Nitrogen-containing fused ring compounds and their applications in organic electroluminescent devices

Abstract

The present invention relates to a nitrogen-containing fused ring compound and its application in an organic electroluminescent device. The structure of the nitrogen-containing fused ring compound is shown in Formula I. In Formula I, X and Y are the same or different and are each independently oxygen or sulfur; Z is oxygen, sulfur or N-R, where R is an alkyl group or an aryl group; R 1 、R 2 、R 3 and R 4 are the same or different and are each independently H, an alkyl group, an aryl group or a heteroaryl group, and R 1 、R 2 、R 3 and R 4 one or more of them are heteroaryl groups having a nitrogen heterocycle, and the nitrogen-containing heterocycle is selected from one or more of a pyrimidine ring, a quinoxaline ring, a quinazoline ring and a triazine ring. When L 3 and L 4 do not exist, R 3 and R 4 are not H; L 1 、L 2 、L 3 and L 4 are the same or different and are each independently selected from non-existence, arylene and heteroarylene. When the compound of the present invention is applied to an organic electroluminescent device, it has a lower driving voltage and a higher device luminous efficiency.

Description

Technical Field

[0001] The present invention relates to the field of organic electroluminescent devices, and particularly to a nitrogen-containing fused ring compound and its application in organic electroluminescent devices. 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 under the drive of a voltage above 100V, but due to the high drive 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. By vacuum thermal evaporation, a double-layer organic light-emitting diode (OLED) was prepared. At a drive voltage less than 10V, the external quantum efficiency of the aforementioned OLED reached 1%, and the brightness was as high as 1000 Cd / m2, setting off a research boom in OLEDs and promoting further research on organic electroluminescent materials.

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

[0004] Currently, OLEDs or screens still have the defects of high drive 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 drive voltage and luminous efficiency of devices. Therefore, the market urgently needs to develop high-performance electron transport materials to reduce the drive voltage of devices and improve the luminous efficiency of devices. Summary of the Invention

[0006] The purpose of the present invention is to provide a novel nitrogen-containing fused ring compound to overcome the defects of high drive voltage and low luminous efficiency of OLEDs provided by the prior art.

[0007] To this end, in the first aspect of the present application, a nitrogen-containing fused ring compound is provided, and its structure is shown in Formula I:

[0008]

[0009] X and Y are the same or different and are each independently oxygen or sulfur; Z is oxygen, sulfur or N-R, where R is an alkyl or aryl group; R 1 、R2 , R 3 and R 4 are the same or different and are each independently H, alkyl, aryl or heteroaryl, and R 1 , R 2 , R 3 and R 4 one or more of which are 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 are each independently selected from absent, arylene and heteroarylene. When L 3 and L 4 are absent, R 3 and R 4 are not H.

[0010] 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 bonded 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 fused ring compound of the present invention is as shown in the following formula IA:

[0011]

[0012] 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 R 1 , R 2 , R 3 and R 4 one or more of which are C3-C40 heteroaryl having a nitrogen heterocycle selected from one or more of a pyrimidine ring, a quinoxaline ring, a quinazoline ring and a triazine ring.

[0013] According to some embodiments of the present invention, R 1 , R 2 , R 3 and R 4Each independently is H, a C1-C6 alkyl group, a C6-C20 aryl group, or a C3-C40 heteroaryl group, and R 1 、R 2 、R 3 and R 4 One or more of 4 is a C3-C40 heteroaryl group having a nitrogen heterocycle, and the nitrogen-containing heterocycle is selected from one or more of a pyrimidine ring, a quinoxaline ring, a quinazoline ring, and a triazine ring.

[0014] According to some embodiments of the present invention, L 1 、L 2 、L 3 and L 4 Each independently is selected from absent, a C6-C20 arylene group, and a C3-C20 heteroarylene group. According to some embodiments of the present invention, L 1 、L 2 、L 3 and L 4 Each independently is absent, a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a biphenylene group, a dibenzothiophene group, or a dibenzofuran group.

[0015] According to some embodiments of the present invention, R is a C1-C6 alkyl group or a C6-C20 aryl group. In some embodiments, R is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, or a biphenyl group.

[0016] In some embodiments, the structure of the nitrogen-containing fused-ring compound is as shown in the following formula:

[0017]

[0018]

[0019] In some embodiments, the structure of the nitrogen-containing fused-ring compound is as shown in the following formula:

[0020]

[0021] According to some embodiments of the present invention, R 1 and / or R 2 is a C3-C40 heteroaryl group having a nitrogen heterocycle.

[0022] According to some embodiments of the present invention, R 3 and / or R 4 is a C3-C40 heteroaryl group having a nitrogen heterocycle.

[0023] According to some embodiments of the present invention, R 1 、R 2 、R 3 and R 4At most two of them are hydrogen. In some embodiments, R 1 and R 2 are hydrogen.

[0024] According to 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.

[0025] 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; the heteroatoms in the heteroarylene are selected from one or more of nitrogen, oxygen, sulfur, phosphorus and silicon.

[0026] According to some embodiments of the present invention, the heteroaryl containing a nitrogen heterocycle is selected from the following groups:

[0027]

[0028] wherein Ar 1 and Ar 2 are each independently selected from aryl such as C6-C40 aryl and heteroaryl such as C3-C40 heteroaryl, preferably selected from phenyl, biphenyl, naphthyl, dibenzofuranyl and dibenzothiophenyl.

[0029] According to some embodiments of the present invention, Ar 1 and Ar 2 are each independently selected from C6-C20 aryl and C3-C30 heteroaryl. Preferably, 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.

[0030] The nitrogen-containing fused-ring compound described in the present invention can specifically be selected from the following compounds:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040] In a second aspect, the present invention provides the use of the nitrogen-containing fused-ring 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.

[0041] 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 nitrogen-containing fused-ring compound described above.

[0042] 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.

[0043] 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 material used in the present invention is 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.

[0044] 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 thin 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.

[0045] 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.

[0046] 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:

[0047]

[0048] 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, indenoindole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine.

[0049] According to some embodiments of the present invention, the material for forming the electron blocking layer is not particularly limited. Generally, a compound that can satisfy the following first and / or second conditions can be considered for use:

[0050] 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.

[0051] 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.

[0052] 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 spirobifluoreneamine (such as SpMA2), and the structures of some electron blocking materials are similar to those of hole injection materials and hole transport materials.

[0053] 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.

[0054] 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.

[0055] 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, sulfonyl derivatives, cyano derivatives, and xanthene derivatives, but not limited thereto.

[0056] In some preferred embodiments of the present invention, the sulfonyl derivatives have the general formula shown below:

[0057]

[0058] The ketone derivatives have the general formula shown below:

[0059]

[0060] In the general formulas of the above sulfonyl 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-carbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine, or triazine, and groups represented by their substituents.

[0061] According to some embodiments of the present invention, the material of the hole blocking layer may also preferably be a compound satisfying the following first and / or second conditions:

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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 the 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. Examples of the electron injection layer material include LiF, CsF, Cs 2 CO 3 , LiQ, but not limited thereto.

[0066] According to some embodiments of the present invention, the cathode material is usually preferably a material with a small work function, which can enable electrons to be smoothly injected 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.

[0067] The present invention has at least the following specific advantages:

[0068] 1. The parent nucleus of the present invention contains an oxazole or thiazole structure, which belongs to an electron-rich group and has excellent electron transport ability, 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.

[0069] 2. The parent nucleus of the present invention is substituted with a strong electron-withdrawing group, which reduces the LUMO energy level of the compound, that is, reduces the injection barrier. When the compound of the present invention is applied to an organic electroluminescent device, it can effectively reduce the driving voltage of the device.

[0070] 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 increasing the service life of the material at the same time. Specific Embodiments

[0071] The present invention has no particular limitation on the specific method for preparing the foregoing compounds. Those skilled in the art can obtain the foregoing compounds 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 compounds 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 to the present invention.

[0072] 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 mentioned below means 25 ± 1°C.

[0073] Preparation Example 1:

[0074]

[0075] 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-formyl oxazole (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 then filtered to remove the desiccant, obtaining a filtrate. 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%).

[0076] Synthesis of Intermediate B: The synthesis method was the same as that of Intermediate A, and white solid B was obtained (yield: 71.3%).

[0077] Synthesis of Intermediate C: In a 500 ml three-necked flask, Intermediate A (46 mmol) was added to dichloromethane (130 ml) and stirred. At room temperature, Br 2 (92 mmol) was added dropwise. After the addition was completed, the mixture was allowed to react overnight at room temperature. 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 solvent was removed under reduced pressure by rotary evaporation to obtain a residue, which was purified by column chromatography to obtain white solid C (yield: 46.8%).

[0078] Synthesis of Intermediate D: The synthesis method was the same as that of Intermediate C, and white solid D was obtained (yield: 45.2%).

[0079] 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%).

[0080] Synthesis of Intermediate F: The synthesis method was the same as that of Intermediate E, and white solid F was obtained (yield: 77.9%).

[0081] 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 monitored 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%).

[0082] Synthesis of Intermediate H: The synthesis method was the same as that of Intermediate G, and white solid H was obtained (yield: 78.6%).

[0083] Preparation Example 2:

[0084]

[0085] Synthesis of Intermediate I: In a 500 ml three-necked flask, 1-iodo-2-phenoxy-benzene derivative 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, and Intermediate G was added at -78 °C. After addition, it was kept for 1 hour, and then the temperature was raised to room temperature. After 1 hour, the reaction was completed. Water was added to quench the reaction. The organic phase was extracted three times with chloroform, dried over anhydrous sodium sulfate, filtered to remove the desiccant to obtain the filtrate, and concentrated by rotary evaporation to obtain the crude product. The crude product was dissolved in 1,2-dichloroethane, the temperature was lowered to 0 °C, and trifluoromethanesulfonic acid was added dropwise. After the addition was completed, it was heated to reflux for 2 hours, cooled to room temperature, and the solution was adjusted to neutral with an aqueous NaHCO3 solution. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and white solid I was obtained by column chromatography.

[0086] Synthesis of Intermediate J: The synthesis method was the same as that of Intermediate I, and white solid J was obtained.

[0087] Preparation Example 3:

[0088]

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

[0090] Synthesis of Intermediate L: The synthesis method was the same as that of Intermediate I, and white solid L was obtained.

[0091] Preparation Example 4:

[0092]

[0093] Synthesis of Intermediate M: The synthesis method was the same as that of Intermediate I, and white solid M was obtained.

[0094] Synthesis of Intermediate N: The synthesis method is the same as that of Intermediate I, and white solid N is obtained.

[0095] Synthesis of the specific parent nucleus:

[0096]

[0097] Mass spectrometry: C19H18BrClN2O3, theoretical value: 425.94, measured value: 425.9.

[0098] Elemental analysis: theoretical value: C 53.36%, H: 1.89%, N: 6.55%; measured value: C: 53.40%, H: 1.85%, N: 6.50%.

[0099]

[0100] Mass spectrometry: C19H6BrCl3N2O3, theoretical value: 493.86, measured value: 493.9.

[0101] Elemental analysis: theoretical value: C: 45.96%, H: 1.22%, N: 5.64%; measured value: C: 45.95%, H: 1.30%, N: 5.65%.

[0102]

[0103] Mass spectrometry: C19H8BrClN2OS2, theoretical value: 457.89, measured value: 457.9.

[0104] Elemental analysis: theoretical value: C: 49.64%, H: 1.75%, N: 6.09%; measured value: C 49.65%, H: 1.80%, N: 6.00%.

[0105]

[0106] Mass spectrometry: C19H7BrCl2N2OS2, theoretical value 491.86, measured value: 491.9.

[0107] Elemental analysis: theoretical value: C: 46.18%, H: 1.43%, N: 5.67%; measured value: C: 46.20%, H: 1.40%, N: 5.70%.

[0108]

[0109] Mass spectrometry: C19H8BrClN2O2S, theoretical value: 441.92, measured value: 441.9.

[0110] Elemental analysis: Theoretical values: C: 51.43%, H: 1.82%, N: 6.31%; Measured values: C: 51.45%, H: 1.90%, N: 6.30%.

[0111]

[0112] Mass spectrometry: C19H6BrCl3N2O2S, Theoretical value: 509.84, Measured value: 509.8

[0113] Elemental analysis: Theoretical values: C: 44.52%, H: 1.18%, N: 5.47%; Measured values: C: 44.56%, H: 1.21%, N: 5.45%.

[0114]

[0115] Mass spectrometry: C19H7BrCl2N2O2S, Theoretical value: 475.88, Measured value: 475.9

[0116] Elemental analysis: Theoretical values: C: 47.73%, H: 1.48%, N: 5.86%; Measured values: C: 47.75%, H: 1.50%, N: 5.85%.

[0117]

[0118] Mass spectrometry: C19H6BrCl3N2O2S, Theoretical value: 509.84, Measured value: 509.9

[0119] Elemental analysis: Theoretical values: C: 44.52%, H: 1.18%, N: 5.47%; Measured values: C: 44.55%, H: 1.15%, N: 5.50%.

[0120]

[0121] Mass spectrometry: C19H8BrClN2S3, Theoretical value: 473.87, Measured value: 473.9

[0122] Elemental analysis: Theoretical values: C: 47.96%, H1.69%, N: 5.89%; Measured values: C: 48.00%, H: 1.51%, N: 5.91%.

[0123]

[0124] Mass spectrometry: C25H13BrClN3O2, Theoretical value: 500.99, Measured value: 501.0

[0125] Elemental analysis: Theoretical values: C 59.73%, H: 2.61%, N: 8.36%; Measured values: C: 59.75%, H: 2.60%, N: 8.35%.

[0126]

[0127] Mass spectrometry: C25H11BrCl3N3O2, Theoretical value: 568.91, Measured value: 569.0.

[0128] Elemental analysis: Theoretical values: C: 52.53%, H: 1.94%, N: 7.35%; Measured values: C: 52.49%, H: 2.02%, N: 7.26%.

[0129]

[0130] Mass spectrometry: C25H13BrClN3S2, Theoretical value: 532.94, Measured value: 532.9.

[0131] Elemental analysis: Theoretical values: C: 56.14%, H: 2.45%, N: 7.86%; Measured values: C: 56.20%, H: 2.42%, N: 7.87%.

[0132] Preparation Example 5:

[0133]

[0134] 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 [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (0.62 mmol), heat up to reflux and react for 4 h. After HPLC detection shows that the raw materials have reacted completely, cool the reaction solution to room temperature, and then rotary evaporate the reaction solution under reduced pressure to obtain the crude product. Dissolve the crude product in toluene solvent, heat and stir, heat up to reflux, and decolorize through a silica gel column. Rotary evaporate the filtrate under reduced pressure until there is a small amount of solvent left, then add ethanol (250 ml) for slurrying, and recrystallize with toluene / ethanol to obtain a white solid (yield: 53.2%).

[0135] Synthesis of Intermediate 1-2: In a 500 ml three-necked flask, under nitrogen protection, add Intermediate 1-1 (23 mmol), Intermediate I-1 (23 mmol), toluene (100 ml), ethanol (20 ml), water (10 ml), PdCl 2 (dppf) 3(0.23 mmol), containing potassium carbonate (58 mmol), was stirred and heated to 90 °C for overnight reaction. After 20 h, the reaction was cooled to 40 °C, and the crude product was obtained by filtration. The crude product was washed with water (200 ml), and then washed with ethanol (200 ml) to obtain the crude product. The light yellow solid intermediate 1-2 was obtained by silica gel column chromatography (yield: 83.6%).

[0136] Synthesis of Compound 1: The synthesis method was the same as that of intermediate 1-2, and the light yellow solid compound 1 was obtained (yield: 82.4%).

[0137] Mass spectrometry: C49H28N8O3, theoretical value: 776.23, measured value: 776.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.96 - 7.04 (2H, m), 7.14 - 7.22 (4H, m), 7.28 - 7.35 (2H, m), 7.47 - 7.53 (12H, m), 8.32 - 8.40 (8H, m).

[0138] Preparation Example 6:

[0139]

[0140] Synthesis of Intermediate 18-1: The synthesis method was the same as that of intermediate 1-1, and the white solid intermediate 18-1 was obtained (yield: 55.3%).

[0141] Synthesis of Intermediate 18-2: The synthesis method was the same as that of intermediate 1-2, and the light yellow solid intermediate 18-2 was obtained (yield: 85.1%).

[0142] Synthesis of Compound 18: The synthesis method was the same as that of intermediate 1-2, and the light yellow solid compound 18 was obtained (yield: 80.6%).

[0143] Mass spectrometry: C63H38N6O2S, theoretical value: 942.28, measured value: 942.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.96 - 7.02 (4H, m), 7.21 - 7.22 (2H, m), 7.28 - 7.45 (6H, m), 7.46 - 7.51 (6H, m), 7.52 - 7.57 (3H, m), 7.65 - 7.69 (2H, m), 7.71 - 7.75 (4H, m), 7.90 - 7.96 (9H, m), 8.38 - 8.39 (2H, s).

[0144] Preparation Example 7:

[0145]

[0146] Synthesis of Intermediate 61-1: The synthesis method is the same as that of Intermediate 1-2, and pale yellow solid Intermediate 61-2 is obtained (yield: 86.2%).

[0147] Synthesis of Compound 61: The synthesis method is the same as that of Intermediate 1-2, and pale yellow solid Compound 61 is obtained (yield: 82.3%).

[0148] Mass spectrometry: C61H36N8OS2, theoretical value: 960.25, measured value: 960.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.96 - 7.04 (2H, m), 7.23 - 7.41 (4H, m), 7.27 - 7.35 (2H, m), 7.46 - 7.54 (12H, m), 7.94 - 7.97 (8H, s), 8.31 - 8.40 (8H, m).

[0149] Preparation Example 8:

[0150]

[0151] Synthesis of Intermediate 73-1: The synthesis method is the same as that of Intermediate 1-2, and pale yellow solid Intermediate 73-1 is obtained (yield: 84.7%).

[0152] Synthesis of Compound 73: The synthesis method is the same as that of Intermediate 1-2, and pale yellow solid Compound 73 is obtained (yield: 82.4%).

[0153] Mass spectrometry: C69H43N7S2, theoretical value: 1033.30, measured value: 1033.4. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.86 - 7.00 (3H, m), 7.01 - 7.07 (2H, m), 7.11 - 7.21 (8H, m), 7.41 - 7.55 (12H, m), 7.87 - 7.93 (16H, m), 8.18 - 8.20 (2H, s).

[0154] Preparation Example 9:

[0155]

[0156] Synthesis of Intermediate 76-1: The synthesis method is the same as that of Intermediate 1-2, and pale yellow solid Intermediate 76-1 is obtained (yield: 86.7%).

[0157] Synthesis of Intermediate 76-2: The synthesis method is the same as that of Intermediate 1-2, and pale yellow solid Intermediate 76-2 is obtained (yield: 83.5%).

[0158] Synthesis of Compound 76: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid compound 76 was obtained (yield: 80.6%).

[0159] Mass spectrometry: C61H36N8O3, theoretical value: 928.29, measured value: 928.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 7.31 - 7.33 (2H, d), 7.37 - 7.38 (1H, s), 7.40 - 7.41 (1H, s), 7.47 - 7.53 (12H, m), 7.60 - 7.69 (6H, m), 8.14 - 8.21 (4H, m), 8.26 - 8.27 (1H, d), 8.29 - 8.30 (1H, d), 8.32 - 8.40 (8H, m).

[0160] Preparation Example 10:

[0161]

[0162] Synthesis of Intermediate 96-1: The synthesis method was the same as that of Intermediate 1-1, and a pale yellow solid Intermediate 96-1 was obtained (yield: 57.3%).

[0163] Synthesis of Intermediate 96-2: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid Intermediate 96-2 was obtained (yield: 85.3%).

[0164] Synthesis of Intermediate 96-3: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid Intermediate 96-3 was obtained (yield: 84.8%).

[0165] Synthesis of Compound 96: The synthesis method was the same as that of Intermediate 1-2, and a pale yellow solid compound 96 was obtained (yield: 80.3%).

[0166] Mass spectrometry: C53H34N6O2S, theoretical value: 818.25, measured value: 818.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 2.60 - 2.63 (6H, s), 7.53 - 7.44 (10H, m), 7.54 - 7.57 (4H, m), 7.57 - 7.61 (4H, m), 7.91 - 7.97 (8H, m), 8.22 - 8.24 (2H, s).

[0167] Preparation Example 11:

[0168]

[0169] Synthesis of Intermediate 105-1: The synthesis method is the same as that of Intermediate 1-1, and light yellow solid Intermediate 105-1 is obtained (yield: 56.8%).

[0170] Synthesis of Intermediate 105-2: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 105-2 is obtained (yield: 84.7%).

[0171] Synthesis of Intermediate 105-3: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 105-3 is obtained (yield: 83.7%).

[0172] Synthesis of Compound 105: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Compound 105 is obtained (yield: 78.5%).

[0173] Mass spectrometry: C55H35N7O2, theoretical value: 825.29, measured value: 825.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 2.62 - 2.63 (6H, s), 6.98 - 7.02 (1H, m), 7.07 - 7.09 (2H, m), 7.22 - 7.24 (1H, d), 7.35 - 7.37 (2H, d), 7.47 - 7.51 (2H, m), 7.52 - 7.56 (2H, m), 7.63 - 7.67 (4H, m), 7.76 - 7.78 (3H, m), 7.79 - 7.81 (6H, m), 7.90 - 7.92 (2H, m), 7.96 - 7.98 (2H, m), 8.12 - 8.14 (2H, m).

[0174] Preparation Example 12:

[0175]

[0176] Synthesis of Intermediate 119-1: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 119-1 is obtained (yield: 85.3%).

[0177] Synthesis of Intermediate 119-2: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 119-2 is obtained (yield: 83.7%).

[0178] Synthesis of Compound 119: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Compound 119 is obtained (yield: 79.8%).

[0179] Mass spectrometry: C51H34N6S3, theoretical value: 826.20, measured value: 826.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 1.31 - 1.35 (6H, m), 3.02 - 3.06 (4H, m), 7.22 - 7.24 (2H, d), 7.47 - 7.51 (2H, m), 7.52 - 7.56 (2H, m), 7.63 - 7.67 (4H, m), 7.78 - 7.71 (6H, m), 8.00 - 8.04 (4H, m), 8.12 - 8.14 (2H, m), 8.29 - 8.31 (2H, m).

[0180] Preparation Example 13:

[0181]

[0182] Synthesis of Intermediate 125-1: The synthesis method was the same as that of Intermediate 1-2, and pale yellow solid Intermediate 125-1 was obtained (yield: 84.5%).

[0183] Synthesis of Compound 125: The synthesis method was the same as that of Intermediate 1-2, and pale yellow solid Compound 125 was obtained (yield: 81.6%).

[0184] Mass spectrometry: C40H23N5O3, theoretical value: 621.18, measured value: 621.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.93 - 7.00 (2H, m), 7.11 - 7.12 (1H, d), 7.14 - 7.15 (2H, m) 7.17 - 7.19 (1H, d), 7.24 - 7.31 (2H, m), 7.43 - 7.49 (6H, m), 7.57 - 7.65 (3H, m), 8.11 - 8.16 (2H, m), 8.29 - 8.34 (4H, m).

[0185] Preparation Example 14:

[0186]

[0187] Synthesis of Intermediate 143-1: The synthesis method was the same as that of Intermediate 1-1, and pale yellow solid Intermediate 143-1 was obtained (yield: 54.9%).

[0188] Synthesis of Intermediate 143-2: The synthesis method was the same as that of Intermediate 1-2, and pale yellow solid Intermediate 143-2 was obtained (yield: 85.2%).

[0189] Synthesis of Compound 143: The synthesis method was the same as that of Intermediate 1-2, and a light yellow solid compound 143 was obtained (yield: 83.3%).

[0190] Mass spectrometry: C46H25N5O3S, theoretical value: 727.17, measured value: 727.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.99 - 7.02 (4H, m), 7.42 - 7.27 (6H, m), 7.51 - 7.46 (4H, m), 7.69 - 7.59 (6H, m), 8.14 - 8.15 (1H, m), 8.14 - 8.18 (2H, m), 8.32 - 8.36 (2H, m).

[0191] Preparation Example 15:

[0192]

[0193] Synthesis of Intermediate 158-1: The synthesis method was the same as that of Intermediate 1-1, and a light yellow solid Intermediate 158-1 was obtained (yield: 53.6%).

[0194] Synthesis of Intermediate 158-2: The synthesis method was the same as that of Intermediate 1-2, and a light yellow solid Intermediate 158-2 was obtained (yield: 84.6%).

[0195] Synthesis of Compound 158: The synthesis method was the same as that of Intermediate 1-2, and a light yellow solid compound 158 was obtained (yield: 83.2%).

[0196] Mass spectrometry: C52H32N6O2, theoretical value: 772.26, measured value: 772.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.90 - 7.04 (4H, m), 7.05 - 7.07 (1H, m), 7.17 - 7.20 (5H, m), 7.21 - 7.22 (1H, d), 7.23 - 7.24 (2H, m), 7.40 - 7.53 (8H, m), 7.62 - 7.66 (3H, m), 7.73 - 7.74 (1H, m), 7.75 - 7.77 (1H, m), 7.94 - 7.95 (1H, m), 7.97 - 7.99 (1H, m), 8.16 - 8.20 (2H, m), 8.34 - 8.38 (2H, m).

[0197] Preparation Example 16:

[0198]

[0199] Synthesis of Intermediate 173-1: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 173-1 is obtained (Yield: 85.6%).

[0200] Synthesis of Compound 173: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Compound 173 is obtained (Yield: 82.7%).

[0201] Mass Spectrum: C52H31N5OS2, Theoretical Value: 805.20, Measured Value: 805.3. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.95 - 7.03 (2H, m), 7.14 - 7.31 (4H, m), 7.27 - 7.34 (2H, m), 7.47 - 7.54 (9H, m), 7.57 - 7.62 (2H, m), 7.66 - 7.73 (2H, m), 8.00 - 8.06 (2H, m), 8.10 - 8.17 (2H, m), 8.32 - 8.40 (6H, m).

[0202] Preparation Example 17:

[0203]

[0204] Synthesis of Intermediate 227-1: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 227-1 is obtained (Yield: 84.9%).

[0205] Synthesis of Intermediate 227-2: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 227-2 is obtained (Yield: 83.2%).

[0206] Synthesis of Compound 227: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Compound 227 is obtained (Yield: 83.1%).

[0207] Mass Spectrum: C52H31N5OS2, Theoretical Value: 805.20, Measured Value: 805.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.95 - 7.03 (1H, m), 7.14 - 7.18 (1H, m), 7.20 - 7.23 (2H, m), 7.25 - 7.28 (2H, m), 7.30 - 7.31 (1H, m), 7.36 - 7.40 (1H, m), 7.46 - 7.55 (13H, m), 7.93 - 7.97 (2H, m), 7.98 - 8.05 (4H, m), 8.31 - 8.38 (4H, m).

[0208] Preparation Example 18:

[0209]

[0210] Synthesis of Intermediate 212-1: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 212-1 is obtained (yield: 85.6%).

[0211] Synthesis of Intermediate 212-2: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Intermediate 212-2 is obtained (yield: 83.0%).

[0212] Synthesis of Compound 212: The synthesis method is the same as that of Intermediate 1-2, and light yellow solid Compound 212 is obtained (yield: 83.4%).

[0213] Mass Spectrum: C45H26N4O2S, theoretical value: 686.18, measured value: 686.2. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.97 - 7.06 (2H, m), 7.20 - 7.24 (1H, d), 7.29 - 7.36 (1H, m), 7.45 - 7.54 (2H, m), 7.56 - 7.65 (7H, m), 7.66 - 7.71 (2H, m), 7.75 - 7.82 (3H, m), 7.95 - 7.99 (2H, m), 8.10 - 8.15 (1H, m), 8.15 - 8.20 (4H, m), 8.27 - 8.32 (1H, m).

[0214] Device Example 1

[0215] The glass plate coated with ITO transparent conductive layer is 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 all water is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface;

[0216] Place the above-mentioned glass substrate with anode in a vacuum chamber, evacuate to 1×10 -5 Pa, vacuum deposit HAT-CN as the hole injection layer on the above anode layer film, the deposition rate is 0.1 nm / s, and the total film thickness is 1 nm; then deposit the hole transport layer NPB, the deposition rate is 0.1 nm / s, and the thickness is 60 nm;

[0217] Vacuum deposit the electron blocking layer TCTA of the device on the hole transport layer, the deposition rate is 0.1 nm / s, and the total film thickness is 10 nm;

[0218] The light-emitting layer of the device is vacuum-evaporated on top of 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, the evaporation rate of the host material DIC-TRZ is adjusted to 0.1 nm / s, and the guest material Ir(ppy) 3 The evaporation rate is set at a 10% ratio, and the total evaporation film thickness is 30 nm;

[0219] The electron transport layer of the device is vacuum-evaporated on top of the light-emitting layer. Using the method of co-evaporation from multiple sources, the evaporation rates of both ET-1 and Compound 1 are adjusted to 0.1 nm / s, and the total evaporation film thickness is 30 nm;

[0220] A 0.5-nm-thick LiF is vacuum-evaporated on the electron transport layer (ETL) as the electron injection layer, and a 150-nm-thick Al layer is used as the cathode of the device.

[0221] The molecular structures involved are as follows:

[0222]

[0223] Device Examples 2 to 15

[0224] Organic electroluminescent devices of Device Examples 2 to 15 are prepared 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.

[0225] Device Comparative Example 1

[0226] An organic electroluminescent device of Device Comparative Example 1 is prepared 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 compound Ref-1.

[0227]

[0228] Test Example 1

[0229] At a brightness of 10000 cd / m 2 The driving voltages and current efficiencies of the organic electroluminescent devices prepared in Device Examples 1 to 15 and Device Comparative Example 1 are measured, and the results are shown in Table 1.

[0230] Table 1

[0231]

[0232]

[0233] 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 luminescence efficiency when applied to organic electroluminescent devices.

[0234] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of 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 polycyclic compound, the structure of which is shown in Formula I: X and Y are the same or different and are each independently oxygen or sulfur; Z is oxygen, sulfur or N-R, where R is a C1-C6 alkyl group or a C6-C20 aryl group; 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 a pyrimidine ring, a quinoxaline ring, a quinazoline ring and a triazine ring; 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, 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; 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 polycyclic compound according to claim 1, wherein, R is methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, naphthyl, anthracenyl, phenanthryl or biphenyl.

3. The nitrogen-containing polycyclic compound according to claim 1, wherein, R 1 、R 2 、R 3 and R 4 each independently is H, a C1-C6 alkyl group, a C6-C20 aryl group or a C3-C40 heteroaryl group having a nitrogen heterocycle.

4. The nitrogen-containing polycyclic compound according to claim 3, wherein, The C1-C6 alkyl group is methyl, ethyl, n-propyl, isopropyl or n-butyl, and the C6-C20 aryl group is phenyl, naphthyl, anthracenyl, phenanthryl or biphenyl.

5. The nitrogen-containing polycyclic compound according to any one of claims 1-4, wherein, 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.

6. The nitrogen-containing polycyclic compound according to any one of claims 1-4, wherein, 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.

7. The nitrogen-containing polycyclic compound according to any one of claims 1-4, wherein, 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.

8. A nitrogen-containing polycyclic compound, wherein, The nitrogen-containing polycyclic compound is selected from the following compounds:

9. Use of the nitrogen-containing polycyclic compound according to any one of claims 1-8 in an organic electroluminescent device.

10. The use according to claim 9, wherein, In the organic electroluminescent device, the nitrogen-containing polycyclic compound is used as an electron transport material.

11. An organic electroluminescent device, comprising an electron transport layer, and the electron transport layer comprises the nitrogen-containing polycyclic compound according to any one of claims 1-8.

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