An organic compound and its application in OLED devices

Abstract

The present invention belongs to the technical field of organic electroluminescent display devices, and specifically discloses an organic compound, and also discloses the application of the organic compound in an OLED device. The organic compound provided by the present invention is a compound with a novel dehydrogenated fused ring structure, and these novel compounds have a very deep LUMO energy level, so they are very good electron acceptor materials and charge transfer materials, and have very broad industrial application prospects. The organic compound provided by the present invention can be used as a charge transport material, a charge injection material and similar materials in an organic electroluminescent device.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescent display devices, and specifically discloses an organic compound and also discloses the application of the organic compound in an OLED device. Background Art

[0002] Organic electronic devices include, but are not limited to, the following categories: organic light emitting diodes (OLEDs), organic field effect transistors (O-FETs), organic light emitting transistors (OLETs), organic photovoltaics (COPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LEGS), organic laser diodes, and organic plasmonic light emitting devices.

[0003] In 1987, Tang and Van Slyke of Eastman Kodak reported a double-layer organic electroluminescent device, which included an arylamine hole transport layer and a tri-8-hydroxyquinoline aluminum layer as an electron transport layer and a light-emitting layer (Applied Physics Letters, 1987, 51 (12): 913-915). Once a bias voltage is applied to the device, green light is emitted from the device. This invention laid the foundation for the development of modern organic light-emitting diodes (OLEDs). The most advanced can include multiple layers, such as charge injection transport layers, charge and exciton blocking layers, and one or more light-emitting layers between the cathode and anode. Since OLEDs are self-luminous solid-state devices, they offer great potential for display and lighting applications. In addition, the inherent properties of organic materials, such as their flexibility, can make them very suitable for special applications, such as on flexible substrates.

[0004] OLEDs can be divided into three different types according to their light-emitting mechanism. The OLED invented by Tang and Van Slyke is a fluorescent OLED, which only uses singlet light emission. The triplet generated in the device is wasted through non-radiative decay channels. Therefore, the internal quantum efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation has hindered the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which used triplet light emission from heavy metals containing complexes as luminescent bodies, thus being able to harvest singlet and triplet states and achieve 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributed to the commercialization of active matrix OLEDs (AMOLEDs). Recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These luminescent bodies have a small singlet-triplet gap, making it possible for excitons to return from doublets to singlets. In TADF devices, triplet excitons can generate singlet excitons through reverse intersystem crossing, resulting in high IQE.

[0005] In organic light-emitting display devices, hole injection layers and electron injection layers are generally used to promote charge injection. The hole injection layer is a functional layer formed by a single material or more than one material. The single material method generally uses a material with a deep LUMO, while the method with more than one material is formed by doping a P-type, deep LUMO material with a hole transport material. The common point between the two is that deep LUMO materials need to be used. However, deep LUMO materials are not easy to synthesize because they have strong electron-pulling substituents, and it is difficult to have the characteristics of deep LUMO, high stability and high film-forming properties at the same time. For example, although F4-TCNQ (P-type hole injection material) has a deep LUMO, the evaporation temperature is too low, which affects the control of deposition, the reproducibility of production performance and the thermal stability of the device. For another example, HATCN has film-forming problems in the device because of its strong crystallinity, and the LUMO is not deep enough to be used as a P-type doping.

[0006] Given that the hole injection layer has a great influence on the voltage, efficiency and life of OLED devices, it is very important and urgent to develop materials with deep LUMO, high stability and high film-forming properties in organic electroluminescent display devices. Summary of the invention

[0007] The purpose of the present invention is to develop an organic compound having a novel dehydrogenated fused ring structure. The novel compound has a deep LUMO energy level and has the potential to become an excellent hole injection material and p-dopant material.

[0008] Specifically, in a first aspect, the present invention provides an organic compound, comprising a structure represented by formula I:

[0009]

[0010] In Formula I:

[0011] X and Y are selected from the group consisting of NR', CR"R"', O, S, Se at each occurrence, the same or different;

[0012] Z1 and Z2 are selected, identically or differently, from O, S or Se at each occurrence;

[0013] R m , R n R', R", R"', each occurrence is identically or differently selected from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, mercapto, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted alkyl having 7-30 carbon atoms Aralkyl, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, and combinations thereof;

[0014] And R m , R n At least one of R', R", and R'" is a group having at least one electron-withdrawing group; and / or,

[0015] R m , R n Any two adjacent groups among R', R", R", and R'" can be optionally linked to form a ring.

[0016] As an embodiment of the present invention, in Formula I, X and Y are selected from the group consisting of NR', CR"R"', O, and S at each occurrence, the same or different; at least one of R', R", and R"' is a group having at least one electron-withdrawing group.

[0017] As an embodiment of the present invention, the group of the electron withdrawing group, wherein the Hammett constant of the electron withdrawing group is ≥0.05, preferably ≥0.3, more preferably ≥0.5.

[0018] Preferably, the electron withdrawing group is selected from the group consisting of halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, mercapto, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms, substituted or unsubstituted substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

[0019] Further preferably, the electron withdrawing group is selected from the group consisting of F, CF3, OCF3, SF5, SO2CF3, cyano, isocyano, SCN, OCN, pyrimidinyl, triazine, and combinations thereof.

[0020] As an embodiment of the present invention, each occurrence of X and Y is identical or different and is selected from the group consisting of the following structures:

[0021]

[0022] wherein R1 is selected, at each occurrence, identically or differently, from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl,

[0023] sulfonyl, phosphinoyl, mercapto, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms, substituted or unsubstituted alkylsilyl having 3-20 carbon atoms, substituted or unsubstituted arylsilyl having 6-20 carbon atoms, and combinations thereof; preferably, each occurrence of R1 is identically or differently selected from the group consisting of: F, CF3, OCF3, SF5, SO2CF3, cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyano-4fluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazine, and combinations thereof;

[0024] V and W are selected from CR in the same or different order at each occurrence. v R w , NR v , O, S, Se;

[0025] Ar is selected, at each occurrence, identically or differently, from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

[0026] A, R a , R b , R c , R d , R e , R f , R g , R h , R v and R wis selected, at each occurrence, identically or differently, from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, mercapto, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

[0027] wherein A is a group having at least one electron withdrawing group, and for any of the structures, when R a , R b , R c ,

[0028] R d , R e , R f , R g , R h , R v and R w When one or more of the a , R b , R c , R d , R e , R f , R g , R h , R v and R w At least one of them is a group having an electron-withdrawing group; preferably, the group having at least one electron-withdrawing group is selected from the group consisting of: F, CF3, OCF3, SF5, SO2CF3, cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyano-4-fluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazine, and combinations thereof;

[0029] As a preferred embodiment of the present invention, X and Y are selected from the group consisting of the following structures the same or different when they appear each time:

[0030]

[0031] As an embodiment of the present invention, in Formula I, Z1 and Z2 are the same and are selected from O, S or Se.

[0032] As an embodiment of the present invention, in Formula I, each occurrence of Rm and Rn is identically or differently selected from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, alkyl with 1 to 20 carbon atoms, cycloalkyl with 3 to 20 ring carbon atoms, alkoxy with 1 to 20 carbon atoms, alkenyl with 2 to 20 carbon atoms, aryl with 6 to 30 carbon atoms, aryl with 3- 30 carbon atoms, heteroaryl, and any of the following groups substituted by one or more of halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino: alkyl, 3-20 carbon atoms, cycloalkyl, 1-20 carbon atoms, alkoxy, 2-20 carbon atoms, alkenyl, 6-30 carbon atoms, aryl, 3-30 carbon atoms, and combinations thereof;

[0033] Preferably, each occurrence of Rm and Rn is identically or differently selected from the group consisting of hydrogen, deuterium, methyl, isopropyl, NO2, SO2CH3, SCF3, C2F5, OC2F5, OCH3, diphenylmethylsilyl, phenyl, methoxyphenyl, p-methylphenyl, 2,6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, vinyl substituted with one or more of CN or CF3, vinyl substituted with one or more of CN or CF3. substituted ethynyl, dimethylphosphinoyl, diphenylphosphinoyl, F, CF3, OCF3, SF5, SO2CF3, cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis(trifluoromethyl)phenyl, bis(trifluorooxy)phenyl, 4-cyanotetrafluorophenyl, phenyl or biphenyl substituted with one or more of F, CN or CF3, tetrafluoropyridyl, pyrimidinyl, triazine, diphenylboryl, oxaboranthenyl, and combinations thereof;

[0034] Further preferably, each occurrence of Rm and Rn is identically or differently selected from the group consisting of the following structures:

[0035]

[0036]

[0037] As an embodiment of the present invention, the organic compound comprises a structure represented by Formula II:

[0038]

[0039] In formula II, the groups Z, X, Y, Rm, and Rn represent atoms or groups shown in the following table:

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] The structures corresponding to compound numbers 1 to 876, wherein Z, X, Y, Rm and Rn are as follows:

[0055] In compounds 1 to 252, Z corresponds to O, S and Se respectively, X and Y have the same structure, both are A1, Rm and Rn have the same structure, corresponding to B1 to B84 respectively;

[0056] In compounds 253 to 300, Z is all O, X and Y have the same structure, corresponding to A2 and A3, respectively, and Rm and Rn have the same structure, corresponding to B2, B6, B10, B16, B18, B21, B24, B27, B32, B35, B38, B42, B47, B51, B60, B64, B66, B68, B70, B71, B75, B77, B78, and B82, respectively;

[0057] In compounds 301 to 348, Z corresponds to S and Se, respectively; X and Y have the same structure, namely A4; Rm and Rn have the same structure, corresponding to B2, B6, B10, B16, B18, B21, B24, B27, B32, B35, B38, B42, B47, B51, B60, B64, B66, B68, B70, B71, B75, B77, B78, and B82, respectively;

[0058] In compounds 349 to 564, Z corresponds to O, S and Se, respectively; X and Y have the same structure and correspond to A5, A6 and A7, respectively; Rm and Rn have the same structure and correspond to B2, B6, B10, B16, B18, B21, B24, B27, B32, B35, B38, B42, B47, B51, B60, B64, B66, B68, B70, B71, B75, B77, B78 and B82, respectively;

[0059] Compounds 565 to 588, Z, X and Y have the same structure, all are O, Rm and Rn have the same structure, corresponding to B2, B6, B10, B16, B18, B21, B24, B27, B32, B35, B38, B42, B47, B51, B60, B64, B66, B68, B70, B71, B75, B77, B78, B82, respectively;

[0060] In compounds 589 to 636, Z corresponds to S and Se, respectively; X and Y have the same structure, both are O; Rm and Rn have the same structure, corresponding to B2, B6, B10, B16, B18, B21, B24, B27, B32, B35, B38, B42, B47, B51, B60, B64, B66, B68, B70, B71, B75, B77, B78, and B82, respectively;

[0061] In compounds 637 to 660, Z is all O, X and Y have the same structure, both are S, and Rm and Rn have the same structure, corresponding to B2, B6, B10, B16, B18, B21, B24, B27, B32, B35, B38, B42, B47, B51, B60, B64, B66, B68, B70, B71, B75, B77, B78, and B82, respectively;

[0062] In compounds 661 to 768, Z corresponds to O, S and Se, respectively; X and Y have the same structure and correspond to A1, A3, A5 and A7, respectively; Rm and Rn have different structures and are selected from B1 to B84, respectively;

[0063] In compounds 769 to 876, Z corresponds to O, S and Se, respectively; X and Y have different structures and correspond to A1, A3 and A2, A6, respectively; Rm and Rn have the same structures and correspond to B2, B6, B16, B24, B27, B30, B38, B42, B50, B56, B60, B62, B64, B67, B69, B72, B76, and B82, respectively.

[0064] In a second aspect, the present invention provides a use of the organic compound in an organic electroluminescent device.

[0065] Preferably, the organic compound is used in an organic layer of an organic electroluminescent device.

[0066] Further preferably, the organic compound is used in a hole injection layer of an organic electroluminescent device.

[0067] As an embodiment of the present invention, the amount of the organic compound in the hole injection layer is 1% to 100% of the total weight of the hole injection layer.

[0068] In a third aspect, the present invention provides an organic electroluminescent device comprising the organic compound of the present invention.

[0069] Preferably, the organic electroluminescent device comprises an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, and the organic layer comprises the organic compound described in the present invention.

[0070] Further preferably, the organic layer is a hole injection layer, and the hole injection layer comprises the organic compound described in the present invention.

[0071] As an embodiment of the present invention, the hole injection layer further comprises at least one hole transport material.

[0072] Preferably, the hole transport material comprises a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex.

[0073] As an embodiment of the present invention, the molar doping ratio of the organic compound to the hole transport material is 10000:1 to 1:10000.

[0074] As a preferred embodiment of the present invention, the molar doping ratio of the organic compound to the hole transport material is 10:1 to 1:100.

[0075] In a fourth aspect, the present invention provides a display assembly, comprising the organic electroluminescent device of the present invention. The display assembly of the present invention includes, but is not limited to, a flat panel display, a monitor, a medical monitor, a television, a billboard, a lamp for indoor or outdoor lighting and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a smart phone, a tablet computer, a tablet phone, a wearable device, a smart watch, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay, a 3-D display, a vehicle display, and a taillight.

[0076] The organic compound provided by the present invention is a compound with a novel dehydrogenated fused ring structure. These novel compounds have a very deep LUMO energy level, and therefore are very good electron acceptor materials and charge transfer materials, and have the potential to become excellent hole injection materials and excellent p-dopant (P-type dopant) materials, and have very broad industrial application prospects. The organic compound provided by the present invention can be used as a charge transport material, a charge injection material and similar materials in an organic electroluminescent device. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] Figure 1 is the NMR spectrum of compound 64;

[0078] Figure 2 is the NMR spectrum of compound 69;

[0079] Figure 3 is the NMR spectrum of compound 669;

[0080] Figure 4 is the NMR spectrum of compound 676;

[0081] Figure 5 is the NMR spectrum of compound 119;

[0082] Figure 6 This is the NMR spectrum of compound 148. DETAILED DESCRIPTION

[0083] The technical solution of the present invention is described in detail below.

[0084] It should be noted that the materials for the specific layers in the organic light-emitting device described in the present invention can be used in combination with various other materials present in the device. The combination of these materials is described in detail in paragraphs 0132-0161 of U.S. Patent Application US2016 / 0359122M, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0085] The materials described herein as specific layers that can be used in organic light-emitting devices can be used in combination with a variety of other materials present in the device. For example, the compounds disclosed herein can be used in combination with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of U.S. Patent Application US2015 / 0349273M, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0086] In addition, it should be noted that in the above technical solution, the definitions of the substituent terms are as follows:

[0087] Halogens: include fluorine, chlorine, bromine and iodine.

[0088] Alkyl: Contains straight chain and branched chain alkyl. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isobutyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. In addition, the alkyl group may be optionally substituted. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. In addition, the alkyl group may be optionally substituted.

[0089] Cycloalkyl: Contains cyclic alkyl. The cycloalkyl may be a cycloalkyl having 3 to 20 ring carbon atoms, preferably a cycloalkyl having 4 to 10 carbon atoms. Examples of cycloalkyl include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl are preferred. In addition, the cycloalkyl may be optionally substituted.

[0090] Alkenyl: includes straight chain, branched chain and cyclic olefin groups. The alkenyl group may be an alkenyl group containing 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 10 carbon atoms. Examples of alkenyl groups include vinyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexenyl, cyclohexatenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl and norbornenyl. Additionally, alkenyl groups may be optionally substituted.

[0091] Aryl or aromatic group: Both non-fused and fused systems are contemplated. The aryl group may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, biphenyl, triphenylene, fluorene and naphthalene. In addition, aryl can be optionally substituted. Examples of non-condensed aryl include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesitylene and m-quadrenyl. In addition, aryl can be optionally substituted.

[0092] Heterocyclic group or heterocycle: non-aromatic cyclic groups are contemplated. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3-20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-20 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms and boron atoms, and preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclic groups include oxirane, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxopentanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepine and tetrahydrothioxolyl. In addition, the heterocyclic group may be optionally substituted.

[0093] Heteroaryl: A non-fused and fused heteroaromatic group containing 1 to 5 heteroatoms, wherein at least one heteroatom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium and boron atoms. Heteroaryl also refers to heteroaryl. The heteroaryl may be a heteroaryl having 3 to 30 carbon atoms, preferably a heteroaryl having 3 to 20 carbon atoms, and more preferably a heteroaryl having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoxazole, benzothiazole, quinoline, isoxazole, benzofuran, benzothi ...furan, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran, benzofuran Quinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenobenzodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazole and aza analogs thereof. In addition, the heteroaryl group may be optionally substituted.

[0094] Alkoxy: represented by -O-alkyl, -O-cycloalkyl, -O-heteroalkyl or -O-heterocyclic. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl and heterocyclic are the same as above. Alkoxy can be an alkoxy having 1 to 20 carbon atoms, preferably an alkoxy having 1 to 6 carbon atoms. Examples of alkoxy include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. In addition, the alkoxy may be optionally substituted.

[0095] Aryloxy: represented by -O-aryl or -O-heteroaryl. Examples and preferred examples of aryl and heteroaryl are the same as above. Aryloxy may be an aryloxy having 6 to 30 carbon atoms, preferably an aryloxy having 6 to 20 carbon atoms. Examples of aryloxy include phenoxy and biphenyloxy. In addition, aryloxy may be optionally substituted.

[0096] Aralkyl: an alkyl group containing aryl substitution. The aralkyl group may be an aralkyl group having 7 to 30 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 13 carbon atoms. Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthyl-ethyl, 2-β-naphthyl-ethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, substituted alkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl, arylalkyl,

[0097] Alkylsilyl: Silicon groups substituted with alkyl groups. The alkylsilyl group may be an alkylsilyl group having 3 to 20 carbon atoms, preferably an alkylsilyl group having 3 to 10 carbon atoms. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-tert-butylsilyl, triisobutylsilyl, dimethyltert-butylsilyl, methylditert-butylsilyl. In addition, the alkylsilyl group may be optionally substituted.

[0098] Arylsilyl: silicon radical containing at least one aryl substitution. The arylsilyl can be an arylsilyl having 6 to 30 carbon atoms, preferably an arylsilyl having 8 to 20 carbon atoms. Examples of arylsilyl include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyltert-butylsilyl, tritert-butylsilyl, dimethyltert-butylsilyl, methylditert-butylsilyl. In addition, the arylsilyl can be optionally substituted.

[0099] It should be noted that in the above technical scheme, unless otherwise defined, when any one of the terms in the group consisting of the following is used, substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxyl, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, means that any one of alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxyl, ester, sulfinyl, sulfonyl and phosphino may be replaced by one or more selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms. The invention also includes an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group having 1 to 20 carbon atoms, an unsubstituted heterocyclyl group having 3 to 20 ring atoms, an unsubstituted aralkyl group having 7 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 20 carbon atoms, an unsubstituted aryloxy group having 6 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 20 carbon atoms, an unsubstituted alkynyl group having 2 to 20 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, an unsubstituted alkylsilyl group having 3 to 20 carbon atoms, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

[0100] It should be noted that, in the compounds of the present invention, when a molecular fragment is described as a substituent or otherwise connected to another part, its name can be written according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or connecting fragments are considered equivalent.

[0101] It should be noted that in the compounds of the present invention, hydrogen atoms may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Due to its enhanced efficiency and stability of the device, the replacement of other stable isotopes in the compound may be preferred.

[0102] It should be noted that in the compounds of the present invention, multiple substitution refers to the range including disubstitution up to the maximum available substitution. When a substituent in the compounds mentioned in the present disclosure represents multiple substitution (including disubstitution, trisubstitution, tetrasubstitution, etc.), it means that the substituent can exist in multiple available substitution positions on its connection structure, and the substituent existing in multiple available substitution positions can be the same structure or different structures.

[0103] It should be noted that, in the compounds of the present invention, unless clearly defined, for example, adjacent substituents can be optionally connected to form a ring, otherwise adjacent substituents in the compound cannot be connected to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally connected to form a ring, including both the situation where adjacent substituents can be connected to form a ring and the situation where adjacent substituents are not connected to form a ring. When adjacent substituents can be optionally connected to form a ring, the formed ring can be a monocyclic or polycyclic ring, as well as an alicyclic, heteroalicyclic, aromatic or heteroaromatic ring. In this statement, adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0104] The expression that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

[0105]

[0106] The expression that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

[0107]

[0108] Furthermore, the statement that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that, in the case where one of the two substituents bonded to the carbon atoms directly bonded to each other represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:

[0109]

[0110] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. In the examples of material synthesis, unless otherwise stated, all reactions are carried out under nitrogen protection. All reaction solvents are anhydrous and used as they are from commercial sources. The synthetic product uses one or more conventional equipment in the art (including but not limited to Agilent's liquid chromatograph, liquid chromatography-mass spectrometer, gas chromatography-mass spectrometer, differential scanning calorimeter, fluorescence spectrophotometer, electrochemical workstation, sublimator, etc.), and the structure is confirmed and the characteristics are tested by methods well known to those skilled in the art. In the embodiment of the device, the characteristics of the device are also tested by methods well known to those skilled in the art using conventional equipment in the art (including but not limited to the evaporation machine produced by Nanjing Institute of Microscience, the optical test system and life test system produced by Suzhou Fushida, the ellipsometer produced by Wuhan Yiguang Technology, etc.). Since those skilled in the art are aware of the relevant contents such as the use of the above-mentioned equipment and the test method, the inherent data of the sample can be obtained with certainty and without being affected, so the above-mentioned relevant contents are no longer expanded in the present invention.

[0111] The present invention does not limit the preparation method of the compound, and the following compounds are typically but not restrictively exemplified, and their synthesis routes and preparation methods are as follows:

[0112] Synthesis Example 1: Synthesis of Compound 64

[0113]

[0114] The synthetic route is as follows:

[0115]

[0116] The specific preparation process is:

[0117] Step 1: Synthesis of intermediate P1

[0118] In a 500mL clean round-bottom flask, add oxazole-5-carboxylic acid (11.3g, 1.0eq, 0.1mol), phenol (9.4g, 1.0eq, 0.1mol), DCC (30.9g, 1.5eq, 0.15mol), DMAP (0.61g, 0.05eq, 5mmol) and THF (200mL) in sequence, start stirring, replace with nitrogen 3 times, and heat to reflux for 12 hours. After the reaction is completed, cool to room temperature, filter, dissolve the solid in a mixed solution of ethyl acetate and water, separate the liquids, extract with ethyl acetate, combine the organic phases, wash once with sodium chloride aqueous solution, and then dry with anhydrous sodium sulfate. After concentration, separate by column chromatography to obtain off-white solid P1 (12.7g, yield 64%).

[0119] Step 2: Synthesis of intermediate P2

[0120] In a 1L dry round-bottom flask, under nitrogen protection, P1 (19.8g, 1.0eq, 0.1mol), dry DMF (500mL) and ethyl isocyanoacetate (16.95g, 1.5eq, 0.15mol) were added in sequence, the temperature was lowered to 0°C, and then NaH (mass fraction 60%, 8g, 2.0eq, 0.2mol) was added, and the reaction was continued at this temperature for 24 hours. After the reaction was completed, the mixture was extracted with ethyl acetate, the organic phase was separated, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain an off-white solid P2 (16.8g, yield 81%).

[0121] Step 3: Synthesis of intermediate P3

[0122] In a 1L dry round-bottom flask, add P2 (20.8g, 1.0eq, 0.1mol), sodium hydroxide (10g, 2.5eq, 0.25mmol), 400mL ethanol and 100mL water in sequence, replace nitrogen three times, and heat to reflux for 12 hours. After the reaction is completed, cool to room temperature, extract with ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate and separate by column chromatography to obtain an off-white solid P3 (13.3g, yield 74%).

[0123] Step 4: Synthesis of intermediate P4

[0124] In a 1L dry round-bottom flask, under nitrogen protection, P3 (18.0g, 1.0eq, 0.1mol), iodine (38.1g, 1.5eq, 0.15mol), potassium phosphate (21.2g, 1.0eq, 0.1mol) and 400mL acetonitrile were added in sequence, and the temperature was raised to reflux for 10 hours. After the reaction, the temperature was cooled to room temperature, filtered through diatomaceous earth, and the diatomaceous earth was rinsed with an appropriate amount of dichloromethane. The filtrate was concentrated and separated by column chromatography to obtain a light yellow solid P4 (22.3g, yield 85%).

[0125] Step 5: Synthesis of intermediate P5

[0126] In a 1L dry round-bottom flask, under nitrogen protection, P4 (26.2g, 1.0eq, 0.1mol), 3,5-bis(trifluoromethyl)phenylacetylene (23.8g, 1.0eq, 0.1mol), bis(triphenylphosphine)palladium dichloride (0.7g, 0.01eq, 1mmol), triphenylphosphine (0.5g, 0.02eq, 2mmol), cuprous iodide (0.4g, 0.02eq, 2mmol) and 400mL of triethylamine were added in sequence, and the temperature was raised to reflux for 12 hours. After the reaction was completed, the solvent was removed by concentration under reduced pressure, and a light yellow solid P5 (29.0g, yield 78%) was obtained by column chromatography.

[0127] Step 6: Synthesis of intermediate P6

[0128] In a 1L dry round-bottom flask, under nitrogen protection, P5 (37.2g, 1.0eq, 0.1mol), 3,5-bis(trifluoromethyl)bromobenzene (29.3g, 1.0eq, 0.1mol), palladium acetate (0.8g, 0.05eq, 5mmol), 1,1'-bis(diisopropylphosphino)ferrocene (di-Prpf) (2.5g, 0.06eq, 6mmol), triethylenediamine (DABCO) (22.4g, 2eq, 0.2mol) and 400mL of N-methylpyrrolidone were added in sequence, and the temperature was raised to 120°C for 12 hours. After the reaction, the temperature was cooled to room temperature, the solvent was distilled off under reduced pressure, and the liquid was separated by ethyl acetate and water extraction. The organic phase was dried over anhydrous sodium sulfate, and then the solvent was removed to obtain a crude product. The crude product was separated by column chromatography to obtain a light yellow solid P6 (50.2g, yield 86%).

[0129] Step 7: Synthesis of intermediate P7

[0130] In a 1L dry round-bottom flask, under nitrogen protection, solid P6 (58.4g, 1.0eq, 0.1mol) was added to 350mL tetrahydrofuran, and the temperature was cooled to -95℃~-90℃ by liquid nitrogen, and n-butyl lithium (92mL, 2.3eq, 2.5M n-hexane solution) was slowly added dropwise, and the temperature was maintained for 1 hour, and then the temperature was slowly raised to -78℃ and reacted for 6 hours. Then, a tetrahydrofuran solution (100mL) of elemental iodine (76.2g, 3.0eq, 0.3mol) was added, and the temperature was slowly raised to room temperature and reacted overnight, and a small amount of saturated ammonium chloride solution was added to quench, and then diatomaceous earth was directly added to mix the sample, and the white solid product P7 (41.0g, yield 49%) was purified by silica gel column chromatography.

[0131] Step 8: Synthesis of intermediate P8

[0132] In a 1L dry round-bottom flask, under nitrogen protection, malononitrile (39.6g, 6.0eq, 0.6mol) was added to anhydrous 400mL DMF, and NaH (24g, 6.0eq, 0.6mol, 60% content) was added in several times at 0℃, stirred at 0℃ for 10 minutes and at room temperature for 20 minutes, and then P7 (83.6g, 1.0eq, 0.1mol) and tetrakistriphenylphosphine palladium (11.6g, 0.1eq, 0.01mol) were added, and the temperature was raised to 90℃ for 24 hours. After complete conversion, it was poured into ice water, and the pH was adjusted to <1 with dilute hydrochloric acid. After sufficient stirring, a large amount of yellow solid precipitated, and the solid was filtered and collected. Washed with dichloromethane to obtain a yellow solid, and then washed twice with dichloromethane and heptane, filtered to obtain a yellow solid P8 (65.5g, yield 92%).

[0133] Step 9: Synthesis of compound 64

[0134] In a 2L dry round-bottom flask, under nitrogen protection, solid P8 (35.6g, 1.0eq, 0.05mol) was added to anhydrous 1L DCM, cooled to 0°C, and then [bis(trifluoroacetyloxy)iodo]benzene (PIFA) (21.5g, 1.0eq, 0.05mol) was added. Stir at room temperature for 3 days, and the solution was purple-black. The reaction solution was then placed in a 2L single-mouth bottle, the solution was spin-dried to about 100mL, 1L of n-hexane was added thereto, stirred for 10 minutes, and filtered to obtain a dark green solid, which was washed twice with a mixed solvent of dichloromethane and heptane, and finally a dark green solid compound 64 (28.8g, yield 81%) was obtained.

[0135] Product MS (m / e): 710.23; Elemental analysis (C 30 H6O2F 12 N6): Theoretical value C: 50.72%, H: 0.85%, N: 11.83%; Measured value C: 50.69%, H: 0.93%, N: 11.78%.

[0136] 1 HNMR (400MHz, ClCD3) δ: 7.95 (s, 4H), 7.63 (s, 2H). Figure 1 .

[0137] Synthesis Example 2: Synthesis of Compound 69

[0138]

[0139] use Replace 3,5-bis(trifluoromethyl)phenylacetylene with Substituting 3,5-bis(trifluoromethyl)bromobenzene, the material ratio, other raw materials and steps were the same as those in Synthesis Example 1, and 33.6 g of dark green solid compound 69 was obtained.

[0140] Product MS (m / e): 862.47; Elemental analysis (C 42 H 14 O2F 12 N6): Theoretical value C: 58.48%, H: 1.64%, N: 9.74%; Measured value C: 58.53%, H: 1.68%, N: 9.63%.

[0141] 1HNMR (400MHz, ClCD3) δ: 8.13 (d, J = 2.0 Hz, 2H), 8.11–8.05 (m, 2H), 7.88–7.82 (m, 2H), 7.76 (dd, J = 10.6, 2.0 Hz, 2H), 7.48–7.35 (m, 6H). See the NMR spectrum for details. Figure 2 .

[0142] Synthesis Example 3: Synthesis of Compound 669

[0143]

[0144] use Replace 3,5-bis(trifluoromethyl)phenylacetylene with Substituting 3,5-bis(trifluoromethyl)bromobenzene, the material ratio, other raw materials and steps were the same as those in Synthesis Example 1, and 31.1 g of dark green solid Compound 669 was obtained.

[0145] Product MS (m / e): 840.32; Elemental analysis (C 33 H8O3F 16 N6): Theoretical value C: 47.16%, H: 0.96%, N: 10.00%; Measured value C: 47.19%, H: 0.92%, N: 9.97%.

[0146] 1 HNMR (400MHz, ClCD3) δ: 7.66 (d, J = 1.3Hz, 4H), 7.47-7.42 (m, 2H), 7.29-7.23 (m, 2H). Figure 3 .

[0147] Synthesis Example 4: Synthesis of Compound 676

[0148]

[0149] use Replace 3,5-bis(trifluoromethyl)phenylacetylene with Substituting 3,5-bis(trifluoromethyl)bromobenzene, the material ratio, other raw materials and steps were the same as those in Synthesis Example 1, and 34.9 g of dark green solid compound 676 was obtained.

[0150] Product MS (m / e): 984.48; Elemental analysis (C 42 H9O4F 17 N6): Theoretical value C: 51.24%, H: 0.92%, N: 8.54%; Measured value C: 51.27%, H: 0.95%, N: 8.46%.

[0151] 1HNMR (400MHz, ClCD3) δ: 8.29 (t, J = 2.1Hz, 1H), 7.83 (dd, J = 3.5, 2.2Hz, 3H), 7.64 (t, J = 2.2Hz, 1H), 7.53 (dt, J = 4.2, 2.1Hz, 2H), 7.22 (t, J = 2.2Hz, 1H), 7.18 (t, J = 2.2Hz, 1H). See the NMR spectrum. Figure 4 .

[0152] Synthesis Example 5: Synthesis of Compound 119

[0153]

[0154] The synthetic route is as follows:

[0155]

[0156] The specific preparation steps are as follows:

[0157] Step 1: Synthesis of intermediate H1

[0158] In a 500mL clean round-bottom flask, add thiazole-5-carboxylic acid (12.9g, 1.0eq, 0.1mol), phenol (9.4g, 1.0eq, 0.1mol), DCC (30.9g, 1.5eq, 0.15mol), DMAP (0.61g, 0.05eq, 5mmol) and THF (200mL) in sequence, start stirring, replace with nitrogen 3 times, and heat to reflux for 12 hours. After the reaction is completed, cool to room temperature, filter, dissolve the solid in a mixed solution of ethyl acetate and water, separate the liquids, extract with ethyl acetate, combine the organic phases, wash once with sodium chloride aqueous solution, and then dry with anhydrous sodium sulfate. After concentration, separate by column chromatography to obtain light yellow solid H1 (13.3g, yield 65%).

[0159] Step 2: Synthesis of intermediate H2

[0160] In a 1L clean round-bottom flask, add H1 (20.5g, 1.0eq, 0.1mol), Lawesson's reagent (6.1g, 0.15eq, 0.015mol)) and 400mL xylene in turn, heat and stir to reflux reaction for 24 hours. After the reaction is completed, cool to room temperature, remove xylene by rotary evaporation to obtain a crude product, and then dissolve the solid in a mixed solution of ethyl acetate and water, separate the liquids, extract with ethyl acetate, combine the organic phases, wash once with sodium chloride aqueous solution, and then dry with anhydrous sodium sulfate. After concentration, separate by column chromatography to obtain a light yellow solid H2 (18.8g, yield 85%).

[0161] Step 3: Synthesis of intermediate H3

[0162] In a 1L dry round-bottom flask, under nitrogen protection, H2 (22.1g, 1.0eq, 0.1mol), dry DMF (500mL) and ethyl isocyanoacetate (16.95g, 1.5eq, 0.15mol) were added in sequence, the temperature was lowered to 0°C, and then NaH (mass fraction 60%, 8g, 2.0eq, 0.2mol) was added, and the reaction was continued at this temperature for 24 hours. After the reaction was completed, the mixture was extracted with ethyl acetate, the organic phase was separated, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain a light yellow solid H3 (16.1g, yield 67%).

[0163] Step 4: Synthesis of intermediate H4

[0164] In a 1L dry round-bottom flask, H3 (24.0g, 1.0eq, 0.1mol), sodium hydroxide (10g, 2.5eq, 0.25mmol), 400mL ethanol and 100mL water were added in sequence, nitrogen was replaced three times, and the mixture was heated to reflux for 12 hours. After the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, the organic phase was separated, dried with anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain a light yellow solid H4 (15.9g, yield 75%).

[0165] Step 5: Synthesis of intermediate H5

[0166] In a 1L dry round-bottom flask, under nitrogen protection, H4 (21.2g, 1.0eq, 0.1mol), iodine (38.1g, 1.5eq, 0.15mol), potassium phosphate (21.2g, 1.0eq, 0.1mol) and 400mL acetonitrile were added in sequence, and the temperature was raised to reflux for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through diatomaceous earth, and the diatomaceous earth was rinsed with an appropriate amount of dichloromethane. The filtrate was concentrated and separated by column chromatography to obtain a light yellow solid H5 (24.1g, yield 82%).

[0167] Step 6: Synthesis of intermediate H6

[0168] In a 1L dry round-bottom flask, under nitrogen protection, H5 (29.4g, 1.0eq, 0.1mol), 3,4,5-trifluorophenylacetylene (15.6g, 1.0eq, 0.1mol), bistriphenylphosphine palladium dichloride (0.7g, 0.01eq, 1mmol), triphenylphosphine (0.5g, 0.02eq, 2mmol), cuprous iodide (0.4g, 0.02eq, 2mmol) and triethylamine 400mL were added in sequence, and the temperature was raised to reflux for 12 hours. After the reaction was completed, the solvent was removed by concentration under reduced pressure, and light yellow solid H6 (25.8g, yield 80%) was obtained by column chromatography.

[0169] Step 7: Synthesis of intermediate H7

[0170] In a 1L dry round-bottom flask, under nitrogen protection, H6 (32.2g, 1.0eq, 0.1mol), 3,4,5-trifluorobromobenzene (21.0g, 1.0eq, 0.1mol), palladium acetate (0.8g, 0.05eq, 5mmol), 1,1'-bis(diisopropylphosphino)ferrocene (di-Prpf) (2.5g, 0.06eq, 6mmol), triethylenediamine (DABCO) (22.4g, 2eq, 0.2mol) and 400mL of N-methylpyrrolidone were added in sequence, and the temperature was raised to 120°C for 12 hours. After the reaction, the temperature was cooled to room temperature, the solvent was distilled off under reduced pressure, and the liquid was separated by ethyl acetate and water extraction. The organic phase was dried over anhydrous sodium sulfate, and then the solvent was removed to obtain a crude product. The crude product was separated by column chromatography to obtain a light yellow solid H7 (38.0g, yield 84%).

[0171] Step 8: Synthesis of intermediate H8

[0172] In a 1L dry round-bottom flask, under nitrogen protection, solid H7 (45.2g, 1.0eq, 0.1mol) was added to 350mL tetrahydrofuran, and the temperature was cooled to -95℃~-90℃ by liquid nitrogen, and n-butyl lithium (92mL, 2.3eq, 2.5M n-hexane solution) was slowly added dropwise, and the temperature was maintained for 1 hour, and then the temperature was slowly raised to -78℃ and reacted for 6 hours. Then, a tetrahydrofuran solution (100mL) of elemental iodine (76.2g, 3.0eq, 0.3mol) was added, and the temperature was slowly raised to room temperature to react overnight, and a small amount of saturated ammonium chloride solution was added to quench, and then diatomaceous earth was directly added to mix the sample, and the white solid product H8 (31.7g, yield 45%) was purified by silica gel column chromatography.

[0173] Step 9: Synthesis of intermediate H9

[0174] In a 1L dry round-bottom flask, under nitrogen protection, malononitrile (39.6g, 6.0eq, 0.6mol) was added to anhydrous 400mL DMF, and NaH (24g, 6.0eq, 0.6mol, 60% content) was added in several times at 0℃, stirred at 0℃ for 10 minutes and at room temperature for 20 minutes, and then H8 (70.4g, 1.0eq, 0.1mol) and tetrakistriphenylphosphine palladium (11.6g, 0.1eq, 0.01mol) were added, and the temperature was raised to 90℃ for reaction for 24 to 36 hours. After complete conversion, it was poured into ice water, and the pH was adjusted to <1 with dilute hydrochloric acid. After sufficient stirring, a large amount of yellow solid precipitated, and the solid was filtered and collected. Washed with dichloromethane to obtain a yellow solid, and then washed twice with dichloromethane and heptane, filtered to obtain a yellow solid H9 (52.2g, yield 90%).

[0175] Step 10: Synthesis of compound 119

[0176] In a 2L dry round-bottom flask, under nitrogen protection, solid H9 (29.0g, 1.0eq, 0.05mol) was added to anhydrous 1LDCM, cooled to 0°C, and then [bis(trifluoroacetyloxy)iodo]benzene (PIFA) (21.5g, 1.0eq, 0.05mol) was added. Stir at room temperature for 3 days, and the solution was purple-black. The reaction solution was then placed in a 2L single-mouth bottle, the solution was spin-dried to about 100mL, 1L of n-hexane was added thereto, stirred for 10 minutes, and filtered to obtain a dark green solid, which was washed twice with a mixed solvent of dichloromethane and heptane, and finally a dark green solid compound 119 (22.5g, yield 78%) was obtained.

[0177] Product MS (m / e): 578.23; Elemental analysis (C 26 H4S2F6N6): Theoretical value C: 53.98%, H: 0.70%, N: 14.53%; Measured value C: 53.91%, H: 0.73%, N: 14.46%.

[0178] 1 HNMR (400MHz, ClCD3) δ: 7.63–7.54 (m, 4H). Figure 5 .

[0179] Synthesis Example 6: Synthesis of Compound 148

[0180]

[0181] 3,5-bis(trifluoromethyl)phenylacetylene was used to replace 3,4,5-trifluorophenylacetylene, and 3,5-bis(trifluoromethyl)bromobenzene was used to replace 3,4,5-trifluorobromobenzene. The material ratio, other raw materials and steps were the same as those in Synthesis Example 5, and 27.1 g of dark green solid Compound 148 was obtained.

[0182] Product MS (m / e): 742.46; Elemental analysis (C 30 H6S2F 12 N6): Theoretical value C: 48.53%, H: 0.81%, N: 11.32%; Measured value C: 48.47%, H: 0.88%, N: 11.26%.

[0183] 1 HNMR (400MHz, ClCD3) δ: 8.25 (d, J = 2.2Hz, 4H), 7.78 (t, J = 2.1Hz, 2H). Figure 6 .

[0184] Those skilled in the art should be aware that the above preparation method is only an illustrative example, and those skilled in the art can obtain other compound structures of the present invention by improving it.

[0185] The organic electroluminescent device was prepared by using the compound obtained above, as follows.

[0186] Device Example 1

[0187] The steps for preparing the device of this embodiment are as follows: First, the glass substrate with a 120nm thick indium tin oxide (ITO) anode is cleaned and then treated with UV ozone and oxygen plasma. After treatment, the substrate is dried in a glove box filled with nitrogen to remove moisture, and then the substrate is mounted on a substrate holder and loaded into a vacuum chamber. Next, the organic layer is evaporated and the vacuum is about 10 -8 Under the condition of torr The rate of evaporation is carried out on the ITO anode in sequence by thermal vacuum, as follows:

[0188] Compound HT and compound 64 were simultaneously deposited to form a hole injection layer (HIL) with a thickness of

[0189] Compound HT was used as a hole transport layer (HTL) with a thickness of

[0190] Compound EB is used as an electron blocking layer (EBL) with a thickness of

[0191] Then, the main compound A and the compound RD as the dopant are co-evaporated to form an emitting layer (EML) with a thickness of

[0192] Compound HB was used as the hole blocking layer (HBL) with a thickness of

[0193] On the hole blocking layer, compound ET and 8-hydroxyquinoline-lithium (Liq) were co-evaporated as an electron transport layer (ETL) with a thickness of

[0194] Finally, evaporation 8-Hydroxyquinoline-lithium (Liq) was used as an electron injection layer (EIL) and evaporated The device was then transferred back to the glove box and encapsulated with a glass lid to complete the device.

[0195] Device Examples 2-10

[0196] Device Examples 2-10 were prepared with reference to the above-mentioned Device Example 1, except that the composition of the hole injection layer (HIL) was different. The detailed device layer structures and thicknesses of Device Examples 2-10 are shown in Table 1. For layers using more than one material, different compounds were doped in the weight ratios recorded.

[0197] Table 1 also provides device comparative examples, and the preparation method of the device comparative examples is prepared by referring to device example 1. The detailed device layer structure and thickness of the device comparative examples are shown in Table 1. Similarly, for layers using more than one material, different compounds are doped in their recorded weight ratios.

[0198] Table 1 Device structures of device embodiments and comparative examples

[0199]

[0200]

[0201] The structure of some materials used in the device embodiments and comparative examples provided above is as follows:

[0202]

[0203] The performance of the above device embodiments and comparative examples was tested. Table 2 lists the performance of the device embodiments and comparative examples at 10 mA / cm 2 Under the conditions, the voltage (Voltage, V), current efficiency (CE) and device life (LT) of the device embodiments 1-10 and comparative examples 1-3 were measured. 97 )Test results.

[0204] Table 2 Device performance test data

[0205]

[0206] Through the above device test data, we can find that: compared with device comparative example 1, device embodiments 1-6 use the compound of the present invention as a dopant in the hole injection layer, and the device voltage is reduced, the current efficiency is improved, and the life span is unexpectedly improved. It can be seen that the compound of the present invention brings excellent device effects, which can enable the device to obtain higher current efficiency and life span, and has significant improvements in device performance. This proves the unique advantages of the compound of the present invention. It can be seen from the data of device comparative examples 2 and 3 of device embodiments 7 to 10 that when the compound of the present invention is used as a hole injection layer alone, it is better than the comparative example in terms of voltage, current efficiency and life span. The voltage can be reduced by about 0.5V, the current efficiency is improved, and the life span is doubled. It can be seen that when used as a hole injection layer alone, the compound of the present invention is a better choice than the comparative compound.

[0207] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiment, but the present invention is not limited to the above-mentioned detailed method. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of each raw material of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope of the present invention.

Claims

1. An organic compound, characterized in that It has a structure represented by formula I: In Formula I: Z1 and Z2 are selected, identically or differently, from O, S or Se at each occurrence; Each occurrence of X and Y is identical or different and is selected from the group consisting of the following structures: Each occurrence of Rm and Rn is identical or different and is selected from the group consisting of:

2. The compound according to claim 1, characterized in that The Z1 and Z2 are the same and are selected from O, S or Se.

3. The compound according to claim 1 or 2, characterized in that The compound has a structure represented by Formula II: In formula II, the groups Z, X, Y, Rm, and Rn represent atoms or groups shown in the following table:

4. Use of the organic compound according to any one of claims 1 to 3 in an organic electroluminescent device.

5. Use of the organic compound according to any one of claims 1 to 3 in an organic layer of an organic electroluminescent device.

6. Use of the organic compound according to any one of claims 1 to 3 in a hole injection layer of an organic electroluminescent device.

7. The use according to claim 6, characterized in that: The amount of the organic compound in the hole injection layer is 1% to 100% of the total weight of the hole injection layer.

8. An organic electroluminescent device comprising the organic compound according to any one of claims 1 to 3.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic electroluminescent device comprises an anode, a cathode, and at least one organic layer arranged between the anode and the cathode, wherein the organic layer comprises the organic compound according to any one of claims 1 to 3.

10. The organic electroluminescent device according to claim 9, characterized in that: The organic layer is a hole injection layer, and the hole injection layer contains the organic compound according to any one of claims 1 to 3.

11. The organic electroluminescent device according to claim 10, characterized in that: The hole injection layer also contains at least one hole transport material, which includes a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex; wherein the molar doping ratio of the organic compound to the hole transport material is 10000:1 to 1:10000.

12. The organic electroluminescent device according to claim 11, characterized in that: The molar doping ratio of the organic compound to the hole transport material is 10:1 to 1:

100.

13. A display component, characterized in that: The organic electroluminescent device according to claim 8 is included.

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