Preferably, under a nitrogen atmosphere, a solution of n-butyllithium in cyclohexane (n-BuLi, 2.5 M, 1.1-1.5 eq) is slowly added to a solution of intermediate D (1.0 eq.) in ultra-dry mesitylene at -30°C. After stirring at room temperature for 1 hour, a solution of boron tribromide in dichloromethane (BBr3, 1 mol / L, 2.0-2.5 eq.) is added dropwise at -78°C. The mixture is slowly warmed to room temperature and stirred for 2 hours, followed by the addition of N,N-diisopropylethylamine (DIPEA) (2.0-2.5 eq.) at 0°C. Finally, the mixture is heated to 130°C and held for 12 hours. After cooling to room temperature, the reaction solution is poured into a sodium chloride solution and extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the solvent removed by vacuum rotary evaporation. The crude product can be purified by recrystallization from a methanol / dichloromethane system to obtain intermediate E.

[0111] (1.4) Synthesis of intermediate F: Intermediate E, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate F was obtained by post-treatment.

[0112] Preferably, the synthesis of intermediate F is as follows: intermediate E (1.0 eq.), pinacol diboron (1.2-1.5 eq.), 1,1'-bis(diphenylphosphino)ferrocenedichloridopalladium (0.05 eq.), and potassium acetate (8.0-10.0 eq.) are dissolved in ultra-dry 1,4-dioxane. Under a nitrogen atmosphere, the mixture is stirred at 110°C for 12 hours. After cooling to room temperature, the mixture is diluted with dichloromethane and washed three times with deionized water. The organic layer is collected and dried over anhydrous magnesium sulfate. After filtration, the solvent is removed by rotary evaporation under reduced pressure, and the crude product is purified by column chromatography to obtain intermediate F.

[0113] (1.5) Synthesis of Compound No. 1 of Formula (I): Intermediate F, precursor G, tetrakis(triphenylphosphine)palladium, and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol, and deionized water, and reacted under nitrogen. After the reaction, the compound No. 1 of Formula (I) is obtained by post-treatment.

[0114] Preferably, the synthesis of compound No. 1 shown in formula (I) is as follows: intermediate F (1.0 eq.), precursor G (1.0-1.2 eq.), tetrakis(triphenylphosphine)palladium (0.05 eq.) and potassium carbonate (3.0-5.0 eq.) are dissolved in a mixed solvent of toluene, ethanol and deionized water (volume ratio of 4:2:1). Under a nitrogen environment, the mixture is stirred at 100°C for 12 hours. The reaction solution is extracted with dichloromethane, the organic layer is collected and dried over anhydrous magnesium sulfate, and then the solvent is removed under reduced pressure. The crude product is washed with dichloromethane and ethanol in sequence, and filtered to obtain the product, namely compound No. 1 shown in formula (I).

[0115] (2) For compound No. 2 represented by formula (II), its synthesis route is as follows:

[0116]

[0117] (2.1) Synthesis of intermediate I: 2,5-dibromo-1,3-difluorobenzene, precursor H, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen. After the reaction, intermediate I was obtained by post-treatment.

[0118] Preferably, the synthesis of intermediate I: 2,5-dibromo-1,3-difluorobenzene (1.0 eq.), precursor H (1.0-1.1 eq.) and cesium carbonate (2.0-3.0 eq.) are dissolved in ultra-dry N,N-dimethylformamide. Under a nitrogen atmosphere, the mixture is stirred at 160 ° C for 12 hours. After cooling to room temperature, the mixture is diluted with dichloromethane and washed three times with deionized water. The organic layer is collected and dried over anhydrous magnesium sulfate. After filtration, the solvent is removed by rotary evaporation under reduced pressure, and the crude product is purified by column chromatography to obtain intermediate I.

[0119] (2.2) Synthesis of intermediate K: Intermediate I, precursor J, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate I was obtained by post-treatment.

[0120] Preferably, the synthesis of intermediate K: intermediate I (1.0 eq.), precursor J (1.0-1.1 eq.) and cesium carbonate (2.0-3.0 eq.) were dissolved in ultra-dry N,N-dimethylformamide. The mixture was stirred at 160°C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography to obtain intermediate K.

[0121] (2.3) Synthesis of Intermediate L: Under nitrogen protection, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate K dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate L is obtained by post-treatment.

[0122] Preferably, for the synthesis of intermediate L, a solution of n-butyllithium in cyclohexane (n-BuLi, 2.5 M, 1.1-1.5 eq) is slowly added to a solution of intermediate K (1.0 eq.) in ultra-dry mesitylene under a nitrogen atmosphere at -30°C. After stirring at room temperature for 1 hour, a solution of boron tribromide in dichloromethane (BBr3, 1 mol / L, 2.0-2.5 eq.) is added dropwise at -78°C. The mixture is slowly warmed to room temperature and stirred for 2 hours, followed by the addition of N,N-diisopropylethylamine (2.0-2.5 eq.) at 0°C. Finally, the mixture is heated to 130°C and held for 12 hours. After cooling to room temperature, the reaction solution is poured into a sodium chloride solution, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the solvent removed by rotary evaporation under reduced pressure. The crude product can be purified by recrystallization from a methanol / dichloromethane system to obtain intermediate L.

[0123] (2.4) Synthesis of intermediate M: Intermediate L, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate M was obtained by post-treatment.

[0124] Preferably, the synthesis of intermediate M is as follows: intermediate L (1.0 eq.), pinacol diboron (1.2-1.5 eq.), 1,1'-bis(diphenylphosphino)ferrocenedichloridopalladium (0.05 eq.), and potassium acetate (8.0-10.0 eq.) are dissolved in ultra-dry 1,4-dioxane. The mixture is stirred at 110°C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture is diluted with dichloromethane and washed three times with deionized water. The organic layer is collected and dried over anhydrous magnesium sulfate. After filtration, the solvent is removed by rotary evaporation under reduced pressure, and the crude product is purified by column chromatography to obtain intermediate M.

[0125] (2.5) Synthesis of Compound No. 2 of Formula (II): Intermediate M, precursor N, tetrakis(triphenylphosphine)palladium, and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol, and deionized water, and reacted under nitrogen. After the reaction, compound No. 2 of Formula (II) is obtained by post-treatment.

[0126] Preferably, the synthesis of compound No. 2 represented by formula (II) is as follows: intermediate M (1.0 eq.), precursor N (1.0-1.2 eq.), tetrakis(triphenylphosphine)palladium (0.05 eq.), and potassium carbonate (3.0-5.0 eq.) are dissolved in a mixed solvent of toluene, ethanol, and deionized water (volume ratio of 4:2:1). Under a nitrogen atmosphere, the mixture is stirred at 100°C for 12 hours. The reaction solution is extracted with dichloromethane, the organic layer is collected and dried over anhydrous magnesium sulfate, and then the solvent is removed under reduced pressure. The crude product is washed with dichloromethane and ethanol, respectively, and filtered to obtain the product, namely compound No. 2 represented by formula (II).

[0127] (3) For compound No. 3 represented by formula (III), its synthesis route is as follows:

[0128]

[0129] (3.1) Synthesis of intermediate P: 2,5-dibromo-1,3-difluorobenzene, precursor O, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen. After the reaction, intermediate P was obtained by post-treatment.

[0130] Preferably, the synthesis of intermediate P: 2,5-dibromo-1,3-difluorobenzene (1.0 eq.), precursor O (1.0-1.1 eq.) and cesium carbonate (2.0-3.0 eq.) are dissolved in ultra-dry N,N-dimethylformamide. Under a nitrogen atmosphere, the mixture is stirred at 160 ° C for 12 hours. After cooling to room temperature, the mixture is diluted with dichloromethane and washed three times with deionized water. The organic layer is collected and dried over anhydrous magnesium sulfate. After filtration, the solvent is removed by rotary evaporation under reduced pressure, and the crude product is purified by column chromatography to obtain intermediate P.

[0131] (3.2) Synthesis of intermediate R: Intermediate I, precursor J, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate R was obtained by post-treatment.

[0132] Preferably, the synthesis of intermediate R: intermediate P (1.0 eq.), precursor Q (1.0-1.1 eq.) and cesium carbonate (2.0-3.0 eq.) are dissolved in ultra-dry N,N-dimethylformamide. Under a nitrogen environment, the mixture is stirred at 160 ° C for 12 hours. After cooling to room temperature, the mixture is diluted with dichloromethane and washed three times with deionized water. The organic layer is collected and dried over anhydrous magnesium sulfate. After filtration, the solvent is removed by rotary evaporation under reduced pressure, and the crude product is purified by column chromatography to obtain intermediate R.

[0133] (3.3) Synthesis of Intermediate S: Under nitrogen, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate R dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate S is obtained by post-treatment.

[0134] Preferably, for the synthesis of intermediate S: Under a nitrogen atmosphere, a solution of n-butyllithium in cyclohexane (n-BuLi, 2.5 mol / L, 1.1-1.5 eq) is slowly added to a solution of intermediate R (1.0 eq.) in ultra-dry mesitylene at -30°C. After stirring at room temperature for 1 hour, a solution of boron tribromide in dichloromethane (BBr3, 1 mol / L, 2.0-2.5 eq.) is added dropwise at -78°C. The mixture is slowly warmed to room temperature and stirred for 2 hours, followed by the addition of N,N-diisopropylethylamine (2.0-2.5 eq.) at 0°C. Finally, the mixture is heated to 130°C and held for 12 hours. After cooling to room temperature, the reaction solution is poured into a sodium chloride solution and extracted with dichloromethane. The mixture is then dried over anhydrous magnesium sulfate, filtered, and the solvent removed by rotary evaporation under reduced pressure. The crude product can be purified by recrystallization from methanol / dichloromethane to obtain intermediate S.

[0135] (3.4) Synthesis of intermediate T: Intermediate S, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate T was obtained by post-treatment.

[0136] Preferably, the synthesis of intermediate T is as follows: Intermediate S (1.0 eq.), pinacol diboron (1.2-1.5 eq.), 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium (0.05 eq.), and potassium acetate (8.0-10.0 eq.) are dissolved in ultra-dry 1,4-dioxane. The mixture is stirred at 110°C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture is diluted with dichloromethane and washed three times with deionized water. The organic layer is collected and dried over anhydrous magnesium sulfate. After filtration, the solvent is removed by rotary evaporation under reduced pressure, and the crude product is purified by column chromatography to obtain intermediate T.

[0137] (3.5) Synthesis of compound No. 3 represented by formula (III): The intermediate T, precursor U, tetrakis(triphenylphosphine)palladium and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol and deionized water, and reacted under nitrogen protection. After the reaction, compound No. 3 represented by formula (III) is obtained by post-treatment.

[0138] Preferably, the synthesis of compound No. 3 represented by formula (III) is as follows: intermediate T (1.0 eq.), precursor U (1.0-1.2 eq.), tetrakis(triphenylphosphine)palladium (0.05 eq.), and potassium carbonate (3.0-5.0 eq.) are dissolved in a mixed solvent of toluene, ethanol, and deionized water (volume ratio 4:2:1). Under a nitrogen atmosphere, the mixture is stirred at 100°C for 12 hours. The reaction solution is extracted with dichloromethane, the organic layer is collected and dried over anhydrous magnesium sulfate, and then the solvent is removed under reduced pressure. The crude product is washed with dichloromethane and ethanol, and filtered to obtain the product, namely compound No. 3 represented by formula (III).

[0139] The following provides methods for synthesizing representative compounds of the present invention.

[0140] Example 1

[0141] The reaction formula of compound No. 1 (corresponding to compound Z-67) is as follows:

[0142]

[0143] Synthesis of intermediate B: In a 250 mL Schlenk tube, 2,5-dibromo-1,3-difluorobenzene (1.0 eq.), precursor A (1.0 eq.) and cesium carbonate (2.0 eq.) were dissolved in ultra-dry N,N-dimethylformamide. The mixture was stirred at 160 ° C for 12 hours under a nitrogen environment. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. The hydrogen spectrum of intermediate B is shown as follows Figure 1 As shown, 1HNMR(400MHz,Chloroform-d)δ7.40(d,J=8.7Hz,2H),7.05(dd,J=7.6,2.0Hz,1H),6.96 (d, J=8.7Hz, 2H), 6.77 (s, J=1.7Hz, 1H), 1.34 (s, 9H). High resolution ESI-MScalcdforC16H15Br2FO 401.94530,found401.93887.

[0144] Synthesis of intermediate D: In a 250 mL Schlenk tube, intermediate B (1.0 eq.), precursor C (1.0 eq.) and cesium carbonate (2.0 eq.) were dissolved in ultra-dry N,N-dimethylformamide. The mixture was stirred at 160 ° C for 12 hours under a nitrogen environment. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. The hydrogen spectrum of intermediate D is shown as follows Figure 2 As shown, 1 HNMR (400 MHz, Chloroform-d) δ7.40 (d, J=8.5 Hz, 4H), 6.98 (d, J=8.5 Hz, 4H), 6.73 (s, 2H), 1.34 (s, 18H). High resolution ESI-MS calcd for C26H28Br2O2 533.05084, found 533.04999.

[0145] Synthesis of intermediate E: Under a nitrogen environment, a solution of n-butyl lithium dissolved in cyclohexane (n-BuLi, 2.5 mol / L, 1.1 eq) was slowly added to a solution of intermediate D (1.0 eq.) in ultra-dry mesitylene, and the temperature was controlled at -30°C. After stirring at room temperature for 1 hour, a dichloromethane solution of boron tribromide (BBr3, 1 mol / L, 2 eq.) was added dropwise at -78°C. The mixture was slowly warmed to room temperature and stirred for 2 hours, and then N,N-diisopropylethylamine (2 eq.) was added at 0°C. Finally, the mixture was heated to 130°C and maintained for 12 hours. After cooling to room temperature, the reaction solution was poured into a sodium chloride solution and extracted with dichloromethane, then dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude product can be purified by recrystallization from a methanol / dichloromethane system. The hydrogen spectrum of intermediate D is shown in FIG. Figure 3 As shown, 1H NMR (400 MHz, Chloroform-d) δ 8.73 (d, J = 2.5 Hz, 2H), 7.79 (dd, J = 8.8, 2.5 Hz, 2H), 7.48 (d, J = 8.8 Hz, 2H), 7.38 (s, 2H), 1.48 (s, 18H). High-resolution ESI-MS calcd for C26H26BBrO2 461.12820, found 461.12716.

[0146] Synthesis of intermediate F: In a 250 mL Schlenk tube, intermediate E (1.0 eq.), diboronic acid pinacol ester (1.5 eq.), 1,1'-bis(diphenylphosphino)ferrocenedichloridopalladium (0.05 eq.) and potassium acetate (10 eq.) were dissolved in ultra-dry 1,4-dioxane. Stir at 110 ° C for 12 hours under nitrogen. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. The hydrogen spectrum of intermediate F is shown as follows Figure 4 As shown, 1 H NMR (400MHz, Chloroform-d) δ8.76 (d, J=2.5Hz, 2H), 7.78 (dd, J=8.8, 2.5Hz, 2H), 7.65 (s, 2H), 7.49 (d, J=8.8Hz, 2H), 1.49 (s, 18H), 1.41 (s, 12H). High resolution ESI-MS calcd forC32H38B2O4509.30290, found 509.30209.

[0147] Synthesis of compound No. 1: In a 50 mL Schlenk tube, intermediate F (1.0 eq.), precursor G (1.0 eq.), tetrakis(triphenylphosphine)palladium (0.05 eq.) and potassium carbonate (3 eq.) were dissolved in a mixed solvent of toluene, ethanol and deionized water (4:2:1). Under a nitrogen environment, the mixture was stirred at 100 ° C for 12 hours. The solution after the reaction was extracted with dichloromethane, the organic layer was collected and dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The crude product was washed with dichloromethane and ethanol in turn, and the product was filtered to obtain the product. The hydrogen spectrum of compound No. 1 is shown as follows Figure 5 As shown in the mass spectrum Figure 6 As shown, 1H NMR(400MHz,Chloroform-d)δ9.23(d,J=8.4Hz,1H),9.01(d,J=8.3Hz,1H),8.87–8.78(m,2H),8.67(d,J=7.6Hz,1H),8.58(s,1H),8.14–8.02 (m,3H),7.85(d,J=9.1Hz,1H),7.67(s,3H),7.64–7.58(m,2H),7.50–7.40(m,4H),7.11(d,J=8.4Hz,2H),1.52(s,9H),1.36(s,9H). High resolution ESI-MS calcd for C47H39BN4O2703.32388, found 703.32190.

[0148] Example 2

[0149] The reaction formula of compound No. 2 (corresponding to compound Z-150) is as follows:

[0150]

[0151] Synthesis of intermediate I: In a 250 mL Schlenk tube, 2,5-dibromo-1,3-difluorobenzene (1.0 eq.), precursor H (1.0 eq.) and cesium carbonate (2.0 eq.) were dissolved in ultra-dry N,N-dimethylformamide. The mixture was stirred at 160 ° C for 12 hours under a nitrogen environment. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. The hydrogen spectrum of intermediate I is shown as follows Figure 7 As shown, 1 HNMR(400MHz,Chloroform-d)δ7.40(d,J=8.7Hz,2H),7.05(dd,J=7.6,2.0Hz,1H),6.96 (d, J=8.7Hz, 2H), 6.77 (s, J=1.7Hz, 1H), 1.34 (s, 9H). High resolution ESI-MScalcdforC16H15Br2FO 401.94530,found401.93887.

[0152] Synthesis of intermediate K: In a 250 mL Schlenk tube, intermediate I (1.0 eq.), precursor J (1.0 eq.) and cesium carbonate (2.0 eq.) were dissolved in ultra-dry N,N-dimethylformamide. The mixture was stirred at 160 ° C for 12 hours under a nitrogen environment. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. The hydrogen spectrum of intermediate K is shown as follows Figure 8 As shown, 1 HNMR(400MHz,Chloroform-d)δ8.14(s,2H),7.49(s,1H),7.47(s,2H),7.45(s,1H),7.33(s,1H),7.12(s,1H),7.08(d,J=2. 8Hz, 2H), 7.06 (d, J = 2.8Hz, 2H), 1.47 (s, 18H), 1.37 (s, 9H). High resolution ESI-MScalcdforC36H39Br2NO662.14507, found662.14307.

[0153] Synthesis of intermediate L: Under a nitrogen environment, a solution of n-butyl lithium dissolved in cyclohexane (n-BuLi, 2.5 mol / L, 1.1 eq) was slowly added to a solution of intermediate K (1.0 eq.) in ultra-dry mesitylene, and the temperature was controlled at -30°C. After stirring at room temperature for 1 hour, a dichloromethane solution of boron tribromide (BBr3, 1 mol / L, 2 eq.) was added dropwise at -78°C. The mixture was slowly warmed to room temperature and stirred for 2 hours, and then N,N-diisopropylethylamine (2 eq.) was added at 0°C. Finally, the mixture was heated to 130°C and maintained for 12 hours. After cooling to room temperature, the reaction solution was poured into a sodium chloride solution and extracted with dichloromethane, then dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude product can be purified by recrystallization from a methanol / dichloromethane system. The hydrogen spectrum of intermediate L is shown in FIG. Figure 9 As shown, 1HNMR(400MHz,Chloroform-d)δ8.97(d,J=1.9Hz,1H),8.87(d,J=2.5Hz,1H),8.47(d,J=1.9Hz,1H),8.31(d,J=1.4Hz,1H),8 .28–8.21(m,2H),7.81–7.76(m,1H),7.68(dd,J=8.8,2.1Hz,1H),7.51–7.42(m,2H),1.63(s,9H),1.52(s,18H).High resolution ESI-MS calcd for C36H37BBrNO 590.22243, found 590.22101.

[0154] Synthesis of intermediate M: In a 250 mL Schlenk tube, intermediate L (1.0 eq.), diboronic acid pinacol ester (1.5 eq.), 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium (0.05 eq.) and potassium acetate (10 eq.) were dissolved in ultra-dry 1,4-dioxane. Under a nitrogen atmosphere, the mixture was stirred at 110 ° C for 12 hours. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. The hydrogen spectrum of intermediate M is shown as follows Figure 10 As shown, 1 H NMR(400MHz,Chloroform-d)δ9.00(s,1H),8.90(s,1H),8.63(s,1H),8.48(d,J=7.4Hz,2H),8.25(s,1H) ,7.81–7.70(m,3H),7.50(d,J=8.8Hz,1H),1.64(s,9H),1.53(d,J=3.5Hz,18H),1.45(s,12H). High resolution ESI-MS calcd for C36H37BBrNO 638.39823,found638.39624.

[0155] Synthesis of compound No. 2: In a 50 mL Schlenk tube, the intermediate M (1.0 eq.), the precursor N (1.0 eq.), tetrakis(triphenylphosphine)palladium (0.05 eq.) and potassium carbonate (3 eq.) were dissolved in a mixed solvent of toluene, ethanol and deionized water (4:2:1). Under a nitrogen environment, the mixture was stirred at 100 ° C for 12 hours. The solution after the reaction was extracted with dichloromethane, the organic layer was collected and dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The crude product was washed with dichloromethane and ethanol in turn, and the product was filtered to obtain the product. The hydrogen spectrum of compound No. 2 is shown as follows Figure 11As shown in the mass spectrum Figure 12 As shown, 1 HNMR(400MHz,Chloroform-d)δ9.49(s,1H),9.15(d,J=8.2Hz,2H),8.91(s,1H),8.81(s ,1H),8.70(d,J=7.0Hz,2H),8.58–8.49(m,2H),8.44(d,J=1.8Hz,1H),8.20(s,1H),7.9 7(d, J=7.5Hz,2H),7.75(d, J=10.8Hz,1H),7.58(dt, J=15.8,7.6Hz,6H),7.46(d, J=8.7Hz,1H),7.38(t, J=7.4Hz,2H),1.69(s,9H),1.58(s,9H),1.57(s,9H). High resolution ESI-MS calcd for C57H50BN5O 832.41812, found 832.41995.

[0156] Example 3

[0157] The reaction formula of compound No. 3 (corresponding to compound Z-561) is as follows:

[0158]

[0159] Synthesis of Intermediate P: In a 250 mL Schlenk tube, 2,5-dibromo-1,3-difluorobenzene (1.0 eq.), precursor O (1.0-1.1 eq.), and cesium carbonate (2.0-3.0 eq.) were dissolved in ultra-dry N,N-dimethylformamide. The mixture was stirred at 160°C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. 1 HNMR (400 MHz, DMSO) δ8.29 (d, J=1.8 Hz, 2H), 8.01 (dd, J=8.2, 2.2 Hz, 1H), 7.81–7.66 (m, 1H), 7.45 (dd, J=8.6, 1.9 Hz, 2H), 7.00 (d, J=8.6 Hz, 2H), 1.41 (s, 18H). High resolution ESI-MS calcd for C26H26Br2FN 531.0396, found 531.0276.

[0160] Synthesis of intermediate R: In a 250 mL Schlenk tube, intermediate P (1.0 eq.), precursor Q (1.0-1.1 eq.) and cesium carbonate (2.0-3.0 eq.) were dissolved in ultra-dry N,N-dimethylformamide. The mixture was stirred at 160 ° C for 12 hours under a nitrogen environment. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. The hydrogen spectrum of intermediate R is shown as follows Figure 13 As shown, 1 HNMR(400MHz,Chloroform-d)δ8.16(d,J=1.9Hz,4H),7.76(s,2H),7.53(dd,J=8.6,1.9Hz,4H),7. 15(d,J=8.6Hz,4H),1.48(s,36H). High resolution ESI-MScalcdforC46H50Br2N2791.32078, found791.31992.

[0161] Synthesis of Intermediate S: Under nitrogen, a solution of n-butyllithium in cyclohexane (n-BuLi, 2.5 mol / L, 1.1-1.5 eq) was slowly added to a solution of Intermediate R (1.0 eq.) in ultra-dry mesitylene at -30°C. After stirring at room temperature for 1 hour, a solution of boron tribromide in dichloromethane (BBr3, 1 mol / L, 2.0-2.5 eq.) was added dropwise at -78°C. The mixture was slowly warmed to room temperature and stirred for 2 hours, followed by the addition of N,N-diisopropylethylamine (2.0-2.5 eq.) at 0°C. Finally, the mixture was heated to 130°C and held for 12 hours. After cooling to room temperature, the reaction solution was poured into sodium chloride solution and extracted with dichloromethane. The mixture was then dried over anhydrous magnesium sulfate, filtered, and the solvent removed by rotary evaporation under reduced pressure. The crude product was purified by recrystallization from methanol / dichloromethane. The hydrogen spectrum of intermediate S is as follows Figure 14 As shown, 1 HNMR(400MHz,Chloroform-d)δ9.09(d,J=1.9Hz,2H),8.45(d,J=1.8Hz,2H),8.35(s,2H),8 .29–8.22(m,4H),7.68(dd,J=8.8,2.1Hz,2H),1.70(s,18H),1.57(s,18H).High resolution ESI-MScalcd for C46H49BBrN2719.31672, found 719.31656.

[0162] Synthesis of intermediate T: In a 250 mL Schlenk tube, intermediate S (1.0 eq.), diboronic acid pinacol ester (1.2-1.5 eq.), 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium (0.05 eq.) and potassium acetate (8.0-10.0 eq.) were dissolved in ultra-dry 1,4-dioxane. Under a nitrogen atmosphere, the mixture was stirred at 110 ° C for 12 hours. After cooling to room temperature, the mixture was diluted with dichloromethane and washed three times with deionized water. The organic layer was collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by column chromatography. The hydrogen spectrum of intermediate T is shown as follows Figure 15 As shown, 1 H NMR (400 MHz, Chloroform-d) δ9.13 (s, 2H), 8.78 (s, 2H), 8.53 (d, J = 8.8 Hz, 2H), 8.48 (s, 2H), 8.26 (s, 2H), 7.73 (d, J = 8.7 Hz, 2H), 1.67 (s, 18H), 1.54 (s, 18H), 1.49 (s, 12H). High-resolution ESI-MS calcd for C52H60B2N2O2 766.48620, found 766.46978.

[0163] Synthesis of compound No. 3: In a 50 mL Schlenk tube, the intermediate T (1.0 eq.), the precursor U (1.0-1.2 eq.), tetrakis(triphenylphosphine)palladium (0.05 eq.) and potassium carbonate (3.0-5.0 eq.) were dissolved in a mixed solvent of toluene, ethanol and deionized water (volume ratio of 4:2:1). Under a nitrogen environment, the mixture was stirred at 100 ° C for 12 hours. The solution after the reaction was extracted with dichloromethane, the organic layer was collected and dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The crude product was washed with dichloromethane and ethanol in turn, and the product was filtered to obtain the product. The hydrogen spectrum of compound No. 3 is shown as follows Figure 16 As shown in the mass spectrum Figure 17 As shown, 1 H NMR (400 MHz, Chloroform-d) δ9.51 (s, 2H), 9.04 (d, J = 8.3 Hz, 2H), 8.97 (s, 2H), 8.58–8.44 (m, 4H), 8.39 (s, 2H), 8.12 (s, 2H), 7.87 (s, 2H), 7.63–7.31 (m, 9H), 1.72 (s, 18H), 1.56 (s, 18H). High-resolution ESI-MS calcd for C67H61BN6961.51235, found 961.51080.

[0164] Thermogravimetric analysis was performed on Compound No. 1, Compound No. 2 and Compound No. 3 in Examples 1-3 using a thermogravimetric analyzer. Figure 18 As shown in the figure, the decomposition temperature of the materials is above 400°C, indicating that the materials are not easy to decompose under high temperature conditions and have good stability. The OmniFluo 900PL spectrometer was used to measure the decomposition temperature of compounds 1, 2 and 3 in Examples 1-3 at 2×10 -5 The emission spectrum of M in toluene solution is as follows Figure 19 As shown in the figure, the data show that the full width at half maximum (FWHM) of the emission spectra of the three materials in toluene solution are all below 40 nm.

[0165] The present invention also provides an application of the multiple resonance thermally activated delayed fluorescent material, which uses the multiple resonance thermally activated delayed fluorescent material as a functional material for an organic electronic device.

[0166] In some embodiments, the organic electronic devices include organic electroluminescent devices, organic photovoltaic devices (including solar cells and thin-film solar cells), organic sensing elements (including optical sensors and electronic artificial skin sheets), organic display units, and other organic semiconductor devices (including organic thin-film transistors and field-effect transistors).

[0167] In some embodiments, the application involves using the multi-resonant thermally activated delayed fluorescent material as a light-emitting layer material in an organic electroluminescent device. The multi-resonant thermally activated delayed fluorescent material of the present invention exhibits significant application advantages in light-emitting layer materials for organic electroluminescent devices, and this property makes it of great application value in the field of OLED light-emitting materials.

[0168] The present invention also provides an organic electroluminescent device comprising an anode layer, a cathode layer and one or more organic functional layers inserted between the anode layer and the cathode layer, wherein the organic functional layer comprises the multi-resonance thermally activated delayed fluorescent material.

[0169] In some embodiments, the organic functional layer includes a hole transport region, a light-emitting layer, and an electron transport region; the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the light-emitting layer is located between the hole transport region and the electron transport region; wherein the light-emitting layer includes the multiple resonance thermally activated delayed fluorescent material.

[0170] In some embodiments, the material of the anode layer can be a transparent conductive oxide material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof. The material of the cathode layer can be a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof.

[0171] In some embodiments, the hole transport region can be a single-layer hole transport layer (HTL), including single-layer hole transport layers containing only one compound and multilayer hole transport layers containing multiple compounds. The hole transport region can also be expanded to a multilayer structure, including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0172] In some embodiments, the light-emitting layer includes a light-emitting material that can emit different wavelength spectra, and may also include a host material and a photosensitizer. The light-emitting layer is generally composed of a light-emitting material doped in a host material to emit light, and sometimes a photosensitizer is added to improve energy efficiency.

[0173] In some embodiments, the electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multi-layer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0174] In one example, the organic electroluminescent device is fabricated as follows: a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially deposited by vacuum deposition onto glass having an ITO-coated anode, followed by encapsulation. The light-emitting layer is formed by co-evaporating a wide-bandgap host material source, an MR-TADF material source, and a TADF photosensitizer source.

[0175] In one embodiment, the method for preparing an OLED device includes the following steps:

[0176] 1. Scrub the glass plate with the etched anode material with a magic brush dipped in Dcon90 alkaline cleaning agent, then repeatedly ultrasonicate with ethanol, ultrapure water, and ethanol for 15 minutes each time, completely remove moisture in a clean oven, and clean with ozone;

[0177] 2. Place the glass plate into the vacuum evaporator and use a molecular pump to evacuate to 10 -6Below Pa, evaporating a hole injection material on the anode film to form a hole injection layer, with the evaporation rate controlled at 0.1-0.3 nm / s;

[0178] 3. Evaporating a hole transport material on the hole injection layer to form a hole transport layer, with the evaporation rate controlled at 0.5-1 nm / s;

[0179] 4. Evaporate the electron blocking layer on the hole transport layer at a rate of 0.5-1 nm / s;

[0180] 5. Vacuum-deposit the organic light-emitting layer of the device on the electron blocking layer. The organic light-emitting material includes a host material, an MR-TADF light-emitting material, and a sensitizer. Utilize a multi-source co-evaporation method to adjust the evaporation rate of the host material, the sensitizer material, and the light-emitting material so that the compound reaches a preset doping ratio.

[0181] 6. Vacuum-deposit a hole blocking layer on the organic light-emitting layer at a rate of 0.5-1 nm / s;

[0182] 7. Vacuum-deposit an electron transport layer on the hole blocking layer at a rate of 0.5-1 nm / s;

[0183] 8. Vacuum-deposit an electron injection layer on the electron transport layer at a rate of 0.1-0.2 nm / s, and vacuum-deposit Al as the cathode of the device at a rate of 0.5-2 nm / s.

[0184] The organic electroluminescent device related to the present invention is further described below through specific examples.

[0185] Example 4

[0186] The layer structures of the organic electroluminescent devices A1, A2, and A3 are shown below:

[0187] ITO (50nm) / p-dopant:HTL1 (mass ratio 3:97) (10nm) / HTL1 (50nm) / HTL2 (5nm) / xwt% emitter:BH02 (20nm) / ETL1 (5nm) / ETL2:Liq (mass ratio 50:50) (30nm) / Liq (2nm) / Al (120nm)

[0188] The organic light-emitting material (emitter) is compound No. 2, and the doping concentration of the light-emitting material of the present invention is 3wt% (device A1), 5wt% (device A2), and 7wt% (device A3). The material structure used is as follows:

[0189]

[0190] The organic electroluminescent devices A1, A2, and A3 prepared in this embodiment were subjected to a DC voltage and their electroluminescent characteristics were measured. The results showed that the wavelength was 497 nm, the half-peak width was 37 nm, the CIE color coordinates (x, y) = (0.15, 0.57), and the luminescence intensity was 1000 cd / m 2 LT under the brightness 90 (decayed to 90% of the initial brightness) were 963h (A1), 1082h (A2), and 1486h (A3) of green light emission (driving voltage was 2.7V).

[0191] For the organic electroluminescent devices A1, A2, and A3 prepared in this embodiment, the current density, brightness, and photoluminescence spectrum of the organic electroluminescent devices at different voltages were tested using Keithley 2400, and then the current was divided by the luminescent area to obtain the current of the organic electroluminescent device at different voltages. The PR-OLED LT-16 was used to test the lifetime degradation test, and the brightness and radiant energy flux density of the organic electroluminescent devices prepared in Example 4 and the comparative example (see Table 2) at different voltages were tested. According to the current density and brightness of the organic electroluminescent devices at different voltages, the external quantum efficiency EQE and device life were obtained. The results are shown in Table 1. Devices A1, A2, and A3 have a lifetime of 1000 cd / m 2 The operating life under brightness is shown in the figure Figure 20 shown.

[0192] Table 1 Performance evaluation results of organic optoelectronic devices

[0193] Device <![CDATA[V on [V]]> <![CDATA[EQE max [%]]]> <![CDATA[LT 90 [h]]]> A1 2.6 6.7 963 A2 2.7 6.8 1082 A3 2.6 5.9 1486

[0194] As shown in Table 2 below, the organic light emitting layer (other layers are the same as those in Example 4) made of the green light emitting material in the reference in Table 2 has a working brightness of 1000 cdm -2 Lower life performance.

[0195] Table 2 Published green organic optoelectronic devices with an operating brightness of 1000 cdm -2 Comparison of lower life performance

[0196]

[0197]

[0198] The OLED device prepared using the compound of the present invention has a low starting voltage, high luminous efficiency and a better service life, and can meet the requirements of current panel manufacturing companies for high-performance materials.

[0199] In the general compound structure of the present invention, the stability of the molecule is increased by connecting the classic MR-TADF skeleton with the triazine group. While achieving a higher fluorescence quantum yield (PLQY>90%) and color purity, the color of the material can be controlled from blue light to red light through structural optimization.

[0200] The above embodiments apply the luminescent material to the organic light-emitting layer. The inventors predict that the multi-resonance thermally activated delayed fluorescent material of the present invention may also be used in the hole injection layer, hole transport layer, electron transport layer, and electron injection layer as the corresponding functional materials of these layers.

[0201] The above description further details the present invention in conjunction with specific / preferred embodiments, and the specific implementation of the present invention should not be construed as being limited to these descriptions. Persons skilled in the art will appreciate that, without departing from the spirit of the present invention, they may make various substitutions or modifications to the described embodiments, and these substitutions or modifications should be considered to fall within the scope of protection of the present invention. Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "preferred embodiments," "examples," "specific examples," or "some examples" indicates that the specific features, structures, materials, or characteristics described in conjunction with such embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Persons skilled in the art may combine and assemble the different embodiments or examples described in this specification, as well as features of different embodiments or examples, without conflicting opinions. Although the embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions, and modifications may be made herein without departing from the scope of protection of the patent application.

Claims

1. A stable multi-resonance thermally activated delayed fluorescence material, characterized in that: It has a structure shown by formula (I), formula (II) or formula (III): In formula (I), (II), and (III), R1,R2,R5,R6,R7,R 10 ,R 11 ,R 12 ,R 13 each independently represents hydrogen, tert-butyl, phenyl, adamantyl or 3,5-diphenyltriazinyl; R3,R4,R8,R9,R 14 ,R 15 Each represents a single substituent to the maximum permissible substituent, and is independently selected from one of hydrogen, C1-C12 chain alkyl, C5-C6 cycloalkyl, C1-C10 alkoxy, halogen, nitro, hydroxy, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; X1, X2, X3 are each independently selected from oxygen, sulfur or selenium; X4, X5, and X6 are each independently selected from a single bond, dimethyl, diphenyl, fluorene ring-substituted carbon, fluorene ring-substituted silicon, or fluorene ring-substituted germanium.

2. The stable multi-resonance thermally activated delayed fluorescent material according to claim 1, wherein The multiple resonance thermally activated delayed fluorescent material is selected from one of the following compounds Z-1 to Z-657:

3. A method for preparing the multi-resonance thermally activated delayed fluorescent material according to claim 1, characterized in that: The steps include: (1) For compound No. 1 represented by formula (I), its synthesis route is as follows: (1.1) Synthesis of intermediate B: 2,5-dibromo-1,3-difluorobenzene, precursor A, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate B was obtained by post-treatment. (1.2) Synthesis of intermediate D: The intermediate B, precursor C, and cesium carbonate are dissolved in ultra-dry N,N-dimethylformamide, reacted under nitrogen protection, and post-processed to obtain intermediate D; (1.3) Synthesis of Intermediate E: Under nitrogen protection, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate D dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate E is obtained by post-treatment. (1.4) Synthesis of intermediate F: Intermediate E, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate F was obtained by post-treatment. (1.5) Synthesis of Compound No. 1 of Formula (I): Intermediate F, precursor G, tetrakis(triphenylphosphine)palladium, and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol, and deionized water, and reacted under nitrogen. After the reaction, the compound No. 1 of Formula (I) is obtained by post-treatment. (2) For compound No. 2 represented by formula (II), its synthesis route is as follows: (2.1) Synthesis of intermediate I: 2,5-dibromo-1,3-difluorobenzene, precursor H, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen. After the reaction, intermediate I was obtained by post-treatment. (2.2) Synthesis of intermediate K: Intermediate I, precursor J, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate I was obtained by post-treatment. (2.3) Synthesis of Intermediate L: Under nitrogen protection, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate K dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate L is obtained by post-treatment. (2.4) Synthesis of intermediate M: Intermediate L, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate M was obtained by post-treatment. (2.5) Synthesis of Compound No. 2 of Formula (II): Intermediate M, precursor N, tetrakis(triphenylphosphine)palladium, and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol, and deionized water, and reacted under nitrogen. After the reaction, compound No. 2 of Formula (II) is obtained by post-treatment. (3) For compound No. 3 represented by formula (III), its synthesis route is as follows: (3.1) Synthesis of intermediate P: 2,5-dibromo-1,3-difluorobenzene, precursor O, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen. After the reaction, intermediate P was obtained by post-treatment. (3.2) Synthesis of intermediate R: Intermediate I, precursor J, and cesium carbonate were dissolved in ultra-dry N,N-dimethylformamide and reacted under nitrogen protection. After the reaction, intermediate R was obtained by post-treatment. (3.3) Synthesis of Intermediate S: Under nitrogen, a solution of n-butyl lithium dissolved in cyclohexane is added to a solution of Intermediate R dissolved in ultra-dry mesitylene. After a period of reaction, a solution of boron tribromide dissolved in dichloromethane is added dropwise. After stirring and reacting for a period of time, N,N-diisopropylethylamine is added to react. After the reaction, intermediate S is obtained by post-treatment. (3.4) Synthesis of intermediate T: Intermediate S, pinacol diboronate, 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium, and potassium acetate were dissolved in ultra-dry 1,4-dioxane and reacted under nitrogen protection. After the reaction, intermediate T was obtained by post-treatment. (3.5) Synthesis of compound No. 3 represented by formula (III): The intermediate T, precursor U, tetrakis(triphenylphosphine)palladium and potassium carbonate are dissolved in a mixed solvent of toluene, ethanol and deionized water, and reacted under nitrogen protection. After the reaction, compound No. 3 represented by formula (III) is obtained by post-treatment.

4. Use of the multi-resonance thermally activated delayed fluorescence material according to any one of claims 1 to 2, characterized in that: The multi-resonance thermally activated delayed fluorescent material is used as a functional material for an organic electronic device.

5. The use according to claim 4, characterized in that The organic electronic devices include organic electroluminescent devices, organic photovoltaic devices, organic sensor elements, organic display units, organic thin film transistors, and field effect transistors.

6. The use according to claim 5, characterized in that The application is to use the multiple resonance thermally activated delayed fluorescent material as a light-emitting layer material of an organic electroluminescent device.

7. An organic electroluminescent device comprising an anode layer, a cathode layer, and one or more organic functional layers interposed between the anode layer and the cathode layer, characterized in that: The organic functional layer comprises the multi-resonance thermally activated delayed fluorescent material according to any one of claims 1 to 2.

8. The organic electroluminescent device according to claim 7, wherein: The organic functional layer includes a hole transport region, a light-emitting layer, and an electron transport region; the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the light-emitting layer is located between the hole transport region and the electron transport region; wherein the light-emitting layer includes the multiple resonance thermally activated delayed fluorescent material described in any one of claims 1-2.

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