Organic compound, application thereof and organic electroluminescent device containing organic compound

Abstract

The present invention relates to a compound and application thereof, and an organic electroluminescent device comprising the compound, the compound has a structure represented by the following formula: wherein X1 and X2 are respectively and independently N or B; ring A, ring B and ring C are benzene rings; a ring d1 and a ring d2 are respectively and independently a benzene ring or a naphthalene ring; and ring E and ring F each independently represent a C4-C30 aromatic ring. When the compound is used as a luminescent material in an OLED device, the compound shows excellent device performance and stability. The invention also protects the organic light-emitting device adopting the compound with the general formula. # imgabs0 #

Description

Technical Field

[0001] The invention relates to an organic compound and application thereof, and an organic electroluminescent device containing the compound, belonging to the technical field of organic electroluminescence. Background Art

[0002] Organic light emitting diodes (OLED) are a type of device with a sandwich-like structure, including positive and negative electrode film layers and organic functional material layers sandwiched between the electrode film layers. Due to the advantages of high brightness, fast response, wide viewing angle, simple process, and flexibility, OLED devices have attracted much attention in the fields of new display technology and new lighting technology. At present, this technology has been widely used in display panels of new lighting fixtures, smart phones, tablet computers and other products, and will further expand to the application fields of large-size display products such as televisions. It is a new display technology with rapid development and high technical requirements. In order to prepare OLED light-emitting devices with lower driving voltage, better luminous efficiency, and longer device life, and to continuously improve the performance of OLED devices, it is necessary not only to optimize the structure and manufacturing process of OLED devices, but also to continuously conduct in-depth research on the optoelectronic functional materials in OLED devices in order to prepare functional materials with higher performance.

[0003] In 2012, in order to promote the development of ultra-high-definition display, the International Telecommunication Union Radiocommunication Sector (ITU-R) promulgated the BT.2020 standard, whose color gamut is much larger than BT.709, posing new challenges to the construction of OLED. Therefore, improving the color purity of OLED to meet the BT.2020 standard has become an important research direction in this field.

[0004] Studies have shown that the multiple resonance (MR) effect can effectively inhibit the structural relaxation and vibration coupling of molecules, significantly narrow the fluorescence spectrum of the dye, and thus greatly improve the color purity of the device. At present, the multiple resonance effect is mainly induced by alternating nitrogen atoms and boron atoms or carbonyl groups. However, boron atoms and carbonyl groups have high chemical activity. While improving the color purity of the device, it also brings stability problems, limiting the application of this type of material. Therefore, how to prepare multiple resonance materials with good stability is still full of challenges. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a multi-resonance fluorescent dye with a new structure. The specific technical solution is as follows.

[0006] An organic compound having a structure shown in any one of the following formulas (1), (2), (3) or (4):

[0007]

[0008] Among them, X 1 and X 2 are independently N or B;

[0009] Ring A, Ring B, and Ring C are all benzene rings; Ring d 1 、Ring d 2 Each independently represents a benzene ring or a naphthalene ring; Ring E and Ring F each independently represent a C4-C30 aromatic ring;

[0010] The R A , R B , R C , R D , R E and R F R each independently represents a substituent from a single substituent to the maximum permissible number of substituents. A , R B , R C , R D , R E and R F Each is independently selected from one of hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-C36 chain alkyl, substituted or unsubstituted C3-C36 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 thioalkoxy, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C60 monocyclic aryl or condensed ring aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C5-C60 heteroaryl;

[0011] The R A , R B , R C , R D , R E and R F Each of the rings A, B, C, D, E and F is connected to each other by a single bond, or R A , R B , R C , R D , R E and R F Each is fused to the connected ring A, ring B, ring C, ring D, ring E and ring F, and the R A , R B , R C , R D , R E and R F Two adjacent ones are connected to form a ring or not connected to form a ring;

[0012] When the above R A , R B , R C , R D , R E and R F When substituents are present, the substituents are independently selected from one of deuterium, halogen, cyano, amino, C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C6-C60 aryl, and C5-C60 heteroaryl.

[0013] The organic compounds of the present invention are different from the traditional boron nitrogen and carbonyl nitrogen structures. The electronegativity difference between the nitrogen atom or boron atom and the carbon atom is used in the compound structure of the present invention to achieve the regulation of the molecular frontier orbital and obtain a significant multiple resonance effect. Specifically, the compounds of the present invention adopt the parent core structure shown in formula (I), the ring A, the ring B and the ring C all adopt aromatic rings such as benzene rings and naphthalene rings, the ring D adopts fused aromatic hydrocarbons, and the rings E and F are fused to form fused aromatic hydrocarbons. 1 and X 2 are independently selected from B or N. 1 and X 2 Being in the para position of ring A can enhance the electronic synergy and reduce the energy level of the molecule. 1 and X 2 The indole carbazole skeleton is formed. This type of skeleton is relatively special, which is conducive to local distribution of LUMO orbital intervals on atoms, resulting in multiple resonance effects. Ring D and the above-mentioned indole carbazole skeleton are fused in the form of a six-membered ring, which can reduce the bond tension of the molecule and improve chemical stability. Ring E and the above-mentioned indole carbazole skeleton are fused in the form of a five-membered ring, which can enhance the rigidity of the molecular structure, inhibit the structural relaxation of the molecular excited state, and narrow the spectrum. Although ring D and ring E have different connection positions with the parent nucleus, these connection sites do not change the indole carbazole skeleton of the parent nucleus, and the fusion modes of ring D and ring E with the parent nucleus are still the fusion modes of the six-membered ring and the five-membered ring, respectively, which can enhance the chemical stability and structural rigidity of the molecule and achieve a stable narrow emission spectrum. In summary, thanks to the above structural characteristics, the molecular structure of the present invention has a larger rigid conjugated plane, the parent nucleus structure of the indole carbazole-like structure and moderate bond tension, which can achieve a balance between multiple resonance effects and excited state regulation, and obtain higher color purity and efficient and stable performance. Therefore, the compounds of the present invention are expected to be used in the preparation of efficient and stable narrow-spectrum organic light-emitting diodes when used as luminescent dyes, and have great application value in the fields of display and lighting.

[0014] In this specification, the "substituted or unsubstituted" group may be substituted with one substituent or multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the same expressions are involved in the present invention, they all have the same meaning, and the selection range of substituents is as shown above and will not be repeated one by one.

[0015] In the present specification, the expression of Ca to Cb represents that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent.

[0016] In the present specification, the expression of a ring structure crossed by “—” indicates that the connection site is any position on the ring structure that can form a bond.

[0017] In the present specification, “each independently” means that when there are multiple subjects, they may be the same as or different from each other.

[0018] In this specification, unless otherwise specified, the expression of chemical elements generally includes the concept of their isotopes. For example, the expression "hydrogen (H)" includes its isotopes. 1 H (hydrogen or H), 2 The concept of H (deuterium or D); carbon (C) includes 12 C. 13 C, etc., no further details.

[0019] The heteroatom in the heteroaryl group in the present specification generally refers to an atom or an atom group selected from B, N, O, S, P, Si and Se, preferably selected from N, O and S.

[0020] In the present specification, examples of halogen include fluorine, chlorine, bromine, and iodine.

[0021] In this specification, the substituted or unsubstituted C6-C60 aryl includes monocyclic aryl and condensed aryl, and C6-C30 aryl is further preferred. The so-called monocyclic aryl refers to a molecule containing at least one phenyl group. When the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond, such as phenyl, biphenyl, terphenyl, etc. Specifically, the biphenyl includes 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl includes p-terphenyl-4-base, p-terphenyl-3-base, p-terphenyl-2-base, m-terphenyl-4-base, m-terphenyl-3-base and m-terphenyl-2-base. Condensed aryl refers to a molecule containing at least two aromatic rings, and the aromatic rings are not independent of each other but share two adjacent carbon atoms to condense each other. For example, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl, fluoranthenyl, triphenylene, pyrenyl, peryl, The naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthacenyl group is selected from 1-naphthacenyl, 2-naphthacenyl and 9-naphthacenyl. The fluorene derivative group is selected from 9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, 9,9'-spirobifluorene and benzofluorenyl.

[0022] In the present specification, the substituted or unsubstituted C5-C60 heteroaryl includes a monocyclic heteroaryl and a condensed ring heteroaryl, and is further preferably a C5-C30 heteroaryl, and more preferably a C5-C15 heteroaryl. A monocyclic heteroaryl refers to a molecule containing at least one heteroaryl. When the molecule contains one heteroaryl and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl and other groups are independent of each other and connected by a single bond. Examples of monocyclic heteroaryl groups include furanyl, thienyl, pyrrolyl, pyridyl, etc. A condensed ring heteroaryl refers to a molecule containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring), and the two are not independent of each other but share two adjacent atoms and are fused to each other. Examples of fused ring heteroaryl groups include benzofuranyl, benzothiophenyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, acridinyl, isobenzofuranyl, isobenzothiophenyl, benzocarbazolyl, azacarbazolyl, phenothiazinyl, phenazinyl, 9-phenylcarbazolyl, 9-naphthylcarbazolyl, dibenzocarbazolyl, indolocarbazolyl and the like.

[0023] For further explanation, the ring D in formula (I) can be 1 and Ring D 2 Among them, ring d 1 and Ring D 2 Each independently represents one of a C6-C30 aromatic ring and a C4-C30 heteroaromatic ring.

[0024] The organic compound of the present invention further preferably has a structure shown in any one of the following formulas (5), (6), (7) or (8):

[0025]

[0026] In formulas (5)-(8), the X 1 , X 2 , R A , R B , R C, R D , R E , R F 、Ring d 1 and Ring D 2 The definitions of are the same as those in formula (1), formula (2), formula (3) or formula (4).

[0027] The organic compound of the present invention further preferably has a structure shown in any one of the following formulas (9), (10), (11) or (12):

[0028]

[0029] In formulas (9)-(12), the X 1 , X 2 , R A , R B , R C , R D , R E and R F The definitions of are the same as those in formula (1), formula (2), formula (3) or formula (4); the R B , R C , R D , R E and R F Each is linked to the adjacent ring structure via a single bond or fused.

[0030] In the above general formulas of the present invention, preferably, the X 1 and X 2 At the same time, X 1 and X 2 At the same time, X is a B atom; more preferably, 1 and X 2 At the same time it is a N atom.

[0031] The organic compound of the present invention further preferably has a structure represented by the following formula (13), formula (14), formula (15) or formula (16):

[0032]

[0033] In the above general formulas of the present invention, preferably, the R A , R B , R C , R D , R E and R Fare independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylene, pyrenyl, chrysene, peryl, fluoranthenyl, tetraphenylene, pentacene, benzopyrenyl, biphenyl, phenylene, terphenylene, triphenylene, tetraphenylene, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis or trans Indenyl, indenyl, isotrimer, indenyl, spirotrimer, indenyl, spiroisotrimer, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenylcarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthracene oxazolyl, phenanthrazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5 _oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, diarylamine, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, pyrrole, piperidine, methoxy, silicon, or a combination of two of the above substituent groups;

[0034] Preferably, the R A , R B , R C , R D , R E and R FEach of the substituents is independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, adamantyl, fluorine, trifluoromethyl, phenyl, mesityl, naphthyl, anthracenyl, furanyl, tetrahydrofuranyl, pyrrolyl, tetrahydropyrrolyl, thienyl, carbazolyl, triazine, pyridyl, quinolyl, acridinyl, cyano, methoxy, silicon, dimethylamino, triarylamine, fluorenyl, dibenzofuranyl, and dibenzothienyl, or a combination of two of the above substituents.

[0035] Furthermore, the compounds of the general formula (I) of the present invention can preferably include the following specific structural compounds: X-1 to X-375. These compounds are only representative:

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] The present invention also provides an organic electroluminescent device, comprising a substrate, a first electrode, a second electrode and one or more organic layers inserted between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by any one of the above general formula (I) and general formula (1) to formula (12).

[0049] Specifically, an embodiment of the present invention provides an organic electroluminescent device, comprising a substrate, and an anode layer, a plurality of light-emitting functional layers and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and a light-emitting layer is provided between the hole transport layer and the electron transport layer; wherein, preferably, the light-emitting layer contains the general formula compound of the present invention shown in any one of the above general formula (I) and general formula (1) to formula (12).

[0050] In addition, the present invention also protects an organic electroluminescent device containing an organic compound represented by any one of the above general formula (I) and general formula (1) to formula (12) for use in display and lighting devices.

[0051] The organic compounds provided by the present invention that can be used in organic electroluminescent devices have a large-plane indolecarbazole-like structure, in which the difference in electronegativity between heteroatoms and carbon atoms can enhance the multiple resonance effect of the molecule, so that the compound molecule has excellent luminous efficiency and high color purity, and the high bond energy also makes the molecule have better chemical stability and water and oxygen tolerance. When the compounds of the present invention are applied to the doping materials of the light-emitting layer of the organic electroluminescent device, the OLED device has a narrower spectral half-peak width, excellent device performance and longer service life. The organic compounds of the present invention meet the requirements of current panel manufacturers for high-performance materials and show good application prospects. DETAILED DESCRIPTION

[0052] The specific preparation method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the preparation method of the present invention is not limited to these synthesis examples.

[0053] Various chemicals used in the present invention, such as petroleum ether, hydroiodic acid, acetonitrile, sodium chloride, dichloromethane, N,N-dimethylformamide, ethyl acetate, palladium acetate, tetrakistriphenylphosphine palladium, tri-tert-butylphosphine tetrafluoroborate, sodium tert-butoxide, cuprous iodide, tetra-n-butylammonium chloride, toluene, boron tribromide, n-butyl lithium, tetrahydrofuran and other reaction intermediates and other basic chemical raw materials are purchased from Shanghai Titan Technology Co., Ltd. and Shanghai Bid Pharmaceutical Technology Co., Ltd. The mass spectrometer used to determine the following compounds is a ZAB-HS mass spectrometer (manufactured by Micromass, UK).

[0054] The following is a brief description of the synthesis method of the compound of the present invention. 1 and X 2All of them are nitrogen atoms. First, cuprous iodide is used as a catalyst, tetrabutylammonium hydroxide is used as a base, and N,N-dimethylformamide is used as a solvent. The Ullmann reaction is carried out at 120°C to obtain the target compound. 1 and X 2 When X is a different atom in nitrogen and boron respectively, first use cuprous iodide-catalyzed Ullmann reaction to buckle the ring to obtain an intermediate. Further, n-butyl lithium is used to produce lithium halogen exchange with the halogen of the intermediate. Then, after adding boron tribromide to carry out lithium-boron metal exchange, Lewis base such as N, N-diisopropylethylamine is added to carry out tandem boro-Friedel-Crafts reaction to obtain the target compound. For X 1 and X 2 All of them are molecules of boron atoms. The synthesis process is similar to the above-mentioned boron removal process. After the intermediates undergo lithium halogen exchange and lithium boron exchange reactions, they undergo boro-Friedel-Crafts reaction in the presence of N, N-diisopropylethylamine to obtain the target compound.

[0055] More specifically, the synthesis methods of representative specific compounds of the present invention are given below.

[0056] Synthesis Example

[0057] Synthesis Example 1:

[0058]

[0059] (1) Synthesis of Compound X-1-1

[0060]

[0061] 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole (4.12 g, 10.00 mmol), (3-chloronaphthalene-2-yl)boric acid (2.27 g, 11.00 mmol), tetrakistriphenylphosphine palladium (35 mg, 0.30 mmol) and potassium carbonate (2.76 g, 20.00 mmol) were added to a 250 mL double-necked flask in sequence. Under a nitrogen atmosphere, 60 mL of toluene, 20 mL of ethanol and 10 mL of water were added, and the reaction was stopped after 12 hours at 90 ° C. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:1) ​​as eluents to obtain yellow powder X-1-1 (3.77 g).

[0062] (2) Synthesis of Compound X-1-2

[0063]

[0064] X-1-1 (2.69 g, 5.00 mmol), (8-chloronaphthalene-1-yl) boronic acid (1.13 g, 5.50 mmol), tetrakistriphenylphosphine palladium (35 mg, 0.30 mmol) and potassium carbonate (1.38 g, 10.00 mmol) were added to a 100 mL two-necked flask in sequence. 30 mL of toluene, 10 mL of ethanol and 50 mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 12 hours at 90 ° C. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain yellow powder X-1-2 (1.2 g).

[0065] (3) Synthesis of Compound X-1

[0066]

[0067] Into a 100mL two-necked round-bottom flask, add intermediate X-1-1 (0.43g, 0.75mmol) and cuprous iodide (0.29g, 1.50mmol), and then add 25mL N,N-dimethylformamide and 2.5mL tetra-n-butylammonium chloride in a nitrogen atmosphere. Then heat to 120°C and react for 24h. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, collect the organic phase and dry it with anhydrous sodium sulfate. After the organic phase is concentrated under reduced pressure, column chromatography is performed to obtain the target compound X-1 (0.31g, 82% yield, HPLC analysis purity 95%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 504.15 Elemental analysis results: Theoretical value: C, 90.45; H, 4.00; N, 5.55 (%); Experimental value: C, 90.42; H, 3.38N, 5.60 (%).

[0068] Synthesis Example 2:

[0069]

[0070] (1) Synthesis of Compound X-2-1

[0071]

[0072] 6-iodo-10-bromo-5,11-dihydroindole[3,2-b]carbazole (4.60 g, 10.00 mmol), (3-chloronaphthalene-2-yl)boric acid (2.27 g, 11.00 mmol), tetrakistriphenylphosphine palladium (35 mg, 0.30 mmol) and potassium carbonate (2.76 g, 20.00 mmol) were added to a 250 mL double-necked flask in sequence. Under a nitrogen atmosphere, 60 mL of toluene, 20 mL of ethanol and 10 mL of water were added, and the reaction was stopped after 12 hours at 90 ° C. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:1) ​​as eluents to obtain yellow powder X-2-1 (2.95 g).

[0073] (2) Synthesis of Compound X-2-2

[0074]

[0075] X-2-1 (2.69 g, 5.00 mmol), (8-chloronaphthalene-1-yl) boronic acid (1.13 g, 5.50 mmol), tetrakistriphenylphosphine palladium (35 mg, 0.30 mmol) and potassium carbonate (1.38 g, 10.00 mmol) were added to a 100 mL two-necked flask in sequence. Under a nitrogen atmosphere, 30 mL of toluene, 10 mL of ethanol and 50 mL of water were added, and the reaction was stopped after 12 hours at 90 ° C. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain yellow powder X-2-2 (0.9 g).

[0076] (3) Synthesis of Compound X-2

[0077]

[0078] Into a 100mL two-necked round-bottom flask, add intermediate X-2-2 (0.57g, 1.00mmol) and cuprous iodide (0.40g, 2.00mmol), and then add 33mL N,N-dimethylformamide and 3.3mL tetra-n-butylammonium chloride in a nitrogen atmosphere. Then heat to 120°C and react for 24h. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, collect the organic phase and dry it with anhydrous sodium sulfate. After the organic phase is concentrated under reduced pressure, column chromatography is performed to obtain the target compound X-2 (0.44g, 87% yield, HPLC analysis purity 92%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 504.15 Elemental analysis results: Theoretical value: C, 90.45; H, 4.00; N, 5.55 (%); Experimental value: C, 90.46; H, 4.02N, 5.52 (%).

[0079] Synthesis Example 3:

[0080]

[0081] (1) Synthesis of Compound X-3-1

[0082]

[0083] 4,10-dibromo-5,11-dihydroindole[3,2-b]carbazole (4.12 g, 10.00 mmol), (3-chloronaphthalene-2-yl)boric acid (2.27 g, 11.00 mmol), tetrakistriphenylphosphine palladium (35 mg, 0.30 mmol) and potassium carbonate (2.76 g, 20.00 mmol) were added to a 250 mL double-necked flask in sequence. Under a nitrogen atmosphere, 60 mL of toluene, 20 mL of ethanol and 10 mL of water were added, and the reaction was stopped after 12 hours at 90 ° C. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:1) ​​as eluents to obtain yellow powder X-3-1 (3.64 g).

[0084] (2) Synthesis of Compound X-3-2

[0085]

[0086] X-3-1 (2.69 g, 5.00 mmol), (8-chloronaphthalene-1-yl) boronic acid (1.13 g, 5.50 mmol), tetrakistriphenylphosphine palladium (35 mg, 0.30 mmol) and potassium carbonate (1.38 g, 10.00 mmol) were added to a 100 mL two-necked flask in sequence. Under a nitrogen atmosphere, 30 mL of toluene, 10 mL of ethanol and 50 mL of water were added, and the reaction was stopped after 12 hours at 90 ° C. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain yellow powder X-3-2 (1.1 g).

[0087] (3) Synthesis of Compound X-3

[0088]

[0089] In a 100mL two-necked round-bottom flask, the intermediate X-3-2 (0.57g, 1.00mmol) and cuprous iodide (0.40g, 2.00mmol) were added respectively, and 33mL N,N-dimethylformamide and 3.3mL tetra-n-butylammonium chloride were added in sequence under a nitrogen atmosphere. Then the temperature was raised to 120°C for 24h. After the reaction was completed, the mixture was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was collected and dried with anhydrous sodium sulfate. After the organic phase was concentrated under reduced pressure, column chromatography was performed to obtain the target compound X-3 (0.36g, 71% yield, HPLC analysis purity 96%) as a yellow-orange solid. MALDI-TOF-MS results: Molecular ion peak: 504.12 Elemental analysis results: Theoretical value: C, 90.45; H, 4.00; N, 5.55 (%); Experimental value: C, 90.41; H, 4.03N, 5.56 (%).

[0090] Synthesis Example 4:

[0091]

[0092] (1) Synthesis of Compound X-16-1

[0093]

[0094] This example is basically the same as the synthesis of compound X-1-1, except that: in this example, 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole is replaced with 6,12-dibromo-2,8-di-tert-butyl-5,11-dihydroindole[3,2-b]carbazole. The target compound X-16-1 (2.67 g) is obtained as a light yellow powder.

[0095] (2) Synthesis of Compound X-16-2

[0096]

[0097] The synthesis of this example is basically the same as that of compound X-1-2, except that X-1-1 is replaced by X-16-1 in this example to obtain the target compound X-16-2 (1.04 g) as a yellow powder.

[0098] (3) Synthesis of Compound X-16

[0099]

[0100] This example is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced by X-16-2 in this example. The target compound X-16 (0.28 g, 75% yield, HPLC analysis purity 98%) is a red solid. MALDI-TOF-MS results: molecular ion peak: 616.27 Elemental analysis results: theoretical value: C, 89.58; H, 5.88; N, 4.54 (%); experimental value: C, 89.57; H, 5.85N, 4.58 (%).

[0101] Synthesis Example 5:

[0102]

[0103] (1) Synthesis of Compound X-18-1

[0104]

[0105] This example is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole is replaced with 4,10-dibromo-2,8-di-tert-butyl-5,11-dihydroindole[3,2-b]carbazole in this example. The target compound X-18-1 (2.73 g) is obtained as a light yellow powder.

[0106] (2) Synthesis of Compound X-18-2

[0107]

[0108] The synthesis of this example is basically the same as that of compound X-1-2, except that X-1-1 is replaced by X-18-1 in this example to obtain the target compound X-18-2 (1.21 g) as a yellow powder.

[0109] (3) Synthesis of Compound X-18

[0110]

[0111] This example is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced by X-18-2 in this example. The target compound X-18 (0.35 g, 83% yield, HPLC analysis purity 96%) is a yellow-orange solid. MALDI-TOF-MS results: molecular ion peak: 616.32 Elemental analysis results: theoretical value: C, 89.58; H, 5.88; N, 4.54 (%); experimental value: C, 89.65; H, 5.86N, 4.49 (%).

[0112] Synthesis Example 6:

[0113]

[0114] (1) Synthesis of Compound X-57-1

[0115]

[0116] This example is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole is replaced with 6-iodo-10-bromo-2,8-adamantane-5,11-dihydroindole[3,2-b]carbazole in this example. The target compound X-57-1 (3.14 g) is obtained as a light yellow powder.

[0117] (2) Synthesis of Compound X-57-2

[0118]

[0119] The synthesis of this example is basically the same as that of compound X-1-2, except that X-1-1 is replaced by X-57-1 in this example to obtain the target compound X-57-2 (1.36 g) as a yellow powder.

[0120] (3) Synthesis of Compound X-57

[0121]

[0122] This example is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced by X-57-2 in this example. The target compound X-57 (0.29 g, 80% yield, HPLC analysis purity 95%) is an orange solid. MALDI-TOF-MS results: molecular ion peak: 772.31 Elemental analysis results: theoretical value: C, 90.12; H, 6.26; N, 3.62 (%); experimental value: C, 90.15; H, 6.27; N, 3.58 (%).

[0123] Synthesis Example 7:

[0124]

[0125] (1) Synthesis of Compound X-81-1

[0126]

[0127] In a 100mL two-necked flask, X-1 (1.02g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.72g, 4.04mmol) was added in batches. The mixture was protected from light for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed using petroleum ether and dichloromethane (v / v=1:2) as eluents to obtain red powder X-81-1 (0.79g).

[0128] (2) Synthesis of Compound X-81

[0129]

[0130] X-81-1 (0.36 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-81 (0.25 g, 80% yield, HPLC analysis purity 99%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 740.33 Elemental analysis results: Theoretical value: C, 90.78; H, 5.44; N, 3.78 (%); Experimental value: C, 90.71; H, 5.48; N, 3.81 (%).

[0131] Synthesis Example 8:

[0132]

[0133] (1) Synthesis of Compound X-83-1

[0134]

[0135] In a 100mL two-necked flask, X-3 (1.02g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.72g, 4.04mmol) was added in batches. The mixture was protected from light for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:2) as eluents to obtain yellow-orange powder X-83-1 (0.84g).

[0136] (2) Synthesis of Compound X-83

[0137]

[0138] X-83-1 (0.36 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-83 (0.28 g, 87% yield, HPLC analysis purity 97%) as a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 740.38 Elemental analysis results: Theoretical value: C, 90.78; H, 5.44; N, 3.78 (%); Experimental value: C, 90.83; H, 5.42; N, 3.75 (%).

[0139] Synthesis Example 9:

[0140]

[0141] (1) Synthesis of Compound X-134-1

[0142]

[0143] In a 100mL two-necked flask, X-57 (1.56g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was protected from light and reacted for 24 hours. 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed using petroleum ether and dichloromethane (v / v=1:2) as eluents to obtain orange powder X-134-1 (1.37g).

[0144] (2) Synthesis of Compound X-134

[0145]

[0146] X-134-1 (0.85 g, 1.00 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. 4 mL of tetrahydrofuran and 1 mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-134 (0.66 g, 87% yield, HPLC analysis purity 97%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 890.48 Elemental analysis results: Theoretical value: C, 90.30; H, 6.56; N, 3.14 (%); Experimental value: C, 90.24; H, 6.60; N, 3.12 (%).

[0147] Synthesis Example 10:

[0148]

[0149] (1) Synthesis of Compound X-141

[0150]

[0151] X-81-1 (0.66 g, 1.00 mmol), carbazole (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol) and sodium tert-butoxide (192 mg, 2 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added and the reaction was stopped at 110 ° C for 24 hours. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:3) as eluents to obtain the target compound X-141 (0.42 g, 50% yield, HPLC analysis purity 93%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 834.32 Elemental analysis results: Theoretical value: C, 89.19; H, 4.10; N, 6.71 (%); Experimental value: C, 89.22; H, 4.05; N, 6.73 (%).

[0152] Synthesis Example 11:

[0153]

[0154] (1) Synthesis of Compound X-148

[0155]

[0156] X-83-1 (0.36 g, 0.50 mmol), triphenylamine boric acid (0.32 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped at 85 ° C for 24 hours. Cool to room temperature, add 200 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:3) as eluents to obtain the target compound X-148 (0.28 g, 80% yield, HPLC analysis purity 95%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 990.38 Elemental analysis results: Theoretical value: C, 89.67; H, 4.68; N, 5.65 (%); Experimental value: C, 89.70; H, 4.66; N, 5.64 (%).

[0157] Synthesis Example 12:

[0158]

[0159] (1) Synthesis of Compound X-156

[0160]

[0161] X-81-1 (0.36 g, 0.50 mmol), 9,9-dimethyl-3-fluoreneboronic acid (0.24 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-156 (0.31 g, 86% yield, HPLC analysis purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 888.33 Elemental analysis results: Theoretical value: C, 91.86; H, 4.99; N, 3.15 (%); Experimental value: C, 91.87; H, 5.00; N, 3.13 (%).

[0162] Synthesis Example 13:

[0163]

[0164] (1) Synthesis of Compound X-156

[0165]

[0166] X-81-1 (0.36 g, 0.50 mmol), 9,9-dimethyl-4-fluoreneboronic acid (0.24 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-171 (0.28 g, 77% yield, HPLC analysis purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 888.31 Elemental analysis results: Theoretical value: C, 91.86; H, 4.99; N, 3.15 (%); Experimental value: C, 91.84; H, 5.00; N, 3.16 (%).

[0167] Synthesis Example 14:

[0168]

[0169] (1) Synthesis of Compound X-195-1

[0170]

[0171] In a 100mL two-necked flask, X-2 (1.01g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was protected from light and reacted for 24 hours. 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed using petroleum ether and dichloromethane (v / v=2:3) as eluents to obtain orange powder X-195-1 (1.37g).

[0172] (2) Synthesis of Compound X-195-2

[0173]

[0174] X-195-1 (0.62 g, 1.00 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. 4 mL of tetrahydrofuran and 1 mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 200 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain an orange solid X-195-2 (0.68 g).

[0175] (3) Synthesis of Compound X-195-3

[0176]

[0177] In a 100mL two-necked bottle, X-195-2 (0.63g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain orange powder X-195-3 (0.70g).

[0178] (4) Synthesis of Compound X-195

[0179]

[0180] X-195-3 (0.39 g, 0.50 mmol), 9-phenyl-9H-carbazole-4-ylboronic acid (0.32 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain the target compound X-195 (0.34 g, 81% yield, HPLC analysis purity 98%) as a dark red solid. MALDI-TOF-MS results: Molecular ion peak: 1104.2 Elemental analysis results: Theoretical value: C, 90.19; H, 4.74; N, 5.07 (%); Experimental value: C, 90.18; H, 4.75; 5.07 (%).

[0181] Synthesis Example 15:

[0182]

[0183] (1) Synthesis of Compound X-204-1

[0184]

[0185] In a 100mL two-necked flask, X-3 (1.02g, 2.02mmol) was dissolved in 25mL N,N-dimethylformamide. Cooled to 0°C, N-bromosuccinimide (0.72g, 4.04mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed using petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain yellow-orange powder X-204-1 (0.92g).

[0186] (2) Synthesis of Compound X-204

[0187]

[0188] X-204-1 (1.65 g, 2.50 mmol), 2,4,6-trimethylphenylboronic acid (0.90 g, 5.50 mmol), tetrakistriphenylphosphine palladium (85 mg, 0.075 mmol) and potassium carbonate (0.85 g, 6.25 mmol) were added to a 100 mL double-necked flask in sequence. Under a nitrogen atmosphere, 20 mL of tetrahydrofuran and 5 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 200 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain yellow-orange solid X-204-2 (1.28 g).

[0189] (3) Synthesis of Compound X-204-3

[0190]

[0191] In a 100mL two-necked bottle, X-204-2 (1.48g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.72g, 4.04mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain yellow-orange powder X-204-3 (1.22g).

[0192] (4) Synthesis of Compound X-204

[0193]

[0194] X-204-3 (0.36 g, 0.50 mmol), 9,9-dimethyl-4-fluoreneboronic acid (0.24 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-204 (0.23 g, 87% yield, HPLC analysis purity 97%) as a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 1125.42 Elemental analysis results: Theoretical value: C, 91.78; H, 5.73N, 2.49 (%); Experimental value: C, 91.79; H, 5.71N, 2.50 (%).

[0195] Synthesis Example 16:

[0196]

[0197] (1) Synthesis of Compound X-206-1

[0198]

[0199] This example is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole is replaced with 6,12-dibromo-2,8-dicyano-5,11-dihydroindole[3,2-b]carbazole in this example. The target compound X-206-1 (2.25 g) is obtained as a light yellow powder.

[0200] (2) Synthesis of Compound X-206-2

[0201]

[0202] The synthesis of this example is basically the same as that of compound X-1-2, except that X-1-1 is replaced by X-206-1 in this example to obtain the target compound X-206-2 (0.87 g) as a yellow powder.

[0203] (3) Synthesis of Compound X-206

[0204]

[0205] The synthesis of this example is basically the same as that of compound X-1, except that X-1-2 needs to be replaced by X-206-2 in this example. The target compound X-206 (0.20 g, 75% yield, HPLC analysis purity 98%) is a dark red solid. MALDI-TOF-MS results: molecular ion peak: 554.13 Elemental analysis results: theoretical value: C, 86.63; H, 3.27; N, 10.10 (%); experimental value: C, 86.60; H, 3.29; N, 10.11 (%).

[0206] Synthesis Example 17:

[0207]

[0208] (1) Synthesis of Compound X-211-1

[0209]

[0210] This example is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole is replaced with 6,12-dibromo-3,7-dicyano-5,11-dihydroindole[3,2-b]carbazole in this example. The target compound X-211-1 (1.52 g) is obtained as a light yellow powder.

[0211] (2) Synthesis of Compound X-211-2

[0212]

[0213] The synthesis of this example is basically the same as that of compound X-1-2, except that X-1-1 is replaced by X-211-1 in this example to obtain the target compound X-211-2 (0.92 g) as a yellow powder.

[0214] (3) Synthesis of Compound X-211

[0215]

[0216] The synthesis of this example is basically the same as that of compound X-1, except that X-1-2 needs to be replaced with X-211-2 in this example. The target compound X-211 (0.32 g, 82% yield, HPLC analysis purity 97%) is a dark red solid. MALDI-TOF-MS results: Molecular ion peak: 554.15 Elemental analysis results: Theoretical value: C, 86.63; H, 3.27; N, 10.10 (%); Expected value: C, 86.61; H, 3.28; N, 10.11 (%).

[0217] Synthesis Example 18:

[0218]

[0219] (1) Synthesis of Compound X-228-1

[0220]

[0221] This example is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole is replaced with 4,10-dibromo-2,8-dicyano-5,11-dihydroindole[3,2-b]carbazole in this example. The target compound X-228-1 (1.97 g) is obtained as a light yellow powder.

[0222] (2) Synthesis of Compound X-228-2

[0223]

[0224] The synthesis of this example is basically the same as that of compound X-1-2, except that X-1-1 is replaced by X-228-1 in this example to obtain the target compound X-228-2 (1.03 g) as a yellow powder.

[0225] (3) Synthesis of Compound X-228-3

[0226]

[0227] The synthesis of this example is basically the same as that of compound X-1, except that X-1-2 is replaced by X-228-2 in this example. The target compound X-228-3 (0.35 g) is a yellow-orange solid.

[0228] (4) Synthesis of Compound X-228-4

[0229]

[0230] In a 100mL two-necked bottle, X-228-3 (1.11g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain yellow-orange powder X-228-4 (0.74g).

[0231] (5) Synthesis of Compound X-228

[0232]

[0233] X-228-1 (0.37 g, 1.00 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL two-necked bottle in sequence. 4 mL of tetrahydrofuran and 1 mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 200 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain yellow-orange solid X-228-2 ((0.47 g, 79% yield, HPLC analysis purity 96%), which is an orange solid. MALDI-TOF-MS results: molecular ion peak: 672.23 elemental analysis results: theoretical value: C, 87.48; H, 4.20; N, 8.33 (%); experimental value: C, 87.50; H, 4.21; N, 8.30 (%).

[0234] Synthesis Example 19:

[0235]

[0236] (1) Synthesis of Compound X-230

[0237]

[0238] X-228-4 (0.63 g, 1.00 mmol), diphenylamine (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol) and sodium tert-butoxide (192 mg, 2 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added and the reaction was stopped at 110 ° C for 24 hours. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain the target compound X-230 (0.44 g, 77% yield, HPLC analysis purity 95%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 721.24 Elemental analysis results: Theoretical value: C, 86.53; H, 3.77; N, 9.70 (%); Experimental value: C, 86.56; H, 3.78; N, 9.66 (%).

[0239] Synthesis Example 20:

[0240]

[0241] (1) Synthesis of Compound X-246-1

[0242]

[0243] In a 100mL two-necked bottle, X-195 (0.87g, 1.50mmol) and cuprous cyanide (0.40g, 4.4mmol) were dissolved in 25mL 1-methylpyrrolidone. Under nitrogen protection, the temperature was raised to 150℃ for 24h. After the reaction was completed, it was cooled to room temperature, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:2) as eluents to obtain orange-red powder X-246-1 (0.69g).

[0244] (2) Synthesis of Compound X-246-2

[0245]

[0246] In a 100mL two-necked bottle, X-246-1 (1.07g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.72g, 4.04mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain red powder X-246-1 (0.85g).

[0247] (3) Synthesis of Compound X-246

[0248]

[0249] X-246-2 (0.34 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:3) as eluents to obtain the target compound X-246 (0.30 g, 86% yield, HPLC analysis purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 765.33 Elemental analysis results: Theoretical value: C, 89.38; H, 5.13; N, 5.49 (%); Experimental value: C, 89.40; H, 5.14; N, 5.46 (%).

[0250] Synthesis Example 21:

[0251]

[0252] (1) Synthesis of Compound X-251-1

[0253]

[0254] X-228-4 (0.66 g, 1.00 mmol), diphenylamine (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol) and sodium tert-butoxide (192 mg, 2 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added and the reaction was stopped after 24 hours at 110 ° C. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain an orange solid X-251 (0.54 g).

[0255] (2) Synthesis of Compound X-251-2

[0256]

[0257] In a 100mL two-necked bottle, X-251-1 (0.84g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:2) as eluents to obtain orange powder X-251-2 (0.61g).

[0258] (3) Synthesis of Compound X-251

[0259]

[0260] X-251-2 (0.50 g, 0.50 mmol) and cuprous cyanide (0.40 g, 4.4 mmol) were added to a 25 mL double-necked flask and dissolved in 25 mL 1-methylpyrrolidone. Under nitrogen protection, the temperature was raised to 150 ° C and reacted for 24 h. After the reaction was completed, it was cooled to room temperature, 200 mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:3) as eluents to obtain the target compound X-251 (0.19 g, 77% yield, HPLC analysis purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 888.31 Elemental analysis results: Theoretical value: C, 86.47; H, 4.08; N, 9.45 (%); Experimental value: C, 86.49; H, 4.07; N, 9.44 (%).

[0261] Synthesis Example 22:

[0262]

[0263] (1) Synthesis of Compound X-255

[0264]

[0265] X-246-2 (0.34 g, 0.50 mmol), 9,9-dimethyl-4-fluoreneboronic acid (0.24 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. 4 mL of tetrahydrofuran and 1 mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-255 (0.35 g, 87% yield, HPLC analysis purity 96%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 913.33 Elemental analysis results: Theoretical value: C, 90.66; H, 4.74; N, 4.60 (%); Experimental value: C, 90.67; H, 4.73; N, 4.60 (%).

[0266] Synthesis Example 23:

[0267]

[0268] (1) Synthesis of Compound X-260-1

[0269]

[0270] X-83-1 (0.33 g, 0.50 mmol), (2-(9H-carbazole-9-yl)phenyl)boric acid (0.33 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 200 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain yellow solid X-260-1 (0.40 g).

[0271] (2) Synthesis of Compound X-260-2

[0272]

[0273] In a 100mL two-necked bottle, X-260-1 (0.99g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:2) as eluents to obtain orange powder X-260-2 (0.76g).

[0274] (3) Synthesis of Compound X-260

[0275]

[0276] X-260-2 (0.57 g, 0.50 mmol) and cuprous cyanide (0.40 g, 4.4 mmol) were added to a 25 mL double-necked flask and dissolved in 25 mL 1-methylpyrrolidone. Under nitrogen protection, the temperature was raised to 150 ° C and reacted for 24 h. After the reaction was completed, it was cooled to room temperature, 200 mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:3) as eluents to obtain the target compound X-260 (0.39 g, 62% yield, HPLC analysis purity 97%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 1036.35 Elemental analysis results: Theoretical value: C, 88.01; H, 3.89; N, 8.10 (%); Experimental value: C, 88.00; H, 3.90; N, 8.10 (%).

[0277] Synthesis Example 24:

[0278]

[0279] (1) Synthesis of Compound X-261-1

[0280]

[0281] X-195-1 (0.58 g, 1.00 mmol), diphenylamine (167 mg, 1.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol) and sodium tert-butoxide (192 mg, 2 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added and the reaction was stopped after 24 hours at 110 ° C. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain red solid X-261-1 (0.47 g).

[0282] (2) Synthesis of Compound X-261-2

[0283]

[0284] In a 100mL two-necked bottle, X-261-1 (0.67g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was protected from light and reacted for 24 hours. 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain red powder X-261-2 (0.60g).

[0285] (3) Synthesis of Compound X-261

[0286]

[0287] X-261-2 (0.34 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-261 (0.39 g, 90% yield, HPLC analysis purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 907.36 Elemental analysis results: Theoretical value: C, 89.93; H, 5.44; N, 4.63 (%); Experimental value: C, 89.95; H, 5.45; N, 4.60 (%).

[0288] Synthesis Example 25:

[0289]

[0290] (1) Synthesis of Compound X-265-1

[0291]

[0292] In a 100mL two-necked bottle, X-83 (1.48g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.72g, 4.04mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain yellow-orange powder X-265-1 (0.73g).

[0293] (2) Synthesis of Compound X-265

[0294]

[0295] X-265-1 (0.90 g, 1.00 mmol), carbazole (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol) and sodium tert-butoxide (192 mg, 2 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added and the reaction was stopped at 110 ° C for 24 hours. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain the target compound X-265 (0.62 g, 79% yield, HPLC analysis purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 1071.44 Elemental analysis results: Theoretical value: C, 89.69; H, 5.08; N, 5.23 (%); Experimental value: C, 89.70; H, 5.09; N, 5.21.

[0296] Synthesis Example 26:

[0297]

[0298] (1) Synthesis of Compound X-271-1

[0299]

[0300] X-195-1 (0.58 g, 1.00 mmol), (4-(9H-carbazole-9-yl)phenyl)boric acid (0.33 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 200 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain an orange solid X-271-1 (0.37 g).

[0301] (2) Synthesis of Compound X-271-2

[0302]

[0303] In a 100mL two-necked bottle, X-271-1 (0.75g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was reacted for 24 hours in the dark, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain orange powder X-271-2 (0.58g).

[0304] (3) Synthesis of Compound X-271

[0305]

[0306] X-271-2 (0.45 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:3) as eluents to obtain the target compound X-271 (0.32 g, 75% yield, HPLC analysis purity 98%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 903.06 Elemental analysis results: Theoretical value: C, 74.43; H, 3.23; N, 4.65 (%); Experimental value: C, 74.45; H, 3.24; N, 4.62 (%).

[0307] Synthesis Example 27:

[0308]

[0309] (1) Synthesis of Compound X-276

[0310]

[0311] X-81-1 (0.36 g, 0.50 mmol), 1-naphthaleneboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-276 (0.22 g, 78% yield, HPLC analysis purity 99%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 756.24 Elemental analysis results: Theoretical value: C, 92.04; H, 4.26; N, 3.70 (%); Experimental value: C, 92.07; H, 4.27; N, 3.66 (%).

[0312] Synthesis Example 28:

[0313]

[0314] (1) Synthesis of Compound X-283

[0315]

[0316] X-83-1 (0.36 g, 0.50 mmol), anthracene-9-yl-boric acid (0.24 g, 1.10 mmol), tetratriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-283 (0.21 g, 83% yield, HPLC analysis purity 98%) as a yellow-orange solid. MALDI-TOF-MS results: Molecular ion peak: 856.26 Elemental analysis results: Theoretical value: C, 92.50; H, 4.23; N, 3.27 (%); Experimental value: C, 92.49; H, 4.24; N, 3.27 (%).

[0317] Synthesis Example 29:

[0318]

[0319] (1) Synthesis of Compound X-293-1

[0320]

[0321] X-195-1 (0.58 g, 1.00 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked bottle in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 200 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain orange solid X-293-1 (0.51 g).

[0322] (2) Synthesis of Compound X-293-2

[0323]

[0324] In a 100mL two-necked bottle, X-293-1 (0.75g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.36g, 2.02mmol) was added in batches. The mixture was reacted in the dark for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain orange powder X-293-2 (0.55g).

[0325] (3) Synthesis of Compound X-293

[0326]

[0327] X-293-2 (0.39 g, 0.50 mmol), anthracene-9-yl-boric acid (0.24 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:3) as eluents to obtain the target compound X-293 (0.23 g, 45% yield, HPLC analysis purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 1097.38 Elemental analysis results: Theoretical value: C, 91.86; H, 4.31; N, 3.83 (%); Experimental value: C, 91.88; H, 4.33; N, 3.79 (%).

[0328] Synthesis Example 30:

[0329]

[0330] (1) Synthesis of Compound X-316-1

[0331]

[0332] 2-naphthoboryl ester (2.54 g, 10.00 mmol), 2',3',5',6'-tetrabromo-1,1',4,1"-terphenyl (5.42 g, 10.00 mmol), tetrakistriphenylphosphine palladium (0.35 g, 0.30 mmol) and potassium carbonate (3.45 g, 25.00 mmol) were added to a 100 mL two-necked flask in sequence. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 100 mL of ethyl acetate and extract with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=5:1) as eluents to obtain white powder X-316-1 (3.6 g).

[0333] (2) Synthesis of Compound X-316-2

[0334]

[0335] 1-Naphthoboryl ester (1.27 g, 5.00 mmol), X-316-1 (2.70 g, 5.00 mmol), tetrakistriphenylphosphine palladium (0.35 g, 0.30 mmol) and potassium carbonate (3.45 g, 25.00 mmol) were added to a 100 mL double-necked flask in sequence. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 100 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:1) as eluents to obtain light yellow powder X-316-2 (3.6 g).

[0336] (2) Synthesis of Compound X-316

[0337]

[0338] Slowly add n-butyl lithium solution (10mL, 2.50M, 25.00mmol) to a tert-butylbenzene (80mL) solution of X-316-2 (3.19g, 5.00mmol) at 0°C, and then heat to 60°C and react for 3 hours each. After the reaction is completed, cool to -30°C, slowly add boron tribromide (6.26g, 25.00mmol), and continue stirring at room temperature for 0.5 hours. Add N, N-diisopropylethylamine (4.83g, 37.5mmol) at room temperature, and continue to react at 145°C for 5 hours before stopping. The reaction is cooled to room temperature, extracted with dichloromethane and water, and the organic phase is collected and dried with anhydrous sodium sulfate. After the organic phase was concentrated under reduced pressure, column chromatography was performed using petroleum ether and dichloromethane (petroleum ether: dichloromethane = 1:1) as eluents to obtain the target compound X-316 (0.38 g, 25% yield, HPLC analysis purity 97%) as a red solid. MALDI-TOF-MS results: molecular ion peak: 498.18 Elemental analysis results: theoretical value: C, 91.61; H, 4.05 (%); experimental value: C, 91.55; H, 4.07 (%).

[0339] Synthesis Example 30:

[0340]

[0341] (1) Synthesis of Compound X-316-1

[0342]

[0343] 2-naphthoboryl ester (2.54 g, 10.00 mmol), 2',3',5',6'-tetrabromo-1,1',4,1"-terphenyl (5.42 g, 10.00 mmol), tetrakistriphenylphosphine palladium (0.35 g, 0.30 mmol) and potassium carbonate (3.45 g, 25.00 mmol) were added to a 100 mL two-necked flask in sequence. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 100 mL of ethyl acetate and extract with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=5:1) as eluents to obtain white powder X-316-1 (3.6 g).

[0344] (2) Synthesis of Compound X-316-2

[0345]

[0346] 1-Naphthoboryl ester (1.27 g, 5.00 mmol), X-316-1 (2.70 g, 5.00 mmol), tetrakistriphenylphosphine palladium (0.35 g, 0.30 mmol) and potassium carbonate (3.45 g, 25.00 mmol) were added to a 100 mL double-necked flask in sequence. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 100 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:1) as eluents to obtain light yellow powder X-316-2 (3.6 g).

[0347] (2) Synthesis of Compound X-316

[0348]

[0349] Slowly add n-butyl lithium solution (10mL, 2.50M, 25.00mmol) to a tert-butylbenzene (80mL) solution of X-316-2 (3.19g, 5.00mmol) at 0°C, and then heat to 60°C and react for 3 hours each. After the reaction is completed, cool to -30°C, slowly add boron tribromide (6.26g, 25.00mmol), and continue stirring at room temperature for 0.5 hours. Add N, N-diisopropylethylamine (4.83g, 37.5mmol) at room temperature, and continue to react at 145°C for 5 hours before stopping. The reaction is cooled to room temperature, extracted with dichloromethane and water, and the organic phase is collected and dried with anhydrous sodium sulfate. After the organic phase was concentrated under reduced pressure, column chromatography was performed using petroleum ether and dichloromethane (petroleum ether: dichloromethane = 1:1) as eluents to obtain the target compound X-316 (0.38 g, 25% yield, HPLC analysis purity 97%) as a red solid. MALDI-TOF-MS results: molecular ion peak: 498.18 Elemental analysis results: theoretical value: C, 91.61; H, 4.05 (%); experimental value: C, 91.55; H, 4.07 (%).

[0350] Synthesis Example 31:

[0351]

[0352] (1) Synthesis of Compound X-323-1

[0353]

[0354] The synthesis of this example is basically the same as that of compound X-316-1, except that an equal amount of halogenated compound needs to be replaced in this example. The target compound X-323-1 (4.5 g) is a light yellow solid.

[0355] (2) Synthesis of Compound X-323-2

[0356]

[0357] The synthesis of this example is basically the same as that of compound X-316-2, except that X-316-1 is replaced by X-323-1 in this example. The target compound X-323-2 (4.5 g) is a light yellow solid.

[0358] (3) Synthesis of Compound X-323

[0359]

[0360] This example is basically the same as the synthesis of compound X-316, except that X-316-2 needs to be replaced by X-323-2 in this example. The target compound X-323 (0.37 g, 25% yield, HPLC analysis purity 97%) is an orange solid. MALDI-TOF-MS results: Molecular ion peak: 610.23 Elemental analysis results: Theoretical value: C, 90.51; H, 5.94 (%); Expected value: C, 90.56; H, 5.96 (%).

[0361] Synthesis Example 32:

[0362]

[0363] (1) Synthesis of Compound X-331-1

[0364]

[0365] In a 100mL two-necked bottle, X-316 (1.02g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.72g, 4.04mmol) was added in batches. The mixture was protected from light for 24 hours, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:2) as eluents to obtain red powder X-331-1 (0.80g).

[0366] (2) Synthesis of Compound X-331

[0367]

[0368] X-331-1 (0.36 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-331 (0.23 g, 49% yield, HPLC analysis purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 734.31 Elemental analysis results: Theoretical value: C, 91.57; H, 5.49 (%); Experimental value: C, 91.62; H, 5.46 (%).

[0369] Synthesis Example 33:

[0370]

[0371] (1) Synthesis of Compound X-251-1

[0372]

[0373] X-331-1 (0.66 g, 1.00 mmol), carbazole (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol) and sodium tert-butoxide (192 mg, 2 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added and the reaction was stopped at 110 ° C for 24 hours. Cool to room temperature, add 200 mL of dichloromethane and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=3:2) as eluents to obtain the target compound X-335 (0.58 g, 68% yield, HPLC analysis purity 96%) as a dark red solid. MALDI-TOF-MS results: Molecular ion peak: 828.28 Elemental analysis results: Theoretical value: C, 89.87; H, 4.14; N, 3.38 (%); Experimental value: C, 89.94; H, 4.13; N, 3.34 (%).

[0374] Synthesis Example 34:

[0375]

[0376] (1) Synthesis of Compound X-336

[0377]

[0378] X-331-1 (0.36 g, 0.50 mmol), 9,9-dimethyl-4-fluoreneboronic acid (0.26 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. 4 mL of tetrahydrofuran and 1 mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-336 (0.25 g, 46% yield, HPLC analysis purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 882.33 Elemental analysis results: Theoretical value: C, 92.53; H, 5.02 (%); Experimental value: C, 92.52; H, 5.01 (%).

[0379] Synthesis Example 35:

[0380]

[0381] (1) Synthesis of Compound X-341

[0382]

[0383] X-331-1 (0.36 g, 0.50 mmol), anthracene-9-yl-boric acid (0.24 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-341 (0.27 g, 43% yield, HPLC analysis purity 98%) as a dark red solid. MALDI-TOF-MS results: Molecular ion peak: 850.33 Elemental analysis results: Theoretical value: C, 93.19; H, 4.27 (%); Experimental value: C, 93.22; H, 4.25 (%).

[0384] Synthesis Example 36:

[0385]

[0386] (1) Synthesis of Compound X-346-1

[0387]

[0388] 2,3-Dibromonaphthalene (2.84 g, 10.00 mmol), 2-benzene-1,4-diboron ester-9-hydrogen-carbazole (4.95 g, 10.00 mmol), tetrakistriphenylphosphine palladium (0.35 g, 0.30 mmol) and potassium carbonate (3.45 g, 25.00 mmol) were added to a 250 mL double-necked flask in sequence. Under a nitrogen atmosphere, 100 mL of tetrahydrofuran and 25 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 200 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=2:1) ​​as eluents to obtain a light yellow solid X-346-1 (3.6 g).

[0389] (2) Synthesis of Compound X-346-2

[0390]

[0391] 1,8-Dibromonaphthalene (1.42 g, 5.00 mmol), 2-benzene-1,4-diboron ester-9-hydrogen-carbazole (2.87 g, 5.00 mmol), tetrakistriphenylphosphine palladium (0.18 g, 0.15 mmol) and potassium carbonate (1.73 g, 12.50 mmol) were added to a 100 mL double-necked flask in sequence. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cool to room temperature, add 100 mL of ethyl acetate and extract with water. Collect the organic phase, dry it over anhydrous sodium sulfate, and remove the organic solvent under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain yellow solid X-346-2 (1.9 g).

[0392] (3) Synthesis of Compound X-346-3

[0393]

[0394] Add intermediate X-346-2 (3.25 g, 5.00 mmol) and cuprous iodide (1.00 g, 5.00 mmol) to a 250 mL two-necked round-bottom flask, and add 60 mL N, N-dimethylformamide and 6 mL tetra-n-butylammonium chloride in sequence under a nitrogen atmosphere. Then heat to 120 ° C and react for 12 hours. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, collect the organic phase and dry it with anhydrous sodium sulfate. After the organic phase is concentrated under reduced pressure, column chromatography is performed to obtain an orange solid X-346-3 (1.3 g).

[0395] (4) Synthesis of Compound X-346

[0396]

[0397] Slowly add n-butyl lithium solution (0.8 mL, 2.50 M, 2.00 mmol) to a tert-butylbenzene (20 mL) solution of X-346-3 (1.14 g, 2.00 mmol) at 0°C, and then heat to 60°C and react for 3 hours each. After the reaction is completed, cool to -30°C, slowly add boron tribromide (0.52 g, 2.00 mmol), and continue stirring at room temperature for 0.5 hours. Add N, N-diisopropylethylamine (0.50 g, 4.00 mmol) at room temperature, and continue to react at 145°C for 5 hours before stopping. The reaction is cooled to room temperature, extracted with dichloromethane and water, and the organic phase is collected and dried with anhydrous sodium sulfate. After the organic phase was concentrated under reduced pressure, column chromatography was performed using petroleum ether and dichloromethane (petroleum ether: dichloromethane = 1:1) as eluents to obtain the target compound X-346 (0.21 g, 19% yield, HPLC analysis purity 97%) as a red solid. MALDI-TOF-MS results: molecular ion peak: 501.18 Elemental analysis results: theoretical value: C, 91.03; H, 4.02; N, 2.79 (%); experimental value: C, 90.97; H, 4.06; N, 2.80 (%).

[0398] Synthesis Example 37:

[0399]

[0400] (1) Synthesis of Compound X-356-1

[0401]

[0402] The synthesis of this example is basically the same as that of compound X-346-1, except that in this example, equal amounts of boron ester and bromide need to be replaced. The target compound X-356-1 (2.8 g) is a white solid.

[0403] (2) Synthesis of Compound X-356-2

[0404]

[0405] The synthesis of this example is basically the same as that of compound X-346-2, except that in this example, 2-benzene-1,4-diboron-9H-carbazole is replaced with an equal amount of X-356-1. The target compound X-356-2 (1.7 g) is a light yellow solid.

[0406] (3) Synthesis of Compound X-356-3

[0407]

[0408] The synthesis of this example is basically the same as that of compound X-346-3, except that in this example, X-346-2 needs to be replaced with an equal amount of X-356-2. The target compound X-356-3 (1.2 g) is a yellow solid.

[0409] (4) Synthesis of Compound X-356

[0410]

[0411] This example is basically the same as the synthesis of compound X-346, except that X-346-3 needs to be replaced by X-356-3 in this example. The target compound X-356 (0.29 g, 25% yield, HPLC analysis purity 97%) is a red solid. MALDI-TOF-MS results: Molecular ion peak: 769.75 Elemental analysis results: Theoretical value: C, 90.49; H, 6.28; N, 1.82 (%); Expected value: C, 90.52; H, 6.26; N, 1.83 (%).

[0412] Synthesis Example 38:

[0413]

[0414] (1) Synthesis of Compound X-361-1

[0415]

[0416] In a 100mL two-necked bottle, X-346 (1.02g, 2.02mmol) was dissolved in 25mL of dichloromethane. Cooled to 0°C, N-bromosuccinimide (0.72g, 4.04mmol) was added in batches. The mixture was protected from light and reacted for 24 hours. 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed using petroleum ether and dichloromethane (v / v=1:2) as eluents to obtain red powder X-361-1 (0.63g).

[0417] (2) Synthesis of Compound X-361

[0418]

[0419] X-361-1 (0.36 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. 4 mL of tetrahydrofuran and 1 mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-361 (0.22 g, 53% yield, HPLC analysis purity 98%), as a red solid. MALDI-TOF-MS results: Molecular ion peak: 737.35 Elemental analysis results: Theoretical value: C, 91.17; H, 5.47; N, 1.90 (%); Experimental value: C, 91.18; H, 5.48; N, 1.89 (%).

[0420] Synthesis Example 39:

[0421]

[0422] (1) Synthesis of Compound X-366

[0423]

[0424] X-361-1 (0.36 g, 0.50 mmol), 9,9-dimethyl-4-fluoreneboronic acid (0.26 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-366 (0.29 g, 42% yield, HPLC analysis purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 885.37 Elemental analysis results: Theoretical value: C, 92.19; H, 5.01; N, 1.58 (%); Experimental value: C, 92.17; H, 5.02; N, 1.59 (%).

[0425] Synthesis Example 40:

[0426]

[0427] (1) Synthesis of Compound X-371

[0428]

[0429] X-361-1 (0.36 g, 0.50 mmol), anthracene-9-yl-boric acid (0.24 g, 1.10 mmol), tetrakistriphenylphosphine palladium (17 mg, 0.015 mmol) and potassium carbonate (0.17 g, 1.25 mmol) were added to a 25 mL double-necked flask in sequence. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 ° C. Cooled to room temperature, 200 mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. Column chromatography was performed with petroleum ether and dichloromethane (v / v=1:1) as eluents to obtain the target compound X-371 (0.15 g, 39% yield, HPLC analysis purity 96%) as a dark red solid. MALDI-TOF-MS results: Molecular ion peak: 853.33 Elemental analysis results: Theoretical value: C, 92.84; H, 4.27; N, 1.64 (%); Experimental value: C, 92.85; H, 4.26; N, 1.64 (%).

[0430] The technical effects and advantages of the present invention are demonstrated and verified by applying the compounds of the present invention to organic electroluminescent devices to test actual performance.

[0431] Specifically, the method for preparing the organic electroluminescent device in the embodiment of the present invention comprises the following steps:

[0432] 1. The glass plate coated with the anode material was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0433] 2. Place the glass plate with the anode in a vacuum chamber and evacuate to 1×10 -5 ~9×10 -3 Pa, vacuum evaporating a hole injection material on the anode layer to form a hole injection layer at a rate of 0.1-0.5 nm / s;

[0434] 3. Vacuum evaporation of hole transport material on the hole injection layer to form a hole transport layer at a rate of 0.1-0.5nm / s.

[0435] 4. Vacuum evaporate the electron blocking layer on the hole transport layer at a rate of 0.1-0.5nm / s;

[0436] 5. The organic light-emitting layer of the device is vacuum-evaporated on the electron blocking layer. The organic light-emitting layer material can be a single component or a multi-component. The multi-component material can include a main material, a sensitizer or a dye, etc., or any combination thereof. The multi-source co-evaporation method is used to adjust the evaporation rate of the main material, the evaporation rate of the sensitizer material, and the evaporation rate of the dye so that the dye reaches a preset doping ratio;

[0437] 6. Vacuum-deposit a hole blocking layer on the organic light-emitting layer at a rate of 0.1-0.5 nm / s;

[0438] 7. Vacuum evaporating the electron transport material of the device on the hole blocking layer to form an electron transport layer, with the evaporation rate being 0.1-0.5 nm / s;

[0439] 8. LiF was vacuum evaporated at 0.1-0.5nm / s on the electron transport layer as the electron injection layer, and Al was vacuum evaporated at 0.5-1nm / s as the cathode of the device.

[0440] The organic electroluminescent device of the present invention is further described below through specific embodiments.

[0441] Device Example 1

[0442] The structure of the organic electroluminescent device prepared in this embodiment is as follows:

[0443] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-1(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0444] Among them, the anode material is ITO; the hole injection layer material is HI, the total thickness is generally 5-30nm, and the present embodiment is 10nm; the hole transport layer material is HT, the total thickness is generally 5-500nm, and the present embodiment is 30nm; Host is the main material of the wide band gap of the organic light-emitting layer, the compound X-1 of the present invention is a dye and the doping concentration is 2wt%, the thickness of the organic light-emitting layer is generally 1-200nm, and the present embodiment is 30nm; the electron transport layer material is ET, the thickness is generally 5-300nm, and the present embodiment is 30nm; LiF (0.5nm) and metal aluminum (150nm) are selected as the electron injection layer and cathode materials.

[0445] A DC voltage was applied to the organic electroluminescent device D1 prepared in this example to measure the 10 cd / m2 The characteristics of light emission are orange light emission with a wavelength of 561 nm, a half-peak width of 22 nm, CIE color coordinates (x, y) = (0.42, 0.54), and an external quantum efficiency EQE of 4.2% (driving voltage is 2.7 V).

[0446] Device Example 2

[0447] The preparation method is the same as that of device embodiment 1, except that the wide bandgap host material Host used in the light-emitting layer is replaced by a TADF host TD1. The specific device structure is as follows:

[0448] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD1:2wt%X-1(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0449] The device performance of the organic electroluminescent device D2 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 564nm, a half-peak width of 22nm, CIE color coordinates (x, y) = (0.44, 0.52), and an external quantum efficiency EQE of 18.1% (driving voltage is 2.7V).

[0450] Device Example 3

[0451] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by X-2 from X-1.

[0452] The device structure is as follows:

[0453] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-2(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0454] The device performance of the organic electroluminescent device D3 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 535nm, a half-peak width of 20nm, CIE color coordinates (x, y) = (0.25, 0.62), and an external quantum efficiency EQE of 4.4% (driving voltage is 2.8V).

[0455] Device Example 4

[0456] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-1 by X-2. The device structure is as follows:

[0457] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-2(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0458] The device performance of the organic electroluminescent device D4 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 536nm, a half-peak width of 22nm, CIE color coordinates (x, y) = (0.25, 0.60), and an external quantum efficiency EQE of 19.3% (driving voltage is 2.8V).

[0459] Device Example 5

[0460] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-3 instead of X-1. The device structure is as follows:

[0461] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-3(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0462] The device performance of the organic electroluminescent device D5 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 505nm, a half-peak width of 18nm, CIE color coordinates (x, y) = (0.15, 0.60), and an external quantum efficiency EQE of 4.6% (driving voltage is 3.0V).

[0463] Device Example 6

[0464] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-1 by X-3. The device structure is as follows:

[0465] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-3(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0466] The device performance of the organic electroluminescent device D6 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 505nm, a half-peak width of 18nm, CIE color coordinates (x, y) = (0.15, 0.60), and an external quantum efficiency EQE of 24.1% (driving voltage is 3.0V).

[0467] Device Example 7

[0468] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-16 instead of X-1. The device structure is as follows:

[0469] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-16(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0470] The device performance of the organic electroluminescent device D7 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 575nm, a half-peak width of 25nm, CIE color coordinates (x, y) = (0.50, 0.42), and an external quantum efficiency EQE of 3.9% (driving voltage is 2.7V).

[0471] Device Example 8

[0472] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-16. The device structure is as follows:

[0473] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-16(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0474] The device performance of the organic electroluminescent device D8 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 576nm, a half-peak width of 26nm, CIE color coordinates (x, y) = (0.50, 0.42), and an external quantum efficiency EQE of 21.7% (driving voltage is 2.7V).

[0475] Device Example 9

[0476] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-18 instead of X-1. The device structure is as follows:

[0477] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-18(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0478] The device performance of the organic electroluminescent device D9 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 516nm, a half-peak width of 22nm, CIE color coordinates (x, y) = (0.19, 0.70), and an external quantum efficiency EQE of 4.6% (driving voltage is 3.0V).

[0479] Device Example 10

[0480] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-18. The device structure is as follows:

[0481] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-18(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0482] The device performance of the organic electroluminescent device D10 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 516nm, a half-peak width of 22nm, CIE color coordinates (x, y) = (0.20, 0.69), and an external quantum efficiency EQE of 18.4% (driving voltage is 3.0V).

[0483] Device Example 11

[0484] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-57 instead of X-1. The device structure is as follows:

[0485] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-57(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0486] The device performance of the organic electroluminescent device D11 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are yellow light emission with a wavelength of 541 nm, a half-peak width of 25 nm, CIE color coordinates (x, y) = (0.33, 0.56), and an external quantum efficiency EQE of 3.8% (driving voltage is 2.8 V).

[0487] Device Example 12

[0488] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-1 by X-57. The device structure is as follows:

[0489] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-57(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0490] The device performance of the organic electroluminescent device D12 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are yellow light emission with a wavelength of 541 nm, a half-peak width of 27 nm, CIE color coordinates (x, y) = (0.33, 0.56), and an external quantum efficiency EQE of 20.4% (driving voltage is 2.8 V).

[0491] Device Example 13

[0492] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-81 instead of X-1. The device structure is as follows:

[0493] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-81(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0494] The device performance of the organic electroluminescent device D13 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 578nm, a half-peak width of 22nm, CIE color coordinates (x, y) = (0.51, 0.39), and an external quantum efficiency EQE of 3.6% (driving voltage is 2.6V).

[0495] Device Example 14

[0496] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-81 from X-1. The device structure is as follows:

[0497] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-81(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0498] The device performance of the organic electroluminescent device D14 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 578nm, a half-peak width of 23nm, CIE color coordinates (x, y) = (0.50, 0.40), and an external quantum efficiency EQE of 18.4% (driving voltage is 2.6V).

[0499] Device Example 15

[0500] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-83 instead of X-1. The device structure is as follows:

[0501] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-83(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0502] The device performance of the organic electroluminescent device D15 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are yellow light emission with a wavelength of 552nm, a half-peak width of 20nm, CIE color coordinates (x, y) = (0.35, 0.58), and an external quantum efficiency EQE of 3.6% (driving voltage is 2.7V).

[0503] Device Example 16

[0504] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-83 from X-1. The device structure is as follows:

[0505] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-83(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0506] The device performance of the organic electroluminescent device D16 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are yellow light emission with a wavelength of 553nm, a half-peak width of 22nm, CIE color coordinates (x, y) = (0.35, 0.59), and an external quantum efficiency EQE of 23.1% (driving voltage is 2.7V).

[0507] Device Example 17

[0508] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-171 instead of X-1. The device structure is as follows:

[0509] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-171(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0510] The device performance of the organic electroluminescent device D17 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 576nm, a half-peak width of 22nm, CIE color coordinates (x, y) = (0.45, 0.50), and an external quantum efficiency EQE of 4.5% (driving voltage is 2.7V).

[0511] Device Example 18

[0512] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-171 from X-1. The device structure is as follows:

[0513] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-171(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0514] The device performance of the organic electroluminescent device D18 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2The characteristics of light emission are orange light emission with a wavelength of 576nm, a half-peak width of 24nm, CIE color coordinates (x, y) = (0.50, 0.45), and an external quantum efficiency EQE of 23.1% (driving voltage is 2.7V).

[0515] Device Example 19

[0516] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-195 instead of X-1. The device structure is as follows:

[0517] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-195(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0518] The device performance of the organic electroluminescent device D19 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are yellow light emission with a wavelength of 544 nm, a half-peak width of 20 nm, CIE color coordinates (x, y) = (0.40, 0.52), and an external quantum efficiency EQE of 3.3% (driving voltage is 2.8 V).

[0519] Device Example 20

[0520] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-195 from X-1. The device structure is as follows:

[0521] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-195(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0522] The device performance results of the organic electroluminescent device D20 prepared in this example are as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are yellow light emission with a wavelength of 545nm, a half-peak width of 21nm, CIE color coordinates (x, y) = (0.39, 0.51), and an external quantum efficiency EQE of 18.8% (driving voltage is 2.8V).

[0523] Device Example 21

[0524] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-204 instead of X-1. The device structure is as follows:

[0525] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-204(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0526] The device performance of the organic electroluminescent device D25 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 512nm, a half-peak width of 18nm, CIE color coordinates (x, y) = (0.22, 0.69), and an external quantum efficiency EQE of 4.8% (driving voltage is 3.0V).

[0527] Device Example 22

[0528] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-204 from X-1. The device structure is as follows:

[0529] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-204(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0530] The device performance of the organic electroluminescent device D26 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 512nm, a half-peak width of 18nm, CIE color coordinates (x, y) = (0.21, 0.69), and an external quantum efficiency EQE of 23.1% (driving voltage is 3.0V).

[0531] Device Example 23

[0532] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-246 instead of X-1. The device structure is as follows:

[0533] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-246(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0534] The device performance of the organic electroluminescent device D27 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m2 The characteristics of light emission are yellow light emission with a wavelength of 558nm, a half-peak width of 24nm, CIE color coordinates (x, y) = (0.39, 0.55), and an external quantum efficiency EQE of 3.4% (driving voltage is 2.8V).

[0535] Device Example 24

[0536] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-246 from X-1. The device structure is as follows:

[0537] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-246(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0538] The device performance of the organic electroluminescent device D28 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are yellow light emission with a wavelength of 558nm, a half-peak width of 24nm, CIE color coordinates (x, y) = (0.38, 0.55), and an external quantum efficiency EQE of 21.3% (driving voltage is 2.8V).

[0539] Device Example 25

[0540] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-260 instead of X-1. The device structure is as follows:

[0541] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-260(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0542] The device performance of the organic electroluminescent device D29 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 566nm, a half-peak width of 32nm, CIE color coordinates (x, y) = (0.42, 0.52), and an external quantum efficiency EQE of 3.3% (driving voltage is 2.8V).

[0543] Device Example 26

[0544] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-260 from X-1. The device structure is as follows:

[0545] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-260(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0546] The device performance results of the organic electroluminescent device D30 prepared in this example are as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 568 nm, a half-peak width of 33 nm, CIE color coordinates (x, y) = (0.42, 0.50), and an external quantum efficiency EQE of 19.0% (driving voltage is 2.8 V).

[0547] Device Example 27

[0548] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-276 instead of X-1. The device structure is as follows:

[0549] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-276(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0550] The device performance of the organic electroluminescent device D23 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 585nm, a half-peak width of 24nm, CIE color coordinates (x, y) = (0.53, 0.40), and an external quantum efficiency EQE of 4.3% (driving voltage is 2.6V).

[0551] Device Example 28

[0552] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-276 from X-1. The device structure is as follows:

[0553] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-276(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0554] The device performance of the organic electroluminescent device D24 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are orange light emission with a wavelength of 588nm, a half-peak width of 24nm, CIE color coordinates (x, y) = (0.53, 0.38), and an external quantum efficiency EQE of 23.4% (driving voltage is 2.6V).

[0555] Device Example 29

[0556] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by X-1 instead of X-283. The device structure is as follows:

[0557] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-283(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0558] The device performance of the organic electroluminescent device D21 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 513nm, a half-peak width of 21nm, CIE color coordinates (x, y) = (0.18, 0.70), and an external quantum efficiency EQE of 4.2% (driving voltage is 3.0V).

[0559] Device Example 30

[0560] The preparation method is the same as that of device example 1, except that the wide bandgap host material Host in the light-emitting layer is replaced by a TADF host TD, and the dye is replaced by X-283 from X-1. The device structure is as follows:

[0561] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-283(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0562] The device performance of the organic electroluminescent device D22 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 513nm, a half-peak width of 21nm, CIE color coordinates (x, y) = (0.18, 0.70), and an external quantum efficiency EQE of 25.5% (driving voltage is 3.0V).

[0563] Comparative Device Example 1

[0564] The preparation method is the same as that of device example 1, except that the compound X-1 of the present invention used in the light-emitting layer is replaced by the compound TTPA in the prior art. The specific device structure is as follows:

[0565] ITO / HI(10nm) / HT(40nm) / Host:2wt%TTPA(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0566] The device performance results of the organic electroluminescent device DD1 prepared in this embodiment are as follows: when a DC voltage is applied and the characteristics of the luminescence at 10 cd / m2 are measured, green light with a wavelength of 529 nm, a half-peak width of 54 nm, CIE color coordinates (x, y) = (0.29, 0.59), and an external quantum efficiency EQE of 3.5% can be obtained (the driving voltage is 2.7 V).

[0567] Comparative Device Example 2

[0568] The preparation method is the same as that of device example 2, except that the compound X-1 of the present invention used in the light-emitting layer is replaced by the compound TTPA in the prior art. The specific device structure is as follows:

[0569] ITO / HI(10nm) / HT(40nm) / TD:2wt%TTPA(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0570] The device performance of the organic electroluminescent device DD2 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 530nm, a half-peak width of 52nm, CIE color coordinates (x, y) = (0.30, 0.59), and an external quantum efficiency EQE of 15.7% (driving voltage is 2.7V).

[0571] Comparative Device Example 3

[0572] The preparation method is the same as that of device embodiment 1, except that the compound X-1 of the present invention used in the light-emitting layer is replaced by the compound 2F-BN in the prior art. The specific device structure is as follows:

[0573] ITO / HI(10nm) / HT(40nm) / Host:2wt%2F-BN(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0574] The device performance of the organic electroluminescent device DD3 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 501nm, a half-peak width of 40nm, CIE color coordinates (x, y) = (0.16, 0.60), and an external quantum efficiency EQE of 13.7% (driving voltage is 3.0V).

[0575] Comparative Device Example 4

[0576] The preparation method is the same as that of device embodiment 2, except that the compound X-1 of the present invention used in the light-emitting layer is replaced by the compound 2F-BN in the prior art. The specific device structure is as follows:

[0577] ITO / HI(10nm) / HT(40nm) / TD1:2wt%2F-BN(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0578] The device performance of the organic electroluminescent device DD4 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are green light emission with a wavelength of 502nm, a half-peak width of 40nm, CIE color coordinates (x, y) = (0.16, 0.60), and an external quantum efficiency EQE of 17.6% (driving voltage is 3.0V).

[0579] Comparative Device Example 5

[0580] The preparation method is the same as that of device embodiment 1, except that the compound X-1 of the present invention used in the light-emitting layer is replaced by the compound DM1 in the prior art. The specific device structure is as follows:

[0581] ITO / HI(10nm) / HT(40nm) / Host:2wt%DM1(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0582] The device performance of the organic electroluminescent device DD5 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are blue light emission with a wavelength of 480nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.15, 0.20), and an external quantum efficiency EQE of 3.1% (driving voltage is 3.2V).

[0583] Comparative Device Example 6

[0584] The preparation method is the same as that of device embodiment 2, except that the compound X-1 of the present invention used in the light-emitting layer is replaced by the compound DM1 in the prior art. The specific device structure is as follows:

[0585] ITO / HI(10nm) / HT(40nm) / TD1:2wt%DM1(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0586] The device performance of the organic electroluminescent device DD6 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of light emission are blue light emission with a wavelength of 482nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.15, 0.21), and an external quantum efficiency EQE of 14.4% (driving voltage is 3.2V).

[0587] The structural formulas of various organic materials used in the above embodiments are as follows:

[0588]

[0589]

[0590]

[0591] The specific performance data of the organic electroluminescent devices D1 to D30 and devices DD1, DD2, DD3, DD4, DD5 and DD6 prepared in the above-mentioned device embodiments are shown in Tables 1 and 2 below.

[0592] Table 1:

[0593]

[0594]

[0595] Table 2:

[0596]

[0597]

[0598] It can be seen from the data in Table 1 and Table 2 that compared with the compounds TTPA, 2F-BN and DM1 in the prior art, the compounds of the present invention have a narrower fluorescence spectrum half-width, and belong to a new type of stable MR type narrow spectrum fluorescent dye. Although the classic green fluorescent dye TTPA has a higher fluorescence quantum yield, due to the wider fluorescence emission spectrum, TTPA is difficult to meet the requirements of BT2020 for color purity. In comparison, 2F-BN uses the electronegativity difference of boron nitrogen atoms to achieve a multiple resonance effect and obtain a narrow emission fluorescence spectrum. However, the chemical stability of boron atoms is poor, and the single triplet energy level difference of the molecule is smaller, which slows down the exciton dynamics process. Compound DM1, as a class of traditional fluorescent dyes, also has a narrow fluorescence spectrum and a shorter fluorescence lifetime, but the electron cloud distribution of this type of material is limited and delocalized, and the energy band is larger, and a higher driving voltage is often required, so it also faces the problem of stability. In the present invention, we have invented a new type of multiple resonance fluorescent dye system. Different from the traditional boron nitrogen and carbonyl nitrogen structures, the present invention uses the electronegativity difference of heteroatoms and carbon atoms to achieve a multiple resonance effect. Among them, the introduction of the six-membered fused ring effectively expands the molecular conjugation area, widens the molecular single triplet energy level difference, further accelerates the exciton dynamics process, and improves the device stability. Therefore, the fusion mode of the five-membered ring plus the six-membered ring can achieve a balance between narrow spectrum efficient luminescence and high stability. From the above results, it can be seen that the electroemission spectrum of the embodiment has a small half-peak width, confirming that it has an effective multiple resonance effect. At the same time, the molecule has excellent luminescence efficiency, and the PLQY is above 90%. Utilizing the sensitization effect of the thermally activated delayed fluorescence host, the embodiment also shows excellent device stability, which is significantly improved compared to the comparative example DD4, proving the great advantages of the molecular structure in the present invention in improving device efficiency and stability. In view of its excellent efficiency, color purity and stability, the above-mentioned compounds should have good application prospects.

[0599] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. For those skilled in the art, according to the idea of ​​the present invention, there will be changes in the specific implementation methods and application scopes. The content of this specification should not be understood as limiting the present invention.

Claims

1. An organic compound having a structure as shown in any one of formula (1), formula (2), formula (3) or formula (4): in, X 1 and X 2 are independently N or B; Ring A, Ring B and Ring C are all benzene rings; Ring D 1 、Ring d 2 Each independently is a benzene ring or a naphthalene ring; Ring E and Ring F each independently represent a C4-C30 aromatic ring; The R A , R B , R C , R D , R E and R F Each independently represents a substituent group from a single substituent group to the maximum number of substituents allowed; R A , R B , R C , R D , R E and R F Each is independently selected from one of hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-C36 chain alkyl, substituted or unsubstituted C3-C36 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 thioalkoxy, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C60 monocyclic aryl or condensed ring aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C5-C60 heteroaryl; The R A , R B , R C , R D , R E and R F Each of the rings A, B, C, D, E and F is connected to each other by a single bond, or R A , R B , R C , R D , R E and R F Each is fused to the connected ring A, ring B, ring C, ring D, ring E and ring F; When the above R A , R B , R C , R D , R E and R F When substituents are present, the substituents are independently selected from one of deuterium, halogen, cyano, amino, C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C6-C60 aryl, and C5-C60 heteroaryl.

2. The organic compound according to claim 1, having a structure as shown in any one of the following formulas (5), (6), (7) or (8): In formula (5) to formula (8), the X 1 , X 2 , R A , R B , R C , R D , R E , R F 、Ring d 1 and Ring D 2 The definitions of are the same as those in formula (1), formula (2), formula (3) or formula (4).

3. The organic compound according to claim 1, having a structure as shown in any one of the following formulas (9), (10), (11) or (12): In formula (9) to formula (12), the X 1 , X 2 , R A , R B , R C , R D , R E and R F The definitions of are the same as those in formula (1), formula (2), formula (3) or formula (4); And when X 1 and X 2 When both are N: In formula (9), R B , R C Each independently is not selected from fluorenyl, 9,9-dimethylfluorenyl, naphthyl; R D , R E and R F Not selected from hydrogen; In formula (10), R A Not selected from cyano, trimethylphenyl, R B , R C are independently not selected from the group consisting of trimethylphenyl, phenyl and carbazole; R D , R E and R F All are hydrogen; In formula (12), R A R is not selected from hydrogen, cyano, phenyl, trimethylphenyl; B , R C Each of the following is independently not selected from fluorenyl, 9,9-dimethylfluorenyl, a combination of phenyl and carbazole, and anthracene; R D , R E and R F All are hydrogen.

4. According to any one of claims 1 to 3, the organic compound, wherein X 1 and X 2 At the same time it is a N atom.

5. According to any one of claims 1 to 3, the organic compound, R A , R B , R C , R D , R E and R F are independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylene, pyrenyl, chrysene, peryl, fluoranthenyl, tetraphenylene, pentacene, benzopyrenyl, biphenyl, phenylene, terphenylene, triphenylene, tetraphenylene, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis or trans Indenyl, indenyl, isotrimer, indenyl, spirotrimer, indenyl, spiroisotrimer, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenylcarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthracene oxazolyl, phenanthrazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5 The substituted groups may be selected from the group consisting of oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, diarylamine, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, pyrrole, piperidine, methoxy, and silicon, or a combination of two of the above substituted groups.

6. According to any one of claims 1 to 3, the organic compound, R A , R B , R C , R D , R E and R F Each of the substituents is independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, adamantyl, fluorine, trifluoromethyl, phenyl, mesityl, naphthyl, anthracenyl, furanyl, tetrahydrofuranyl, pyrrolyl, tetrahydropyrrolyl, thienyl, carbazolyl, triazine, pyridyl, quinolyl, acridinyl, cyano, methoxy, silicon, dimethylamino, triarylamine, fluorenyl, dibenzofuranyl, and dibenzothienyl, or a combination of two of the above substituents.

7. The compound of the general formula according to claim 1 is selected from the following specific structural compounds:

8. Use of the compound described in any one of claims 1 to 7 as a functional material in an organic electronic device, wherein the organic electronic device includes an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet-type scanner or an electronic paper.

9. Use of the compound according to claim 8 as a light-emitting layer material in an organic electroluminescent device.

10. An organic electroluminescent device, comprising a first electrode, a second electrode and one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer comprises a hole transport region, a light-emitting layer and an electron transport region, wherein the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and a light-emitting layer is provided between the hole transport region and the electron transport region, wherein the light-emitting layer contains a compound as described in any one of claims 1 to 7.

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