A nitrogen-containing heterocyclic organic compound and use thereof in an OLED device

Abstract

The application provides a nitrogen-containing heterocyclic organic compound and application thereof. The organic compound of the application has a structure represented by H-L-E, wherein H has a structure shown in formula 1, L is selected from an arylene group having 6-30 carbon atoms, a heteroarylene group having 3-30 carbon atoms, or a combination thereof, and E has a structure shown in formula 2. The compound of the application can be used as a host material of a light-emitting layer in an organic electroluminescent device, has a significantly reduced evaporation temperature, better thermal stability, can effectively reduce energy consumption, and improve device efficiency and reduce device driving voltage.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescence, and in particular relates to a nitrogen-containing heterocyclic organic compound, an organic electroluminescent device containing the compound, and applications of the compound. 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 photovoltaic devices (COPVs), dye-sensitized solar cells (DSSCs), organic photodetectors, 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 that included an arylamine hole transport layer and a tris-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 was applied to the device, green light was emitted from the device. This invention laid the foundation for the development of modern organic light-emitting diodes (OLEDs). The most advanced ones can include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light-emitting layers between the cathode and anode. Because 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 categorized into three different types based on their emission mechanism. The OLED invented by Tang and Van Slyke is a fluorescent OLED. It uses only singlet emission. Triplet states generated in the device are wasted through non-radiative decay channels. As a result, 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 use triplet emission from heavy metal complexes as the emitter. This allows for the harvesting of both singlet and triplet states, achieving an IQE of 100%. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributed to the commercialization of active-matrix OLEDs (AMOLEDs). More recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, enabling excitons to return from the doublet state to the singlet state. In TADF devices, triplet excitons can generate singlet excitons through reverse intersystem crossing, resulting in high IQE.

[0005] OLEDs can also be classified into small molecule and polymer OLEDs based on the form of the material used. A small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of a small molecule can be large as long as it has a precise structure. Dendrimers with a well-defined structure are considered small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with pendant luminescent groups. If post-polymerization occurs during the manufacturing process, small molecule OLEDs can become polymer OLEDs. There are various OLED manufacturing methods. Small molecule OLEDs are usually manufactured by vacuum thermal evaporation. Polymer OLEDs are manufactured by solution methods such as spin coating, inkjet printing, and nozzle printing. Small molecule OLEDs can also be manufactured by solution methods if the material can be dissolved or dispersed in a solvent.

[0006] The luminescent color of OLEDs can be achieved through the structural design of luminescent materials. OLEDs can include one or more luminescent layers to achieve the desired spectrum. Green, yellow and red OLEDs, phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still have problems such as unsaturated blue, short device life and high operating voltage. Commercial full-color OLED displays usually adopt a hybrid strategy, using blue fluorescence and phosphorescent yellow, or red and green. At present, the efficiency of phosphorescent OLEDs decreases rapidly under high brightness conditions, which remains a problem. In addition, it is expected to have a more saturated luminescent spectrum, higher efficiency and longer device life.

[0007] Many of the main materials reported so far still have room for improvement. In order to meet the industry's increasing demands, especially the demand for higher device efficiency, longer device life and lower driving voltage, new materials still need further research and development. Summary of the Invention

[0008] The object of the present invention is to provide an organic compound, in particular a carbazole-azaphenazine macrocyclic structure compound, which can be used as a host material in an organic electroluminescent device, has the advantages of significantly reducing the evaporation temperature and driving voltage, higher device efficiency and better thermal stability, can effectively reduce energy consumption, is more conducive to the device manufacturing process, and provides better device performance.

[0009] To achieve the above object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides an organic compound having a structure represented by the formula HLE, wherein H has a structure represented by the formula 1, where the formula 1 is:

[0011]

[0012] In Formula 1, Ring 1, Ring 2, Ring 3 and Ring 4 are each independently selected from an unsaturated carbocyclic ring having 5 to 30 carbon atoms or an unsaturated heterocyclic ring having 3 to 30 carbon atoms;

[0013] X is selected from O, S, Se, NR N 、SiR a R b , PR or BR;

[0014] R X Each occurrence of the same or different means mono-, poly- or no-substitution;

[0015] Each occurrence of L is selected from an arylene group having 6 to 30 carbon atoms, a heteroarylene group having 3 to 30 carbon atoms, or a combination thereof; optionally, the arylene group or heteroarylene group referred to by L is replaced by one or more R L replaced by;

[0016] E has a structure represented by Formula 2:

[0017]

[0018] In Formula 2, Z1 to Z5 are selected from NR N or CR a R b , and at least one of Z1 to Z5 is selected from NR N ;

[0019] R, RX 、R N 、R L 、R a and R b is selected, at each occurrence, identically or differently, from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3 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 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, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

[0020] Adjacent substituents R, R X 、R N 、R L 、R a and R b optionally linked to form a ring;

[0021] “*” indicates the position where L is bonded.

[0022] According to some embodiments of the present invention, in Formula 1, Ring 1, Ring 2, Ring 3 and Ring 4 are each independently selected from a 5-membered unsaturated carbocyclic ring, an aromatic ring having 6-30 carbon atoms, or a heteroaromatic ring having 3-30 carbon atoms. In some embodiments, Ring 1, Ring 2, Ring 3 and Ring 4 are each independently selected from an aromatic ring having 6-18 carbon atoms, or a heteroaromatic ring having 3-18 carbon atoms. In some embodiments, Ring 1, Ring 2, Ring 3 and Ring 4 are each independently selected from a benzene ring or a six-membered heteroaromatic ring. In some specific embodiments, Ring 1, Ring 2, Ring 3 and Ring 4 are each independently selected from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a furan ring, a thiophene ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyran ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a dibenzofuran ring, a dibenzothiophene ring or a carbazole ring.

[0023] In some embodiments, at least two of Ring 1, Ring 2, Ring 3, and Ring 4 are selected from benzene rings. In some specific embodiments, any two of Ring 1, Ring 2, Ring 3, and Ring 4 are selected from benzene rings, or any three of Ring 1, Ring 2, Ring 3, and Ring 4 are selected from benzene rings, or Ring 1, Ring 2, Ring 3, and Ring 4 are all benzene rings.

[0024] According to some embodiments of the present invention, X is selected from O, S, Se or NR N In some preferred embodiments, X is O. In some preferred embodiments, X is S.

[0025] According to some embodiments of the present invention, H in the compound has a structure shown in Formula 1-1:

[0026]

[0027] In formula 1-1, R X The definition of X is the same as that of formula 1.

[0028] In some preferred embodiments, in Formula 1-1, R X is hydrogen, deuterium, halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 18 carbon atoms. X is hydrogen, deuterium, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, biphenyl or naphthyl.

[0029] In some specific embodiments, the structure of H in the compound is selected from the structures numbered H1 to H108, or a structure obtained by partially or completely replacing hydrogen in any of the structures numbered H1 to H108 with deuterium; wherein the structures corresponding to numbers H1 to H108 are, in order:

[0030]

[0031]

[0032]

[0033]

[0034] “*” indicates the positions where H and L are bonded.

[0035] According to some preferred embodiments of the present invention, L is connected to H and E in the compound respectively through two adjacent ring atoms on the arylene or heteroarylene ring.

[0036] According to some embodiments of the invention, each occurrence of L is selected from structures represented by Formula LM-1 to Formula LM-6:

[0037]

[0038] Among them, A 1 To A 6 Each occurrence is selected from NR L or CR L1 R L2 ; Z is selected from O, S, Se and SiR each time it appears a R b Group composed of R L1 and R L2 The definition is the same as R L , R L The definition of is as above;

[0039] “*” indicates the position where H and L are bonded, Indicates the position where E and L are bonded.

[0040] In some preferred embodiments, L in the compound is selected from the structure shown in the above formula LM-1 or formula LM-2.

[0041] In some preferred embodiments, in formula LM-1, A 1 To A 4 Each occurrence is the same or different selection from CR L1 R L2 In some preferred embodiments, in formula LM-2, A 1 To A 6 Each occurrence is the same or different selection from CR L1 R L2 .

[0042] In some embodiments, in Formula LM-1 to Formula LM-6, R L 、R L1 and R L2 each is independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl having 3-10 carbon atoms, substituted or unsubstituted heteroalkyl having 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3-10 carbon atoms, substituted or unsubstituted aralkyl having 7-18 carbon atoms, substituted or unsubstituted aryl having 6-18 carbon atoms, substituted or unsubstituted heteroaryl having 3-18 carbon atoms, and combinations thereof.

[0043] In some embodiments, the structure of L in the compound is one of the structures numbered L-1 to L-40, or a structure obtained by partially or completely replacing the hydrogen in any of the structures numbered L-1 to L-40 with deuterium; wherein the structures corresponding to numbers L-1 to L-40 are, in order:

[0044]

[0045] According to some embodiments of the present invention, E in the compound is selected from the structure represented by Formula 2-1:

[0046]

[0047] wherein Z1 to Z3 are each independently selected from NR N or CR a R b , and at least two of Z1 to Z3 are NR N ; R N 、R a and R b The definition is the same as that of formula 2; Ar1 ​​and Ar2 are identically or differently selected from substituted or unsubstituted aryl groups having 6-18 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-18 carbon atoms at each occurrence, wherein the substituents involved in Ar1 and Ar2 are selected from deuterium, halogen (such as fluorine, chlorine, bromine, iodine, etc.), cyano, alkyl groups having 1-10 carbon atoms (such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, etc.), cycloalkyl groups having 3-10 carbon atoms (such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), aryl groups having 6-15 carbon atoms (such as phenyl, naphthyl, biphenyl, etc.) and combinations thereof.

[0048] In some preferred embodiments, in Formula 2-1, Z1 to Z3 are all NR N .

[0049] In some embodiments, R N Each occurrence is identically or differently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 10 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted aralkyl having 7 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 10 carbon atoms, substituted or unsubstituted aryloxy having 6 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, and combinations thereof. In some preferred embodiments, R N For hydrogen.

[0050] In some preferred embodiments, in Formula 2-1, Ar1 and Ar2 are selected from the group consisting of phenyl, deuterated phenyl, methylphenyl, fluorophenyl, tert-butylphenyl, trideuterated methylphenyl, biphenyl, naphthyl, deuterated naphthyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, carbazolyl, pyridyl, pyrimidinyl, 4-cyanophenyl, 3-cyanophenyl, triphenylene, and combinations thereof.

[0051] In some preferred embodiments, Ar1 and Ar2 are identically or differently selected from the group consisting of:

[0052]

[0053] In some preferred embodiments, E in the compound is selected from the structure represented by formula 2-1-1:

[0054]

[0055] In formula 2-1-1, Ar1 and Ar2 are defined the same as in formula 2-1.

[0056] In some preferred embodiments, Ar1 and Ar2 are each independently selected from phenyl and dibenzofuranyl. In some specific embodiments, Ar1 and Ar2 are both phenyl. In some specific embodiments, Ar1 is phenyl and Ar2 is dibenzofuranyl.

[0057] In some preferred embodiments, the structure of E in the compound is: one of the structures shown in numbers E1 to E44, or a structure obtained by partially or completely replacing hydrogen in any of the structures shown in numbers E1 to E44 with deuterium; wherein the structures corresponding to numbers E1 to E44 are, in order:

[0058]

[0059]

[0060] In some embodiments, H in the compound is selected from the group consisting of structures shown by numbers H1 to H108 above, L is selected from the group consisting of structures shown by numbers L-1 to L-40 above, and E is selected from the group consisting of structures shown by numbers E1 to E44 above. Optionally, the hydrogen in the compound is partially or completely replaced by deuterium.

[0061] In some embodiments, the compound is selected from compounds corresponding to numbers C1 to C600, or compounds obtained by partially or completely replacing hydrogen in any of the structures corresponding to numbers C1 to C600 with deuterium. The structures represented by numbers C1 to C600 have a structure of HLE, wherein H, L, and E correspond to the following Table 1:

[0062] Table 1

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070] In a second aspect, the present invention provides use of the above organic compound in preparing an organic electroluminescent device.

[0071] In some embodiments, the compound is used as a host material of a light-emitting layer in an organic electroluminescent device.

[0072] In a third aspect, the present invention provides an organic electroluminescent device, comprising a light-emitting layer, wherein the host material of the light-emitting layer contains the organic compound of the present invention.

[0073] In some embodiments, the organic electroluminescent device includes: an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode, and the host material of the light-emitting layer contains the organic compound of the present invention.

[0074] In some embodiments, the light-emitting layer further comprises a dopant. In some embodiments, the dopant contained in the organic electroluminescent device of the present application can be at least one phosphorescent or fluorescent dopant, preferably a phosphorescent dopant. The phosphorescent dopant material is not particularly limited, but can be preferably selected from metalized complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), more preferably ortho-metalized complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and even more preferably ortho-metalized iridium complex compounds. In some embodiments, the doping concentration (mass percentage) of the dopant is 1wt% to 20wt% relative to the host material in the light-emitting layer, preferably 1wt% to 10wt%, more preferably 2wt% to 8wt%.

[0075] Preferably, the organic electroluminescent device further comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0076] In a fourth aspect, the present application provides a display assembly / device comprising the organic compound of the first aspect of the present application or the organic electroluminescent device of the third aspect of the present application.

[0077] The present application has the following beneficial effects: The novel azacarbazole-naphthoxazine macrocyclic compound disclosed in the present application can be used as a host material in an electroluminescent device. The compound designed in this way contains both a hole transport unit and an electron transport unit, so that the molecules of these compounds can simultaneously transport holes and electrons, bringing unexpected effects, so that this novel compound has the effects of significantly reducing the evaporation temperature and driving voltage, effectively improving the device efficiency, having better thermal stability, effectively reducing the energy consumption, being conducive to the device manufacturing process, and further providing better device performance. BRIEF DESCRIPTION OF DRAWINGS

[0078] Figure 1 It is a schematic diagram of an organic light-emitting device in a specific embodiment of the present application.

[0079] Figure 2 It is a schematic diagram of an organic light-emitting device in another specific embodiment of the present application.

[0080] The reference signs are as follows:

[0081] 100, first organic light-emitting device, 101, substrate, 110, anode, 120, hole injection layer, 130, hole transport layer, 140, electron blocking layer, 150, light-emitting layer, 160, hole blocking layer, 170, electron transport layer, 180, electron injection layer, 190, cathode, 102, encapsulation layer, 200, second organic light-emitting device. DETAILED DESCRIPTION

[0082] The technical solutions of the present invention are described in detail below through specific examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. Any other equivalent changes or modifications that do not depart from the spirit disclosed by the present invention should be included in the scope of the claims.

[0083] OLEDs can be manufactured on a variety of substrates, such as glass, plastic, and metal. Figure 1 A first organic light-emitting device 100 is shown schematically and non-limitingly. The figure is not necessarily drawn to scale, and some layer structures in the figure may be omitted as needed. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light-emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180 and a cathode 190. The device 100 can be manufactured by depositing the described layers in sequence. The properties and functions of each layer and exemplary materials are described in more detail in columns 6-10 of U.S. Patent No. 7,279,704 B2, the entire contents of which are incorporated herein by reference.

[0084] There are many more examples of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. An example of a host material is disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, incorporated by reference in their entireties, disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg:Ag with an overlying transparent, conductive, sputter-deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, incorporated by reference in their entireties. An example of an injection layer is provided in U.S. Patent Application Publication No. 2004 / 0174H6, incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174H6, incorporated by reference in its entirety.

[0085] The above layered structures are provided by way of non-limiting examples. The functionality of an OLED can be achieved by combining the various layers described above, or some layers can be omitted entirely. It can also include other layers not explicitly described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimal performance. Any functional layer can include several sublayers. For example, a light-emitting layer can have two layers of different light-emitting materials to achieve a desired emission spectrum.

[0086] In one embodiment, an OLED can be described as having an "organic layer" disposed between a cathode and an anode. The organic layer can include one or more layers.

[0087] OLED also requires encapsulation layers, such as Figure 2 The second organic light emitting device 200 is shown schematically and non-limitingly. Figure 1 The difference is that an encapsulation layer 102 can also be included above cathode 190 to protect against harmful environmental substances such as moisture and oxygen. Any material that can provide an encapsulation function can be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly on the outside of the OLED device. Multilayer thin-film encapsulation is described in U.S. Patent No. 7,968,146 B2, the entire contents of which are incorporated herein by reference.

[0088] Devices manufactured according to embodiments of the present invention can be incorporated into various consumer products having one or more electronic component modules (or units) of the device. Some examples of these consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, smartphones, tablet computers, tablet phones, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, microdisplays, 3-D displays, vehicle displays, and taillights.

[0089] The materials and structures described herein can also be used in other organic electronic devices listed above.

[0090] Definition of terms

[0091] As used herein, the term "vicinal ring atoms" includes two ring atoms in adjacent positions on the same ring in a monocyclic, bicyclic or polycyclic ring system; it also includes two ring atoms in adjacent positions on different rings in a bicyclic or polycyclic ring system, for example Positions 1 and 8; positions 4 and 5 on the naphthalene ring.

[0092] As used herein, the term "halogen or halide" includes fluorine, chlorine, bromine and iodine.

[0093] As used herein, the term "alkyl" includes straight and branched chain alkyl groups. Alkyl groups can be alkyl groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 12 carbon atoms, and more preferably alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, 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, alkyl groups can 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, alkyl groups can be optionally substituted.

[0094] As used herein, the term "alkenyl" is a straight, branched or cyclic non-aromatic hydrocarbon group comprising one or more carbon-carbon double bonds. Alkenyl can be a straight, branched or cyclic non-aromatic hydrocarbon group having 2 to 20 carbon atoms and one or more carbon-carbon double bonds, preferably an alkenyl group having 2 to 12 carbon atoms, including but not limited to vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, isobutenyl, butadienyl, 1-pentenyl, 2-pentenyl, isopentenyl, 1,3-pentadienyl, 1,4-pentadienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,5-hexadienyl, 2,4-hexadienyl or 1,3,5-hexatrienyl. In addition, alkenyl can be optionally substituted.

[0095] As used herein, the term "cycloalkyl" encompasses cyclic alkyl groups. A cycloalkyl group may be one having 3 to 20 ring carbon atoms, preferably one having 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. Of the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and 4,4-dimethylcyclohexyl are preferred. In addition, the cycloalkyl group may be optionally substituted.

[0096] The term "heteroalkyl" as used herein includes a group in which one or more carbon atoms in an alkyl chain is replaced by a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a silicon atom, a germanium atom and a boron atom. The heteroalkyl group can be a heteroalkyl group having from 1 to 20 carbon atoms, preferably a heteroalkyl group having from 1 to 10 carbon atoms, more preferably a heteroalkyl group having from 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethyloxymethyl, ethoxymethyloxymethyl, ethoxyethyloxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, t-butyldimethylsilyl, triethylsilyl, triisopropylsilyl, trimethylsilylmethyl, trimethylsilyl ethyl, trimethylsilylisopropyl. In addition, the heteroalkyl group can be optionally substituted.

[0097] The term "carbocyclyl" as used herein is interchangeable with "carbocyclic ring" and means a non-aromatic, saturated or partially unsaturated monocyclic, polycyclic ring system composed of carbon atoms as ring atoms, and also includes aromatic rings composed of carbon atoms as ring atoms. In addition, the carbocyclyl group can be optionally substituted.

[0098] The term "heterocyclyl" as used herein is interchangeable with "heterocyclic ring", "carbocyclic heteroring", "carbocyclic heteroring group" and includes both aromatic cyclic groups and non-aromatic cyclic groups. The aromatic cyclic groups include heteroaromatic ring groups having from 3 to 18 ring atoms, at least one of which is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom and a boron atom. The non-aromatic heterocyclyl groups include saturated heterocyclic ring groups having from 3 to 30 ring atoms and unsaturated non-aromatic heterocyclic ring groups having from 3 to 30 ring atoms, at least one of which is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom and a boron atom, with preferred non-aromatic heterocyclyl groups being those having from 3 to 7 ring atoms which include at least one heteroatom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclyl groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thi- epinyl, azepinyl and tetrahydrothiopyranyl. In addition, the heterocyclyl group can be optionally substituted.

[0099] As used herein, the term "aryl or aromatic group" includes both non-fused and fused systems. 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, the aryl group may be optionally substituted. Examples of non-fused aryl groups 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, the aryl group may be optionally substituted.

[0100] As used herein, the term "heteroaryl" encompasses non-fused and fused heteroaromatic groups containing from 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. A heteroaryl group also refers to a heteroaryl group. The heteroaryl group may have from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, and more preferably from 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, Quinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenobenzodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazole and aza analogs thereof. In addition, the heteroaryl group may be optionally substituted.

[0101] As used herein, the term "alkoxy" is represented by -O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or -O-heterocyclyl. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl, and heterocyclyl groups are the same as those described above. The alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy, and ethoxymethyloxy. In addition, the alkoxy group may be optionally substituted.

[0102] As used herein, the term "aryloxy" refers to -O-aryl or -O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as those described above. The aryloxy group may be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the aryloxy group include phenoxy and biphenyloxy. In addition, the aryloxy group may be optionally substituted.

[0103] As used herein, the term "aralkyl" encompasses aryl-substituted alkyl groups. 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 aralkyl groups 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.Alkyl group can be substituted alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl, alkyl,

[0104] The term "alkylsilyl or silyl" as used herein encompasses silyl groups substituted by the groups listed above for the alkyl group, specifically including: methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl and the like.

[0105] As used herein, the term "aryl silanyl" refers to groups comprising any of the foregoing aryl groups and silanyl groups.

[0106] As used herein, the term "aza" in the terms "aza-dibenzofuran, aza-dibenzothiophene" and the like means that one or more C-H groups in the corresponding aromatic fragment are replaced with a nitrogen atom. For example, aza-triphenylenes include dibenzo[f,h]quinoline, dibenzo[f,h]quinoline and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the aza derivatives described above will occur to those of ordinary skill in the art and all such analogs are intended to be encompassed by the terms described herein.

[0107] In the present disclosure, unless otherwise defined, when any of the terms from the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilicon, substituted arylsilane, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphine, when used, means that any of the alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilicon, arylsilane, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphine groups can be substituted with one or more selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted heterocyclyl having 3 to 20 ring atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkynyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilicon having 3 to 20 carbon atoms, unsubstituted arylsilane having 6 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphine and combinations thereof.

[0108] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, it can be written by its name according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or attached fragments are considered to be equivalent.

[0109] In the compounds described herein, 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. The replacement of other stable isotopes in compounds may be preferred because it enhances device efficiency and stability.

[0110] In the compounds described herein, multiple substitution refers to a range including disubstitution up to the maximum number of available substitutions. When a substituent in a compound described herein represents multiple substitutions (including disubstitution, trisubstitution, tetrasubstitution, etc.), it means that the substituent can be present at multiple available substitution positions on its connected structure, and the substituents present at multiple available substitution positions can have the same structure or different structures.

[0111] In the compounds mentioned in the present disclosure, unless explicitly defined, for example, adjacent substituents can optionally be 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 optionally be connected to form a ring, including both situations where adjacent substituents can be connected to form a ring and situations where adjacent substituents are not connected to form a ring. When adjacent substituents can optionally be connected to form a ring, the ring formed can be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic rings. 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.

[0112] In the present invention, the expression that adjacent substituents can be optionally linked to form a ring is also intended 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:

[0113]

[0114] The statement that adjacent substituents can optionally be 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 via a chemical bond to form a ring, as can be exemplified by the following formula:

[0115]

[0116] Furthermore, the statement that adjacent substituents can optionally be 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:

[0117]

[0118] In the examples of material synthesis, unless otherwise stated, all reactions were carried out under nitrogen protection. All reaction solvents were anhydrous and used as they were from commercial sources. The synthetic products were prepared using 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 tested for structure confirmation and properties using methods well known to those skilled in the art. In the embodiments of the device, the properties of the device were also tested using conventional equipment in the art (including but not limited to the vapor deposition machine produced by Nanjing Institute of Microbiology, the optical testing system and life test system produced by Suzhou Fushida, the ellipsometer produced by Wuhan Yiguang Technology, etc.) using methods well known to those skilled in the art. Since those skilled in the art are aware of the relevant content such as the use of the above-mentioned equipment and the testing methods, they can obtain the inherent data of the sample with certainty and without being affected. Therefore, the above-mentioned relevant content will not be elaborated in this patent.

[0119] The preparation method of the compound of the present invention is not limited. The following compounds are typically but not limitedly exemplified, and their synthetic routes and preparation methods are as follows:

[0120] Example 1: Synthesis of Compound C1

[0121]

[0122] The synthetic route is as follows:

[0123]

[0124] Specific synthesis steps:

[0125] (1) 10H-phenoloxazine (18.3 g, 1 eq, 100 mmol), o-bromoiodobenzene (28.3 g, 1 eq, 100 mmol), sodium tert-butoxide (14.4 g, 1.5 eq, 150 mmol), Pd2(dba)3 (961 mg, 0.01 eq, 1 mmol) and tri-tert-butylphosphine tetrafluoroborate (580 mg, 0.02 eq, 2 mmol) were added to a 2 L dry round-bottom flask in sequence. Nitrogen was replaced with toluene (200 mL) three times. The temperature was controlled at about 110 ° C and the reaction was carried out for 12 hours. After the reaction was completed, the temperature was cooled to room temperature and adjusted to neutral with 1 M dilute hydrochloric acid. The mixture was allowed to stand for separation. The aqueous phase was extracted with toluene, and the organic phase was separated. The organic phases were combined and dried over anhydrous magnesium sulfate. After concentration, the mixture was separated by column chromatography to obtain white solid compound H1-1 (23.6 g, yield 70%).

[0126] (2) H1-1 (33.7 g, 1.0 eq, 100 mmol), triisopropyl borate (24.44 g, 1.3 eq, 130 mmol) and tetrahydrofuran 400 mL were added in sequence to a 2 L dry round-bottom flask. Under nitrogen protection, n-butyl lithium (52 ​​mL, 1.3 eq, 130 mmol) was added dropwise at about -78 ° C. The addition time was controlled to about 1 hour. After the addition was completed, the temperature was controlled at about -78 ° C for 1 hour. After the reaction was completed, the temperature was returned to 0 ° C and dilute hydrochloric acid was added dropwise until the pH value was less than 3. Stir for 10 minutes, extract with ethyl acetate, separate the organic phase, wash the organic phase with saturated sodium chloride solution three times, wash the organic phase with water once, dry with anhydrous magnesium sulfate, concentrate and slurry with heptane to obtain white solid compound H1-2 (25.8 g, yield 85%).

[0127] (3) H1-2 (30.3 g, 1 eq, 100 mmol), potassium carbonate (27.6 g, 2 eq, 200 mmol), 2-chloro-6-nitrophenyl trifluoromethanesulfonate (30.5 g, 1 eq, 100 mmol), Pd(Ph3)4 (1.115 mg, 0.01 eq, 1 mmol), toluene (320 mL), water (160 mL), and ethanol (160 mL) were added sequentially to a 2 L dry round-bottom flask. The nitrogen atmosphere was replaced three times, and the temperature was controlled at about 75 ° C. The reaction was carried out for 12 hours. After the reaction was completed, the temperature was cooled to room temperature, extracted with toluene, and the organic phase was separated. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and separated by column chromatography to obtain a white solid compound H1-3 (18.6 g, yield 45%).

[0128] (4) H1-3 (41.4 g, 1 eq, 100 mmol), palladium acetate (830 mg, 0.05 eq, 5 mmol), cesium carbonate (65.2 g, 2 eq, 200 mmol), 100 mL DMAc, and 400 mL xylene were added to a 2 L dry round-bottom flask in sequence, and the nitrogen was replaced three times. The temperature was controlled at about 75 ° C. and the reaction was carried out for 12 hours. After the reaction was completed, the temperature was cooled to room temperature, extracted with toluene, and the organic phase was separated. It was dried over anhydrous magnesium sulfate, concentrated, and separated by column chromatography to obtain a white solid compound H1-4 (24.6 g, yield 65%).

[0129] (5) H1-4 (37.8 g, 1 eq, 100 mmol), triphenylphosphine (78.6 g, 3 eq, 300 mmol), and cesium carbonate (65.2 g, 2 eq, 200 mmol) were added to a 2 L dry round-bottom flask in sequence. The temperature was controlled at about 160 ° C for reaction for 5 hours. After the reaction was completed, the temperature was lowered to 100 ° C, 500 mL of toluene was added, and anhydrous zinc chloride (68 g, 5 eq, 500 mmol) was added after stirring. The mixture was stirred for half an hour and filtered. The filtrate was passed through a silica gel column. After desolvation, ethanol was added for crystallization to obtain yellow solid compound H1 (27.7 g, yield 80%).

[0130] (6) In a 2L dry three-necked flask, under nitrogen protection, 2-chloro-4,6-diphenyl-1,3,5-triazine (26.7g, 1.0eq, 100mmol), o-fluorophenylboric acid (15.4g, 1.1eq, 110mmol), potassium carbonate (41.4g, 3.0eq, 300mmol) and palladium 132 (45mg, 0.5g / mol), 400mL of dioxane, and 200mL of water were added in sequence. The temperature was raised to 100℃ and the reaction was carried out for 12 hours. After the reaction was completed, the temperature was lowered to room temperature, filtered, and the bottom of the flask was rinsed with heptane. The obtained solid was dissolved in 100V toluene and passed through a silica gel-alumina flash column. The filtrate was washed with toluene until there was no fluorescence. The obtained filtrate was concentrated to a small amount of solvent and filtered to obtain E1-1 (27.8g, yield 85%).

[0131] (7) H1 (34.6 g, 1.1 eq, 100 mmol), E1-1 (36.0 g, 1 eq, 110 mmol), cesium carbonate (65.2 g, 2 eq, 200 mmol), and 400 mL of DMAc were added to a 2 L dry round-bottom flask in sequence. The temperature was controlled at about 160 ° C and the reaction was carried out for 12 hours. After the reaction was completed, the temperature was cooled to room temperature. 200 mL of water and 500 mL of dichloromethane were added to the system, and the liquids were separated. After the aqueous phase was extracted with dichloromethane, the organic phase was separated, dried over anhydrous magnesium sulfate, concentrated, and separated by column chromatography to obtain white solid compound C1 (32.7 g, yield 50%).

[0132] Product MS (m / e): 653; 1 H NMR (400MHz, CDCl3): δ8.45–8.36(m,4H),8.06(dd,1H),7.97(dd,1H),7.72–7.64(m,2H),7.59(dd,1H),7.5 6–7.45(m,9H),7.44(ddd,1H),7.39(t,1H),7.32(dd,1H),7.30–7.22(m,3H),7.15(ddd,1H),6.92(ddd,2H).

[0133] Example 2: Synthesis of Compound C55

[0134]

[0135] The synthetic route is as follows:

[0136]

[0137] Specific synthesis steps:

[0138] 10H-phenothiazine was used instead of 10H-phenoxazine, and an appropriate material ratio was selected. Other raw materials and steps were the same as in Example 1 to obtain compound C55.

[0139] Product MS (m / e): 380. 1 H NMR (400MHz, CDCl3): δ8.45-8.36(m,4H),7.97(dd,1H),7.76-7.67(m,3H),7.59(dd,1H), 7.56-7.45(m,7H),7.48-7.38(m,5H),7.34-7.30(dddd,4H),7.27(dd,1H),7.18(td,1H).

[0140] Example 3: Synthesis of Compound C109

[0141]

[0142] The synthetic route is as follows:

[0143]

[0144] Compound C109 was obtained by replacing o-fluorophenylboric acid with (8-fluoronaphthalen-1-yl)boric acid, selecting an appropriate material ratio, and using the same other materials and steps as in Example 1. The product MS (m / e) was 703.

[0145] Example 4: Synthesis of Compound C163

[0146]

[0147] The synthetic route is as follows:

[0148]

[0149] Specific synthesis steps:

[0150] To a 2-L dry round-bottom flask, H55 (36.2 g, 1.1 eq, 100 mmol), E1-2 (41.5 g, 1 eq, 110 mmol), cesium carbonate (65.2 g, 2 eq, 200 mmol), and 400 mL of DMAc were added sequentially. The reaction was maintained at approximately 160°C for 12 hours. After the reaction, the temperature was lowered to room temperature, and 200 mL of water and 500 mL of dichloromethane were added. The aqueous phase was extracted with dichloromethane, and the organic phase was separated, dried over anhydrous magnesium sulfate, concentrated, and separated by column chromatography to obtain compound C163 (32.3 g, 46% yield) as a white solid. The product MS (m / e) was 719.

[0151] Example 5: Synthesis of Compound C217

[0152]

[0153] The synthetic route is as follows:

[0154]

[0155] Specific synthesis steps:

[0156] (1) 2-Chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine (63.5 g, 1 eq., 177 mmol), o-fluorophenylboric acid (25.6 g, 1.03 eq., 183 mmol), potassium carbonate (30.42 g, 3 eq., 93.3 mmol), Pd(PPh3)4 (2.05 g, 0.01 eq., 1.77 mmol), and 50% dioxane were added to a 1 L three-necked flask. 0mL, 265mL of water, nitrogen protection, heated to 100℃ and refluxed for 3h, followed the reaction, after the reaction was completed, cooled to room temperature, added 500mL of water and stirred for 0.5h, filtered, and the obtained solid was dissolved in 500mL of dichloromethane. The organic phase was passed through a vacuum column (5cm silica gel-3cm alumina-2cm anhydrous sodium sulfate) and washed with dichloromethane until there was no product. Then the solvent was removed, 2 volumes of toluene were added, heated to 110℃ to dissolve, cooled and crystallized, and filtered to obtain 65.6g of E16-1 with a yield of 88%.

[0157] (2) H1 (34.6 g, 1.1 eq, 100 mmol), E16-1 (45.9 g, 1 eq, 110 mmol), cesium carbonate (65.2 g, 2 eq, 200 mmol), and 400 mL of DMAc were added to a 2 L dry round-bottom flask in sequence. The temperature was controlled at about 160 ° C and the reaction was carried out for 12 hours. After the reaction was completed, the temperature was cooled to room temperature. 200 mL of water and 500 mL of dichloromethane were added to the system, and the liquids were separated. After the aqueous phase was extracted with dichloromethane, the organic phase was separated, dried over anhydrous magnesium sulfate, concentrated, and separated by column chromatography to obtain white solid compound C217 (37.9 g, yield 51%).

[0158] Product MS (m / e): 743. 1 H NMR (400MHz, CDCl3): δ8.44-8.37(m,2H),7.98(ddd,2H),7.84(dd,1H),7.72-7.64(m,2H), 7.66-7.56(m,4H),7.56-7.41(m,9H),7.39-7.23(m,5H),7.18-7.11(m,2H),6.92(ddd,2H).

[0159] Example 6: Synthesis of Compound C271

[0160]

[0161] The synthetic route is as follows:

[0162]

[0163] Specific synthesis steps:

[0164] To a 2-L dry round-bottom flask, H55 (36.2 g, 1.1 eq, 100 mmol), E16-1 (45.9 g, 1 eq, 110 mmol), cesium carbonate (65.2 g, 2 eq, 200 mmol), and 400 mL of DMAc were added sequentially. The reaction was maintained at approximately 160°C for 12 hours. After the reaction, the temperature was lowered to room temperature, and 200 mL of water and 500 mL of dichloromethane were added. The aqueous phase was extracted with dichloromethane, and the organic phase was separated, dried over anhydrous magnesium sulfate, concentrated, and separated by column chromatography to obtain compound C271 (41.7 g, 55% yield) as a white solid. The product MS (m / e) was 759.

[0165] Example 7: Synthesis of Compound C325

[0166]

[0167] The synthetic route is as follows:

[0168]

[0169] Specific synthesis steps:

[0170] Compound C325 was obtained by replacing o-fluorophenylboric acid with (8-fluoronaphthalen-1-yl)boric acid, selecting an appropriate material ratio, and using the same other starting materials and steps as in Example 5. The product MS (m / e) was 793.

[0171] Example 8: Synthesis of Compound C379

[0172]

[0173] The synthetic route is as follows:

[0174]

[0175] Specific synthesis steps:

[0176] Compound C379 was obtained by replacing E16-1 with E16-2 and selecting appropriate material ratios. Other raw materials and steps were the same as in Example 6. Product MS (m / e): 809.

[0177] 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.

[0178] Device Example 1

[0179] First, a glass substrate with a 120nm thick indium tin oxide (ITO) anode was cleaned and then treated with UV ozone and oxygen plasma. After treatment, the substrate was dried in a nitrogen-filled glove box to remove moisture, and then the substrate was mounted on a substrate holder and loaded into a vacuum chamber. The organic layers specified below were deposited at a vacuum of approximately 10 -8 Torr's case The deposition rate was 1000 nm by thermal vacuum deposition on the ITO anode. At the same time, the compound HT and NDP-9 (weight ratio 98:2) were evaporated as the hole injection layer (HIL) with a thickness of Compound HT was used as the hole transport layer (HTL) with a thickness of Compound EB is used as electron blocking layer (EBL) with a thickness of Then, the compound C1 of the present invention as the main body and the compound RD as the dopant (weight ratio 98:2) were co-evaporated to form an emitting layer (EML) with a thickness of Compound HB was used as the hole blocking layer (HBL) with a thickness of On the hole blocking layer, compound ET and 8-hydroxyquinoline-lithium (Liq) were co-evaporated (weight ratio 50:50) as an electron transport layer (ETL) with a thickness of Finally, evaporation Thickness of 8-hydroxyquinoline-lithium (Liq) as the 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.

[0180] Device Examples 2 to 9

[0181] The method is the same as that of device example 1, except that compounds C55, C109, C163, C217, C271, C325 and C379 of the present invention are used as host materials instead of compound C1 in the light-emitting layer (EML).

[0182] Device Comparative Example 1

[0183] The method is the same as that of device example 1, except that compound A is used as the host material in the emission layer (EML) instead of compound C1 of the present invention.

[0184] The material structure used in the device is shown below:

[0185]

[0186]

[0187] Table 2 lists the 2 The current efficiency (CE) and voltage (V) were measured under the following conditions. To better illustrate the data comparison, the CE and V data of Comparative Example 1 were set to 100%, and the CE and V data of Device Examples 1 to 8 were converted relative to the corresponding data of Comparative Example 1. The relevant data and conversion results are shown in Table 2.

[0188] Table 2

[0189] Device ID Main material Driving voltage (V) Current efficiency CE Example 1 C1 89％ 109％ Example 2 C55 83％ 115％ Example 3 C109 88％ 114％ Example 4 C163 82％ 116％ Example 5 C217 80％ 113％ Example 6 C271 79％ 118％ Example 7 C325 84％ 107％ Example 8 C379 82％ 112％ Comparative Example 1 Compound A 100％ 100％

[0190] As shown in Table 2, at 10 mA / cm 2 Under the current density, the current efficiency of device examples 1 to 9 is improved by 7% to 18% compared with comparative example 1, and the voltage is significantly reduced by 11% to 21%.

[0191] The above data show that the device of the embodiment of the present invention has a significantly improved current efficiency and a significantly reduced driving voltage relative to the device of the comparative example, that is, the compound of the present invention has a hole transport unit having a carbazole-phenazine fused nitrogen macrocyclic structure and an electron transport unit containing a triazine structure connected. Compared with the comparative example compound A, due to the change in the connecting segment, it is different from the compound A in device performance, and unexpectedly, while improving the current efficiency, it significantly reduces the driving voltage of the device, bringing very excellent device effects. This proves the unique advantages of the compound of the present invention.

[0192] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the present invention. Therefore, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific embodiments and preferred embodiments described herein. Many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the present invention. It should be understood that the various theories regarding why the present invention works are not intended to be restrictive.

Claims

1. A nitrogen-containing heterocyclic organic compound having a structure represented by the formula HLE, wherein H in the compound is selected from the group consisting of the following structures: "*" indicates the position of bonding with H and L; L in the compound is selected from the group consisting of the following structures: "*" indicates the position where H and L are bonded, Indicates the position where E and L are bonded; E in the compound is selected from the group consisting of the following structures: Indicates the position where E and L are bonded.

2. The organic compound according to claim 1, characterized in that The compound is selected from the compounds corresponding to the numbers in the following table, or compounds obtained by partially or completely replacing hydrogen in any structure corresponding to the numbers in the following table with deuterium, wherein H, L and E in the structures shown in the numbers in the following table correspond to the following:

3. Use of the organic compound according to any one of claims 1 to 2 in the preparation of an organic electroluminescent device.

4. The use according to claim 3, characterized in that The compound is used as a host material of a light-emitting layer in an organic electroluminescent device.

5. An organic electroluminescent device comprising a light-emitting layer, wherein a host material of the light-emitting layer contains the organic compound according to any one of claims 1 to 2.

6. The organic electroluminescent device according to claim 5, characterized in that: The light-emitting layer further contains at least one phosphorescent or fluorescent dopant.

7. The organic electroluminescent device according to claim 6, characterized in that: The dopant accounts for 1 wt% to 20 wt% of the total mass of the main material of the light-emitting layer.

8. The organic electroluminescent device according to claim 6, characterized in that: The dopant accounts for 1 wt% to 10 wt% of the total mass of the main material of the light-emitting layer.

9. The organic electroluminescent device according to claim 6, characterized in that: The dopant accounts for 2 wt% to 8 wt% of the total mass of the main material of the light-emitting layer.

10. The organic electroluminescent device according to claim 5, characterized in that: The device includes an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode.

11. The organic electroluminescent device according to claim 5, characterized in that: The organic electroluminescent device further includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

12. A display component / device comprising the organic electroluminescent device according to claim 5.

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