Nitrogen-containing organic compounds, their applications, and organic electroluminescent devices

Abstract

The present invention relates to a nitrogen-containing organic compound, its application, and an organic electroluminescent device. The nitrogen-containing organic compound is represented by Formula I or II, where X and Y are the same or different, and each independently is oxygen or sulfur; R 1 、R 2 、R 3 and R 4 are the same or different, and each independently is H, alkyl, aryl, or heteroaryl, and at least one of R 1 、R 2 、R 3 and R 4 is a C3-C40 heteroaryl having a nitrogen heterocycle, and the nitrogen-containing heterocycle is selected from a pyrimidine ring, a quinoxaline ring, a quinazoline ring, and a triazine ring; L 1 、L 2 、L 3 and L 4 are the same or different, and each independently is selected from absent, arylene, and heteroarylene. When L 3 and L 4 are absent, R 3 and R 4 are not H. When the organic electroluminescent compound of the present invention is applied to an organic electroluminescent device, it has a lower driving voltage and higher device luminescence efficiency.

Description

Technical Field

[0001] The present invention relates to the field of organic electroluminescent devices, and particularly relates to a nitrogen-containing organic compound, its application, and an organic electroluminescent device. Background Art

[0002] The phenomenon of organic electroluminescence was first discovered by Pope et al. in 1963. They found that a single crystal of anthracene could emit weak blue light when driven by a voltage above 100V. However, due to the high driving voltage and large thickness of the single crystal anthracene, it did not attract wide attention. It was not until 1987 that Dr. Deng Qingyun et al. of Eastman Kodak Company reported two organic semiconductor materials, aluminum 8-hydroxyquinoline with high fluorescence efficiency and good electron transport properties and aromatic diamine with good hole transport properties. A bilayer organic electroluminescent device (Organic Light-Emitting Diodes, OLED) was prepared by vacuum thermal evaporation. At a driving voltage less than 10V, the external quantum efficiency of the aforementioned OLED reached 1%, and the brightness was as high as 1000 Cd / m2, which set off a research boom in OLEDs and promoted further research on organic electroluminescent materials.

[0003] In recent years, as a new generation of display technology, OLEDs have gradually entered people's field of vision. The broad application prospects and rapid technological progress have made OLEDs one of the most popular research topics in the display field and scientific research product development.

[0004] Currently, OLEDs or screens still have the defects of high driving voltage and low current efficiency. To improve these defects, on the one hand, the device structure and manufacturing process need to be further optimized, and on the other hand, the performance of the materials for each functional layer also needs to be improved.

[0005] The electron migration ability and exciton blocking ability of electron transport materials play a crucial role in the driving voltage and luminous efficiency of the device. Therefore, the market urgently needs to develop high-performance electron transport materials to reduce the driving voltage of the device and improve the luminous efficiency of the device. Summary of the Invention

[0006] The purpose of the present invention is to provide a new organic compound for use as an electron transport material to overcome the defects of high driving voltage and low luminous efficiency of OLEDs provided by the prior art.

[0007] To this end, in the first aspect, the present application provides a nitrogen-containing organic compound, the structure of which is shown in Formula I or II:

[0008]

[0009]

[0010] In Formulas I and II,

[0011] X is oxygen or sulfur; Y is oxygen or sulfur; R 1 、R 2 、R 3 and R 4 are the same or different and each independently is H, alkyl, aryl or heteroaryl, and one or more of R 1 、R 2 、R 3 and R 4 is heteroaryl having a nitrogen heterocycle selected from one or more of a pyrimidine ring, a quinoxaline ring, a quinazoline ring and a triazine ring; L 1 、L 2 、L 3 and L 4 are the same or different and each independently is selected from absent, arylene and heteroarylene, provided that when L 3 and L 4 are absent, R 3 and R 4 are not H.

[0012] In the present application, when L 1 、L 2 、L 3 or L 4 is absent, it means that R 1 、R 2 、R 3 or R 4 is directly linked to the ring. By way of example, when L 1 、L 2 、L 3 、L 4 are all absent, the structure of the nitrogen-containing organic compound of the present invention is as shown in Formula IA or Formula IIA below:

[0013]

[0014] According to some embodiments of the present invention, R 1 、R 2 、R 3 and R 4 are each independently H, C1-C6 alkyl, C6-C40 aryl or C3-C40 heteroaryl, and one or more of R 1 、R 2 、R 3 and R 4 is C3-C40 heteroaryl having a nitrogen heterocycle.

[0015] According to some embodiments of the present invention, L 1 、L 2 、L 3 and L4 Each is independently selected from absent, C6-C20 arylene, and C3-C20 heteroarylene. In some embodiments of the present invention, L 1 , L 2 , L 3 , and L 4 are each independently absent, phenylene, naphthylene, anthrylene, phenanthrylene, biphenylene, dibenzothiophenylene, or dibenzofuranylene.

[0016] In some embodiments of the present invention, R 1 and R 2 are H, C1-C6 alkyl, C6-C40 aryl, or C3-C40 heteroaryl, and R 3 and / or R 4 is C3-C40 heteroaryl having a nitrogen heterocycle. In some embodiments of the present invention, R 1 and R 2 are H, C1-C3 alkyl, C6-C20 aryl (such as C6 aryl, C10 aryl, C12 aryl, C14 aryl, C16 aryl, or C20 aryl).

[0017] or C3-C40 heteroaryl, and R 3 and / or R 4 is C3-C40 heteroaryl having a nitrogen heterocycle.

[0018] In some embodiments of the present invention, two or three of R 1 , R 2 , R 3 , and R 4 are each independently H, C1-C6 alkyl, or C6-C40 aryl, and the remaining two or one is C3-C40 heteroaryl having a nitrogen heterocycle.

[0019] In some embodiments of the present invention, R 1 and / or R 2 is C3-C40 heteroaryl having a nitrogen heterocycle; or R 3 and / or R 4 is C3-C40 heteroaryl having a nitrogen heterocycle. In some embodiments of the present invention, R 1 and / or R 2 is C3-C40 heteroaryl having a nitrogen heterocycle; and R 3 and / or R 4 is C3-C40 heteroaryl having a nitrogen heterocycle.

[0020] In some embodiments of the present invention, R 1 and R 2 are hydrogen; R 3 and / or R 4is a C3-C40 heteroaryl having a nitrogen heterocycle. According to some embodiments of the present invention, R 1 and R 2 are hydrogen; R 3 and / or R 4 is a C3-C40 heteroaryl having a nitrogen heterocycle, and L 1 、L 2 、L 3 and L 4 are each independently absent, phenylene, naphthylene, anthrylene, phenanthrylene, biphenylene, dibenzothiophenylene or dibenzofuranylene.

[0021] According to some embodiments of the present invention, the heteroatoms in the heteroaryl are selected from one or more of nitrogen, oxygen, sulfur, phosphorus and silicon. According to some embodiments of the present invention, the heteroatoms in the heteroarylene are selected from one or more of nitrogen, oxygen, sulfur, phosphorus and silicon.

[0022] According to some embodiments of the present invention, the heteroaryl having a nitrogen heterocycle is selected from the following groups:

[0023]

[0024] wherein, Ar 1 and Ar 2 are each independently selected from aryl and heteroaryl.

[0025] In some embodiments, Ar 1 and Ar 2 are each independently selected from C6-C40 aryl and C3-C40 heteroaryl. In some embodiments, Ar 1 and Ar 2 are each independently selected from C6-C20 aryl and C3-C40 heteroaryl. In some embodiments, Ar 1 and Ar 2 are each independently selected from phenyl, naphthyl, anthryl, biphenyl, dibenzofuranyl, dibenzothiophenyl, phenyl-substituted naphthyl, phenyl-substituted anthryl, phenyl-substituted biphenyl, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothiophenyl, naphthyl-substituted phenyl, naphthyl-substituted naphthyl, naphthyl-substituted anthryl, naphthyl-substituted biphenyl, naphthyl-substituted dibenzofuranyl, naphthyl-substituted dibenzothiophenyl.

[0026] The nitrogen-containing organic compound of the present invention may specifically be the following compounds:

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035] In a second aspect, the present invention provides an application of the organic compound as described above in an organic electroluminescent device. According to an embodiment of the present invention, in the organic electroluminescent device, the organic compound serves as an electron transport material.

[0036] In a third aspect, the present invention provides an organic electroluminescent device, which includes an electron transport layer, and the electron transport layer contains the organic compound described above.

[0037] According to some embodiments of the present invention, the organic electroluminescent device of the present invention further includes an anode, a hole injection layer, a hole transport layer, an optional electron blocking layer, a light emitting layer, an optional hole blocking layer, an electron injection layer, and a cathode.

[0038] According to some embodiments of the present invention, the anode material for forming the anode generally preferably has a material with a large work function. For example, the anode materials used in the present invention are selected from one or more of the following materials: metals such as vanadium, chromium, copper, and gold, or other alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide, indium zinc oxide, and tin dioxide; combinations of metals and oxides such as zinc oxide:aluminum, but not limited thereto.

[0039] According to some embodiments of the present invention, the material for forming the hole injection layer has the ability to transport holes. Therefore, the material of the hole injection layer has the effect of injecting holes into the anode, has an excellent hole injection effect on the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material, and in addition, has excellent film forming ability. The HOMO of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer.

[0040] According to some embodiments of the present invention, the hole injection material and the hole transport material include at least one of aromatic amine derivatives (such as NPB, SqMA1), hexaazatriphenylene derivatives (such as HACTN), indolocarbazole derivatives, conductive polymers (such as PEDOT / PSS), phthalocyanine or porphyrin derivatives, dibenzoindenofluoreneamine, spirobifluoreneamine, but not limited thereto.

[0041] According to some embodiments of the present invention, the hole injection layer and the hole transport layer can be formed of, for example, an aromatic amine derivative having the following general formula:

[0042]

[0043] The groups of R1 to R9 in the above general formula are each independently selected from a single bond, hydrogen, deuterium, an alkyl group, benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, fluorene, dimethylfluorene, spirobifluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolocarbazole, indeno[1,2-b]carbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine.

[0044] According to some embodiments of the present invention, the material for forming the electron blocking layer is not particularly limited. Generally, any compound that can satisfy the following first and / or second conditions can be considered:

[0045] First: having a relatively shallow LUMO energy level (smaller absolute value), the purpose of which is to reduce the number of electrons leaving the light-emitting layer, thereby increasing the recombination probability of electrons and holes in the light-emitting layer.

[0046] Second: having a relatively large triplet energy, the purpose of which is to reduce the number of excitons leaving the light-emitting layer, thereby increasing the efficiency of exciton conversion to light emission.

[0047] According to some embodiments of the present invention, the material for forming the electron blocking layer includes, but is not limited to, aromatic amine derivatives (such as NPB) and spirobifluoreneamines (such as SpMA2), and the structures of some electron blocking materials are similar to those of hole injection materials and hole transport materials.

[0048] According to some embodiments of the present invention, when the light-emitting material of the light-emitting layer is a material that can emit light in the visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer respectively and combining the holes and electrons, and is preferably a material having good quantum efficiency for fluorescence or phosphorescence.

[0049] According to some embodiments of the present invention, the light-emitting layer may include a host material and a guest material. According to some embodiments of the present invention, the host material of the device contains the compound described in the first aspect of the present invention. According to some embodiments of the present invention, the guest material is preferably a compound that emits light through at least one of phosphorescence, fluorescence, TADF (thermally activated delayed fluorescence), MLCT (metal-to-ligand charge transfer), HLCT (having a hybrid CT state), and triplet-triplet annihilation methods.

[0050] According to some embodiments of the present invention, the host material in the light-emitting layer may include derivatives of perylene, derivatives of anthracene, fluorene derivatives, stilbenyl aryl derivatives, arylamine derivatives, organosilicon derivatives, organoboron derivatives, carbazole-triazine derivatives, acridine derivatives, derivatives containing ketones, sulfone derivatives, cyano derivatives, and xanthene derivatives, but not limited thereto.

[0051] In some preferred embodiments of the present invention, the sulfone derivatives have the general formula shown below:

[0052]

[0053] The ketone derivatives have the general formula shown below:

[0054]

[0055] In the general formulas of the above sulfone derivatives and ketone derivatives, R20, R21, R22, and R23 are each independently selected from a single bond, hydrogen, deuterium, alkyl, benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenylnaphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, fluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolocarbazole, indeno[1,2-b]carbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine, or triazine, and groups represented by their substituents.

[0056] According to some embodiments of the present invention, the material of the hole-blocking layer may preferably also be a compound satisfying the following first and / or second conditions:

[0057] First: having a deeper HOMO energy level (larger absolute value), the purpose of which is to reduce the number of holes leaving the light-emitting layer, thereby increasing the recombination probability of electrons and holes in the light-emitting layer.

[0058] Second: having a larger triplet energy, the purpose of which is to reduce the number of excitons leaving the light-emitting layer, thereby increasing the efficiency of exciton conversion to light emission.

[0059] According to some embodiments of the present invention, the material for forming the hole-blocking layer may include, for example, compounds containing phenanthroline derivatives (such as Bphen, BCP), benzophenanthrene derivatives, benzimidazole derivatives, but not limited thereto.

[0060] According to some embodiments of the present invention, the electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound with the following properties: it has the ability to transport electrons, has the effect of injecting electrons from the cathode, has an excellent effect of injecting electrons into the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from moving to the hole injection layer, and in addition, has excellent thin-film forming ability. Electron injection layer materials include, for example, LiF, CsF, Cs 2 CO 3 , LiQ, but not limited thereto.

[0061] According to some embodiments of the present invention, the cathode material is usually preferably a material with a small work function, which can smoothly inject electrons into the organic material layer. The cathode materials that can be used in the present disclosure can be selected from one or more of the following materials: one or more of Al, Mg, and Ag.

[0062] The present invention has at least the following specific advantages:

[0063] 1. The compound provided by the present invention has appropriate HOMO and LUMO energy levels, can match with adjacent materials, reduce the injection barrier, and at the same time can prevent leakage. When the compound of the present invention is applied to an organic electroluminescent device, it can effectively reduce the driving voltage of the device.

[0064] 2. The compound of the present invention has excellent electron mobility, can increase the recombination probability of electrons and holes, and can increase the light-emitting efficiency of the device when applied to an organic electroluminescent device.

[0065] 3. The parent nucleus of the present invention contains an oxazole or thiazole structure, and O / S is located at the 1st position, which can weaken the intermolecular interaction, avoid intermolecular aggregation, thereby improving the film-forming property of the compound, and at the same time increasing the service life of the material. Detailed embodiments

[0066] The present invention does not particularly limit the specific method for preparing the aforementioned compound. Those skilled in the art can obtain the aforementioned compound of the present invention according to the specific structural formula provided by the present invention in combination with the conventional process routes in the field of organic synthesis. Moreover, several examples are exemplarily listed in the following text of the present invention to illustrate the preparation method of the compound of the present invention. Those skilled in the art can also obtain the specific preparation methods of all the remaining compounds by replacing the types of raw materials according to the preparation methods of the compounds in the following text of the present invention. The present invention will not elaborate on the preparation methods of all the compounds, and those skilled in the art should not understand this as a limitation of the present invention.

[0067] The present invention will be described in detail below with reference to examples. In the following examples, various raw materials used are common commercially available products without special instructions. Unless otherwise specified, the room temperature described below means 25 ± 1°C.

[0068] Preparation Example 1:

[0069]

[0070] Synthesis of Intermediate A: In a 500 ml three-necked flask, 2-bromo-4-iodooxazole (64 mmol) was added to anhydrous THF (175 ml) and stirred under nitrogen protection. The temperature was lowered to -78°C, and 2.5 mol / L n-butyllithium (28.2 ml) was added dropwise. The mixture was kept at -78°C for 1 hour, and 2-chloro-4-formyloxazole (64 mmol) was added at -78°C. The temperature was then raised to room temperature, and the reaction was completed after 1 h. The reaction was quenched with saturated ammonium chloride aqueous solution, and the mixture was extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and filtered to remove the desiccant, and the filtrate was obtained. The filtrate was concentrated by rotary evaporation to obtain a crude product. The crude product was purified by column chromatography to obtain white solid A (yield: 72.9%).

[0071] Synthesis of Intermediate B: The synthesis method was the same as that of Intermediate A, and white solid B was obtained (yield: 71.3%).

[0072] Synthesis of Intermediate C: In a 500 ml three-necked flask, Intermediate A (46 mmol) was added to dichloromethane (130 ml) and stirred. Br 2 (92 mmol) was added dropwise at room temperature, and the reaction was allowed to proceed overnight at room temperature after the addition was complete. After detecting that the raw materials had reacted completely, water (250 ml) was added dropwise to the reaction solution, and the mixture was extracted three times with dichloromethane. The residue was obtained by rotary evaporation under reduced pressure and purified by column chromatography to obtain white solid C (yield: 46.8%).

[0073] Synthesis of Intermediate D: The synthesis method was the same as that of Intermediate C, and white solid D was obtained (yield: 45.2%).

[0074] Synthesis of Intermediate E: In a 500 ml three-necked flask, Intermediate C (20 mmol) was added to dichloromethane (85 ml) and stirred until dissolved. Pyridinium chlorochromate (20 mmol) was added, and the temperature was raised to reflux. After reacting for 8 hours, TLC monitoring showed that the reaction was basically complete. The mixture was cooled to room temperature and filtered by suction to obtain the organic phase, which was concentrated under reduced pressure and purified by column chromatography to obtain white solid E (yield: 80.2%).

[0075] Synthesis of Intermediate F: The synthesis method was the same as that of Intermediate E, and white solid F was obtained (yield: 77.9%).

[0076] Synthesis of Intermediate G: Intermediate E (26 mmol) was added to DMAC solvent (120 ml) and stirred until dissolved. Then copper powder (78 mmol) was added, and the mixture was heated with stirring and refluxed. After reacting for 24 hours, TLC monitoring showed that the reaction was basically complete. It was cooled to room temperature, and a mixture of water (60 ml) and chloroform (120 ml) was added for extraction to obtain the organic phase. After concentration under reduced pressure, white solid G was obtained by column chromatography (yield: 80.5%).

[0077] Synthesis of Intermediate H: The synthesis method was the same as that of Intermediate G, and white solid H was obtained (yield: 78.6%).

[0078] Preparation Example 2:

[0079]

[0080] R = H\Cl

[0081] Synthesis of Intermediate I: In a 500 ml three-necked flask, the iodobenzene compound was added to anhydrous THF under nitrogen protection. The temperature was lowered to -78 °C, and 2.5 M n-butyllithium was added dropwise. It was kept at -78 °C for 1 hour, Intermediate G was added at -78 °C, and after addition, it was kept for 1 hour. Then the temperature was raised to room temperature, and the reaction was completed after 1 h. The reaction was quenched with water, and the organic phase was extracted three times with chloroform. After drying over anhydrous sodium sulfate and filtering the desiccant, the filtrate was obtained. After rotary evaporation, the crude product was obtained, and solid I was obtained by column chromatography.

[0082] Synthesis of Intermediate J: The synthesis method was the same as that of Intermediate I, and solid J was obtained.

[0083] Synthesis of Intermediate K: The synthesis method was the same as that of Intermediate I, and solid K was obtained.

[0084] Synthesis of Intermediate L: The synthesis method was the same as that of Intermediate I, and solid L was obtained.

[0085] Preparation Example 3:

[0086]

[0087] R = H\Cl

[0088] Synthesis of Intermediate M: In a 500 ml three-necked flask, add the o-iodobiphenyl compound to anhydrous THF, protect with nitrogen, cool down to -78 °C, dropwise add 2.5 M n-butyllithium, keep the temperature at -78 °C for 1 hour, add Intermediate G at -78 °C, after addition, keep for 1 hour, then warm up to room temperature, and the reaction is completed after 1 h. Quench with water, extract the organic phase three times with chloroform, filter the desiccant after drying with anhydrous sodium sulfate to obtain the filtrate, rotary evaporate to obtain the crude product, dissolve the crude product in 1,2-dichloroethane, cool down to 0 °C, dropwise add trifluoromethanesulfonic acid, after dropping, heat under reflux for 2 hours, cool to room temperature, adjust the solution to neutral with an aqueous NaHCO3 solution, dry the organic phase with anhydrous sodium sulfate and then rotary evaporate under reduced pressure, and obtain the white solid M through column chromatography.

[0089] Synthesis of Intermediate N: The synthesis method is the same as that of Intermediate N, and the white solid N is obtained.

[0090] According to the above reactions, the following specific parent nucleus structures are obtained:

[0091]

[0092] Mass spectrometry: C19H10BrClN2O2, theoretical value: 411.96, measured value: 412.0.

[0093] Elemental analysis: theoretical value: C: 55.17%, H: 2.44%, N: 6.77%; measured value: C: 55.19%, H: 2.41%, N: 6.76%.

[0094]

[0095] Mass spectrometry: C19H8BrCl3N2O2, theoretical value: 479.88, measured value: 479.9.

[0096] Elemental analysis: theoretical value: C: 47.29%, H: 1.67%, N: 5.81%; measured value: C: 47.32%, H: 1.69%, N: 5.80%.

[0097]

[0098] Mass spectrometry: C19H8BrCl3N2O2, theoretical value: 479.88, measured value: 479.9.

[0099] Elemental analysis: theoretical value: C: 47.29%, H: 1.67%, N: 5.81%; measured value: C: 47.30%, H: 1.65%, N: 5.82%.

[0100]

[0101] Mass spectrometry: C19H9BrCl2N2O2, theoretical value: 445.92, measured value: 445.9.

[0102] Elemental analysis: theoretical value: C: 50.93%, H: 2.02%, N: 6.25%; measured value: C: 50.95%, H: 2.00%, N: 6.27%.

[0103]

[0104] Mass spectrometry: C19H10BrClN2S2, theoretical value: 443.92, measured value: 443.9.

[0105] Elemental analysis: theoretical value: C: 51.19%, H: 2.26%, N: 6.28%; measured value: C: 51.22%, H: 2.25%, N: 6.25%.

[0106]

[0107] Mass spectrometry: C19H8BrCl3N2S2, theoretical value: 511.84, measured value: 511.8.

[0108] Elemental analysis: theoretical value: C: 44.34%, H: 1.57%, N: 5.44%; measured value: C: 44.36%, H: 1.58%, N: 5.48%.

[0109]

[0110] Mass spectrometry: C19H8BrClN2O2, theoretical value: 409.95, measured value: 410.0.

[0111] Elemental analysis: theoretical value: C: 55.44%, H: 1.96%, N: 6.81%; measured value: C: 55.42%, H: 1.98%, N: 6.80%.

[0112]

[0113] Mass spectrometry: C19H6BrCl3N2O2, theoretical value: 477.87, measured value: 477.9.

[0114] Elemental analysis: theoretical value: C: 47.49%, H: 1.26%, N: 5.83%; measured value: C: 47.53%, H: 1.28%, N: 5.81%.

[0115]

[0116] Mass spectrometry: C19H8BrClN2S2, theoretical value: 441.90, measured value: 441.9.

[0117] Elemental analysis: theoretical value: C: 51.43%, H: 1.82%, N: 6.31%; measured value: C: 51.40%, H: 1.83%, N: 6.35%.

[0118]

[0119] Mass spectrometry: C19H6BrCl3N2S2, theoretical value: 509.82, measured value: 509.8.

[0120] Elemental analysis: theoretical value: C: 44.52%, H: 1.18%, N: 5.46%; measured value: C: 44.58%, H: 1.14%, N: 5.43%.

[0121]

[0122] Mass spectrometry: C19H6BrCl3N2S2, theoretical value: 509.82, measured value: 509.8.

[0123] Elemental analysis: theoretical value: C: 44.52%, H: 1.18%, N: 5.46%; measured value: C: 44.55%, H: 1.19%, N: 5.47%.

[0124]

[0125] Mass spectrometry: C19H7BrCl2N2S2, theoretical value: 475.86, measured value: 475.9.

[0126] Elemental analysis: theoretical value: C: 47.72%, H: 1.48%, N: 5.86%; measured value: C: 47.70%, H: 1.44%, N: 5.87%.

[0127] Preparation Example 4:

[0128]

[0129] Synthesis of Intermediate 1-1: In a 500-ml three-necked flask, under nitrogen protection, successively add 1,4-dioxane solvent (165 ml), 2-chloro-4,6-diphenyl-1,3,5-triazine (62 mmol), bis(pinacolato)diboron (62 mmol), potassium acetate (160 mmol), and dichlorobis[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) (0.62 mmol) while stirring. Heat the mixture to reflux for 4 h. After detecting the completion of the reaction of the raw materials by HPLC, cool the reaction solution to room temperature and then rotary evaporate it under reduced pressure to obtain a crude product. Dissolve the crude product in toluene solvent, heat and stir, raise the temperature to reflux, and decolorize it through a silica gel column. Rotary evaporate the filtrate under reduced pressure until there is a small amount of solvent remaining, then add ethanol (250 ml) for pulping, and recrystallize with toluene / ethanol to obtain a white solid (yield: 53.2%).

[0130] Synthesis of Intermediate 1-2: In a 500-ml three-necked flask, under nitrogen protection, add Intermediate 1-1 (47 mmol), Intermediate K-1 (47 mmol), toluene (160 ml), ethanol (40 ml), water (20 ml), PdCl 2 (dppf) 3 (0.47 mmol), and 20 ml of an aqueous solution containing potassium carbonate (118 mmol). Start stirring and heat to 90 °C for overnight reaction. After 20 h, cool the reaction to 40 °C, filter to obtain a crude product. Wash the crude product with water (270 ml), and then wash it with ethanol (270 ml) to obtain a gray solid. Separate the pale yellow solid Intermediate 1-1 by silica gel column chromatography (yield: 85.4%).

[0131] Synthesis of Compound 1: The synthesis method is the same as that of Intermediate 1-1, and a pale yellow solid Compound 1 is obtained (yield: 83.5%).

[0132] Mass spectrometry: C49H30N8O2, theoretical value: 762.25, measured value: 762.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.07 - 7.12 (4H, m), 7.13 - 7.24 (4H, m), 7.26 - 7.30 (2H, m), 7.47 - 7.54 (12H, m), 8.32 - 8.40 (8H, m).

[0133] Preparation Example 5:

[0134]

[0135] Synthesis of Intermediate 22-1: The synthesis method is the same as that of Intermediate 1-2, and a pale yellow solid Intermediate 22-1 is obtained (yield: 86.1%).

[0136] Synthesis of Compound 22: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Compound 22 is obtained (yield: 84.2%).

[0137] Mass spectrometry: C61H36N8O2, theoretical value: 912.30, measured value: 912.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.18 - 7.22 (1H, m), 7.24 - 7.25 (1H, m), 7.28 - 7.35 (2H, m), 7.44 - 7.50 (12H, m), 7.85 - 7.89 (2H, m), 7.92 - 7.94 (8H, s), 7.98 - 8.03 (2H, m), 8.29 - 8.37 (8H, m).

[0138] Preparation Example 6:

[0139]

[0140] Synthesis of Intermediate 35-1: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 35-1 is obtained (yield: 85.7%).

[0141] Synthesis of Compound 35: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Compound 35 is obtained (yield: 84.5%).

[0142] Mass spectrometry: C61H38N8S2, theoretical value: 946.27, measured value: 946.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.07 - 7.12 (4H, m), 7.14 - 7.24 (4H, m), 7.26 - 7.30 (2H, m), 7.46 - 7.54 (12H, m), 7.94 - 7.98 (8H, m), 8.32 - 8.40 (8H, m).

[0143] Preparation Example 7:

[0144]

[0145] Synthesis of Intermediate 49-1: The synthesis method is the same as that of Intermediate 1-1, and white solid 49-1 is obtained (yield: 65.9%)

[0146] Synthesis of Intermediate 49-2: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 49-1 is obtained (yield: 75.3%).

[0147] Synthesis of Compound 49: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Compound 49 is obtained (yield: 75.0%).

[0148] Mass spectrometry: C51H30N6S2, theoretical value: 790.20, measured value: 790.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.20 - 7.25 (1H, m), 7.26 - 7.28 (1H, m), 7.31 - 7.38 (2H, m), 7.45 - 7.53 (7H, m), 7.54 - 7.59 (5H, m), 7.88 - 7.89 (1H, m), 7.91 - 7.96 (9H, m), 8.24 - 8.29 (2H, m), 8.72 - 8.74 (2H, m).

[0149] Preparation Example 8:

[0150]

[0151] Synthesis of Intermediate 58-1: In a 500 ml three-necked flask, under nitrogen protection, successively add Intermediate K-2 (67 mmol), phenylboronic acid (67 mmol), toluene (320 ml), ethanol (50 ml), water (25 ml), and start stirring. Then successively add potassium carbonate (168 mmol) and tetrakis(triphenylphosphine)palladium (0.67 mmol), heat to reflux for 6 h. When HPLC detects that the raw materials have basically reacted, add deionized water (250 ml) to the reaction solution, stir for 10 min, take the organic phase, and dry it with anhydrous magnesium sulfate. Filter the desiccant, rotary evaporate the organic solvent, and separate the residue by silica gel column chromatography to obtain a white solid (yield: 67.7%).

[0152] Synthesis of Intermediate 58-2: The synthesis method is the same as that of Intermediate 58-1, and a white solid is obtained (yield: 68.3%).

[0153] Synthesis of Compound 58: In a 500 ml three-necked flask, under nitrogen protection, add Intermediate 58-2 (34 mmol), Intermediate 1-1 (68 mmol), toluene (180 ml), ethanol (32 ml), water (16 ml), PdCl 2 (dppf) 3 (0.68 mmol), 20 ml of an aqueous solution containing potassium carbonate (119 mmol), start stirring and heat to 90 °C for overnight reaction. After 20 h, cool the reaction to 40 °C, filter to obtain the crude product, wash the crude product with water (250 ml), and then wash it with ethanol (250 ml) to obtain a gray solid. Separate the pale yellow solid Compound 58 by silica gel column chromatography (yield: 81.5%).

[0154] Mass spectrometry: C61H38N8O2, theoretical value: 914.31, measured value: 914.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.40 - 7.45 (4H, m), 7.47 - 7.53 (12H, m), 7.57 - 7.70 (6H, m), 8.15 - 8.21 (4H, m), 8.32 - 8.40 (8H, m), 8.53 - 8.59 (4H, m).

[0155] Preparation Example 9:

[0156]

[0157] Synthesis of Intermediate 74-1: The synthesis method was the same as that of Intermediate 58-1, and a white solid was obtained (yield: 75.4%).

[0158] Synthesis of Intermediate 74-2: The synthesis method was the same as that of Intermediate 58-1, and a white solid was obtained (yield: 74.1%).

[0159] Synthesis of Compound 74: The synthesis method was the same as that of Compound 58, and a pale yellow solid was obtained (yield: 75.3%).

[0160] Mass spectrometry: C63H40N8O2, theoretical value: 940.33, measured value: 940.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 2.61 - 2.63 (6H, s), 7.22 - 7.24 (2H, m), 7.26 - 7.28 (2H, m), 7.47 - 7.53 (12H, m), 7.66 - 7.70 (2H, m), 7.94 - 8.05 (6H, m), 8.33 - 8.39 (8H, m), 8.45 - 8.46 (2H, m).

[0161] Preparation Example 10:

[0162]

[0163] Synthesis of Intermediate 82-1: The synthesis method was the same as that of Intermediate 58-1, and a white solid was obtained (yield: 74.6%).

[0164] Synthesis of Intermediate 82-2: The synthesis method was the same as that of Intermediate 58-1, and a white solid was obtained (yield: 74.8%).

[0165] Synthesis of Intermediate 82-3: The synthesis method was the same as that of Intermediate 1-1, and a white solid was obtained (yield: 72.9%).

[0166] Synthesis of Compound 82: The synthesis method is the same as that of Compound 58, and a pale yellow solid is obtained (yield: 73.6%).

[0167] Mass spectrum: C59H36N6S2, theoretical value: 892.24, measured value: 892.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.38 - 7.43 (4H, m), 7.45 - 7.56 (14H, m), 7.58 - 7.63 (4H, m), 7.73 - 7.81 (2H, m), 7.97 - 8.06 (5H, m), 8.06 - 8.13 (3H, m), 8.28 - 8.36 (4H, m).

[0168] Preparation Example 11:

[0169]

[0170] Synthesis of Intermediate 96 - 1: The synthesis method is the same as that of Intermediate 58 - 1, and a white solid is obtained (yield: 78.2%).

[0171] Synthesis of Intermediate 96 - 2: The synthesis method is the same as that of Intermediate 58 - 1, and a white solid is obtained (yield: 75.4%).

[0172] Synthesis of Intermediate 96 - 3: The synthesis method is the same as that of Intermediate 1 - 1, and a white solid is obtained (yield: 70.6%).

[0173] Synthesis of Compound 96: The synthesis method is the same as that of Compound 58, and a pale yellow solid is obtained (yield: 72.3%).

[0174] Mass spectrum: C61H38N6S2, theoretical value: 918.26, measured value: 918.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 2.72 - 2.76 (6H, s), 7.28 - 7.36 (4H, m), 7.55 - 7.71 (6H, m), 7.76 - 7.83 (6H, m), 7.86 - 7.92 (4H, m), 8.00 - 8.11 (6H, m), 8.24 - 8.25 (2H, m), 8.83 - 8.89 (4H, m).

[0175] Preparation Example 12:

[0176]

[0177] Synthesis of Intermediate 97 - 1: The synthesis method is the same as that of Intermediate 58 - 1, and a white solid is obtained (yield: 76.7%).

[0178] Synthesis of Compound 97: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid was obtained (yield: 74.5%).

[0179] Mass spectrometry: C40H25N5O2, theoretical value: 607.20, measured value: 607.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.05 - 7.12 (4H, m), 7.14 - 7.25 (4H, m), 7.26 - 7.30 (2H, m), 7.46 - 7.53 (6H, m), 7.59 - 7.70 (3H, m), 8.13 - 8.21 (2H, m), 8.32 - 8.40 (4H, m).

[0180] Preparation Example 13:

[0181]

[0182] Synthesis of Intermediate 121-1: The synthesis method was the same as that of Intermediate 58-1, and a white solid was obtained (yield: 76.3%).

[0183] Synthesis of Compound 121: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid was obtained (yield: 82.1%).

[0184] Mass spectrometry: C46H27N5O2, theoretical value: 681.22, measured value: 681.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.17 - 7.21 (1H, m), 7.23 - 7.24 (1H, m), 7.27 - 7.35 (2H, m), 7.43 - 7.50 (6H, m), 7.57 - 7.66 (3H, m), 7.84 - 7.89 (2H, m), 7.91 - 7.94 (4H, m), 8.01 - 8.06 (2H, m), 8.11 - 8.18 (2H, m), 8.28 - 8.36 (4H, m).

[0185] Preparation Example 14:

[0186]

[0187] Synthesis of Intermediate 137-1: The synthesis method was the same as that of Intermediate 58-1, and a white solid was obtained (yield: 75.3%).

[0188] Synthesis of Compound 137: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid was obtained (yield: 82.6%).

[0189] Mass spectrometry: C46H29N5S2, theoretical value: 715.19, measured value: 715.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.03 - 7.10 (4H, m), 7.11 - 7.22 (4H, m), 7.24 - 7.27 (2H, m), 7.44 - 7.54 (9H, m), 7.91 - 7.95 (4H, m), 7.96 - 8.04 (2H, m), 8.29 - 8.37 (4H, m).

[0190] Preparation Example 15:

[0191]

[0192] Synthesis of Intermediate 159-1: The synthesis method is the same as that of Intermediate 58-1, and a white solid is obtained (yield: 78.3%).

[0193] Synthesis of Compound 159: The synthesis method is the same as that of Intermediate 58-1, and a pale yellow solid is obtained (yield: 82.9%).

[0194] Mass spectrometry: C51H30N4S2, theoretical value: 762.19, measured value: 762.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.20 - 7.25 (1H, m), 7.26 - 7.28 (1H, m), 7.31 - 7.38 (2H, m), 7.47 - 7.64 (9H, m), 7.66 - 7.73 (2H, m), 7.75 - 7.83 (1H, m), 7.87 - 7.97 (4H, m), 8.00 - 8.06 (2H, m), 8.07 - 8.15 (5H, m), 8.26 - 8.28 (1H, m), 8.31 - 8.39 (2H, m).

[0195] Preparation Example 16:

[0196]

[0197] Synthesis of Intermediate 171-1: The synthesis method is the same as that of Intermediate 1-1, and a pale yellow solid is obtained (yield: 57.7%).

[0198] Synthesis of Intermediate 171-2: The synthesis method is the same as that of Intermediate 58-1, and a white solid is obtained (yield: 76.9%).

[0199] Synthesis of Intermediate 171-3: The synthesis method is the same as that of Intermediate 58-1, and a white solid is obtained (yield: 78.6%).

[0200] Synthesis of Compound 171: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid was obtained (yield: 80.3%).

[0201] Mass spectrometry: C50H37N5O2, theoretical value: 739.29, measured value: 739.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 1.21 - 1.29 (6H, m), 2.59 - 2.69 (4H, m), 7.08 - 7.12 (2H, m), 7.17 - 7.24 (4H, m), 7.26 - 7.30 (3H, m), 7.37 - 7.53 (8H, m), 7.72 - 7.78 (4H, m), 7.93 - 7.99 (4H, m), 8.53 - 8.59 (2H, m).

[0202] Preparation Example 17:

[0203]

[0204] Synthesis of Intermediate 197-1: The synthesis method was the same as that of Intermediate 58-1, and a white solid was obtained (yield: 75.8%).

[0205] Synthesis of Intermediate 197-2: The synthesis method was the same as that of Intermediate 58-1, and a white solid was obtained (yield: 73.6%).

[0206] Synthesis of Compound 197: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid was obtained (yield: 78.1%).

[0207] Mass spectrometry: C46H27N5S2, theoretical value: 713.17, measured value: 713.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.20 - 7.25 (1H, m), 7.26 - 7.28 (1H, m), 7.31 - 7.38 (1H, m), 7.48 - 7.54 (11H, m), 7.66 - 7.71 (1H, m), 7.88 - 7.93 (1H, m), 7.99 - 8.07 (4H, m), 8.10 - 8.15 (1H, m), 8.32 - 8.40 (4H, m), 8.56 - 8.58 (1H, m), 8.65 - 8.70 (1H, m).

[0208] Device Example 1

[0209] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol (volume ratio 1:1), baked in a clean environment until water was completely removed, cleaned with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam;

[0210] Place the above-mentioned glass substrate with an anode in a vacuum chamber and evacuate it to 1×10 -5 Pa. Vacuum deposit HAT-CN on the above-mentioned anode layer film as a hole injection layer at a deposition rate of 0.1 nm / s and a total deposited film thickness of 1 nm; then deposit a hole transport layer NPB at a deposition rate of 0.1 nm / s and a thickness of 60 nm;

[0211] Vacuum deposit the electron blocking layer TCTA of the device on the hole transport layer at a deposition rate of 0.1 nm / s and a total deposited film thickness of 10 nm;

[0212] Vacuum deposit the light-emitting layer of the device on the electron blocking layer. The light-emitting layer includes a host material and a guest material. Using the method of co-evaporation from multiple sources, adjust the deposition rate of the host material DIC-TRZ to 0.1 nm / s, and the deposition rate of the guest material Ir(ppy) 3 Set at a 10% ratio of the deposition rate, and the total deposited film thickness is 30 nm;

[0213] Vacuum deposit the electron transport layer of the device on the light-emitting layer. Using the method of co-evaporation from multiple sources, adjust the deposition rates of both ET-1 and Compound 1 to 0.1 nm / s, and the total deposited film thickness is 30 nm;

[0214] Vacuum deposit LiF with a thickness of 0.5 nm as an electron injection layer and an Al layer with a thickness of 150 nm as the cathode of the device on the electron transport layer (ETL).

[0215] The molecular structures involved are as follows:

[0216]

[0217] Device Examples 2-14

[0218] Prepare the organic electroluminescent devices of Device Examples 2-14 using a method similar to that of Device Example 1. The difference is that Compound 1 in Device Example 1 is replaced with the compounds shown in Table 1.

[0219] Device Comparative Examples 1-2

[0220] Prepare the organic electroluminescent devices of Device Comparative Examples 1-2 using a method similar to that of Device Example 1. The difference is that Compound 1 in Device Example 1 is replaced with the following compounds Ref-1 and Ref-2, respectively.

[0221]

[0222] Test Example 1

[0223] At a brightness of 10000 cd / m 2Under the above conditions, the driving voltages and current efficiencies of the organic light-emitting devices prepared in Device Examples 1 to 14 and Device Comparative Examples 1 to 2 were measured, and the results are shown in Table 1.

[0224] Table 1

[0225]

[0226]

[0227] The above results show that, compared with the comparative examples, the organic compounds of the present invention have a lower driving voltage and a higher device luminous efficiency when applied to organic light-emitting devices.

[0228] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A nitrogen-containing organic compound, the structure of which is shown in Formula I or II: In Formula I and II, X and Y are the same or different and are each independently oxygen or sulfur; R 1 、R 2 、R 3 and R 4 are the same or different and each independently is H, C1-C6 alkyl, C6-C40 aryl or C3-C40 heteroaryl, and one or more of R 1 、R 2 、R 3 and R 4 is / are C3-C40 heteroaryl having a nitrogen heterocycle selected from one or more of pyrimidine ring, quinoxaline ring, quinazoline ring and triazine ring, and the C3-C40 heteroaryl having a nitrogen heterocycle is selected from the following groups: Ar 1 and Ar 2 each independently selected from phenyl, naphthyl, anthracenyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, phenyl-substituted naphthyl, phenyl-substituted anthracenyl, phenyl-substituted biphenyl, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothiophenyl, naphthyl-substituted phenyl, naphthyl-substituted naphthyl, naphthyl-substituted anthracenyl, naphthyl-substituted biphenyl, naphthyl-substituted dibenzofuranyl, naphthyl-substituted dibenzothiophenyl; L 1 、L 2 、L 3 and L 4 are the same or different and each independently selected from absent, C6-C20 arylene and C3-C20 heteroarylene, When L 3 and L 4 do not exist, R 3 and R 4 are not H.

2. The nitrogen-containing organic compound according to claim 1, characterized in that R 1 、R 2 、R 3 and R 4 Two or three of R, R, R and R are each independently H, C1-C6 alkyl or C6-C40 aryl, and the remaining two or one is C3-C40 heteroaryl having a nitrogen heterocycle.

3. The nitrogen-containing organic compound according to claim 1, characterized in that R 1 and / or R 2 is a C3-C40 heteroaryl having a nitrogen heterocycle; and / or, R 3 and / or R 4 is a C3-C40 heteroaryl having a nitrogen heterocycle.

4. The nitrogen-containing organic compound according to any one of claims 1-3, characterized in that R 1 and / or R 2 is hydrogen; R 3 and / or R 4 is a C3-C40 heteroaryl having a nitrogen heterocycle; and / or L 1 、L 2 、L 3 and L 4 each independently is absent, phenylene, naphthylene, anthrylene, phenanthrylene, biphenylene, dibenzothiophenylene or dibenzofuranylene.

5. The nitrogen-containing organic compound according to any one of claims 1-3, characterized in that the heteroatoms in the heteroaryl group are selected from one or more of nitrogen, oxygen, sulfur, phosphorus and silicon; the heteroatoms in the heteroarylene group are selected from one or more of nitrogen, oxygen, sulfur, phosphorus and silicon.

6. A nitrogen-containing organic compound, characterized in that the nitrogen-containing organic compound is selected from the following compounds:

7. Use of the nitrogen-containing organic compound according to any one of claims 1-6 in an organic electroluminescent device.

8. The use according to claim 7, characterized in that in the organic electroluminescent device, the nitrogen-containing organic compound is used as an electron transport material.

9. An organic electroluminescent device comprising the nitrogen-containing organic compound according to any one of claims 1-6.

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