An organic compound, an organic electroluminescent material and its application

Abstract

The present invention provides an organic compound, an organic electroluminescent material, and their applications. The organic compound has a structure shown in Formula I below. The organic compound provided by the present invention can be used as a hole transport layer and / or luminescence-assisting layer material, effectively transporting holes and blocking electrons, thereby improving exciton utilization. The organic compound has suitable hole mobility, a high Tg, good thermal stability, and the molecules have appropriate distortion and steric hindrance, making the material less susceptible to crystallization. The organic compound can be used in the hole transport layer and / or luminescence-assisting layer of an organic light-emitting device, reducing the device driving voltage and improving the device luminous efficiency and lifespan.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic photoelectric materials, and in particular relates to an organic compound, an organic electroluminescent material and applications thereof. Background Art

[0002] An organic electroluminescent element (so-called organic EL element) is a light-emitting element having a structure in which at least one light-emitting organic layer is inserted between an anode and a cathode as a light-emitting layer. In such a light-emitting element, an electric field is applied between the cathode and anode, injecting electrons from the cathode into the light-emitting layer, and injecting holes from the anode into the light-emitting layer. In the light-emitting layer, the electrons and holes recombine to produce excitons. When these excitons return to a ground state, some of their energy is released as light.

[0003] In addition to the necessary light-emitting layer, OLED devices contain any one or a combination of at least two of the following: hole injection layer, hole transport layer, light-emitting auxiliary layer, light-emitting layer, hole blocking layer, electron buffer layer, electron transport layer, electron buffer layer or electron injection layer, which are used to regulate the injection and transport of electrons and holes.

[0004] There are currently several technical problems with hole transport materials: first, the material's solubility is poor, which will lead to poor cleaning effects of the vapor-deposited film during mass production; second, the material's mobility is too slow, which will cause the overall voltage of the device to be too high; third, the material's mobility is too fast, especially the material's lateral mobility is too fast, which will cause crosstalk between adjacent pixels; fourth, the material's LUMO energy level is too deep to effectively block the migration of electrons that may cross the light-emitting layer; fifth, the material's triplet energy level is low, which cannot effectively block the excitons in the light-emitting layer, resulting in low device luminescence efficiency.

[0005] In order to solve the luminescence problem in the hole transport layer, the method of using a luminescent auxiliary layer between the hole transport layer and the luminescent layer has been studied. The auxiliary organic layer helps to improve the injection efficiency of carriers (holes and electrons) between the interfaces of each layer and balance the transmission of carriers between the layers, thereby improving the brightness and efficiency of the device.

[0006] Research on organic electroluminescent materials has been widely carried out in academia and industry, but so far, stable and efficient organic layer materials for organic electrical components have not been fully developed, and the industrialization process of this technology still faces many key problems. Therefore, the development of new materials has always been an urgent problem to be solved by technical personnel in this field. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the purpose of the present invention is to provide an organic compound, an organic electroluminescent material and their applications. The organic compound provided by the present invention is an organic electroluminescent compound that can be used as a hole transport layer and / or light-assisted layer material, which can reduce the device driving voltage and improve the device luminous efficiency and life.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides an organic compound having a structure shown in Formula I below:

[0010]

[0011] wherein L1, L2, L3, and L4 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 (e.g., C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, etc.) Any one of an arylene group, a substituted or unsubstituted C3-C30 (for example, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, etc.) heteroarylene group;

[0012] R1 and R2 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C C28, C29, C30, etc.) straight chain or branched alkyl, substituted or unsubstituted C3-C30 (for example, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C3 C6-C60 (for example, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, C60, etc.), aryl, any one of substituted or unsubstituted C3-C60 (for example, C3, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, C60, etc.) heteroaryl;

[0013] n is selected from 1 or 2.

[0014] The organic compounds provided by the present invention can be used as hole transport layer and / or luminescence auxiliary layer materials, can effectively transport holes and block electrons, and improve the utilization rate of excitons; have suitable hole mobility, high Tg, good thermal stability, and the molecules have appropriate twisting and steric hindrance, making the material difficult to crystallize; can be used in the hole transport layer and / or luminescence auxiliary layer of organic light-emitting devices, reduce the device driving voltage, and improve the device luminescence efficiency and lifespan.

[0015] In the present invention, the substituents in the substituted arylene group, substituted heteroarylene group, substituted linear or branched alkyl group, substituted cycloalkyl group, substituted aryl group, and substituted heteroaryl group are each independently selected from deuterium, halogen, cyano, C1-C30 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, etc.) straight chain or branched alkyl, C3-C30 (for example, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, etc.) cycloalkyl, C6-C60 (for example, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, C6 0, etc.) aryl or C3-C60 (for example, C3, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, C60, etc.) heteroaryl or any one or a combination of at least two thereof.

[0016] Preferably, the substituents in the substituted arylene group, substituted heteroarylene group, substituted linear or branched alkyl group, substituted cycloalkyl group, substituted aryl group, and substituted heteroaryl group are each independently selected from any one or a combination of at least two of deuterium, halogen, cyano, methyl, phenyl, naphthyl, dibenzofuranyl, dibenzothienyl, or dimethylfluorenyl.

[0017] In the present invention, the organic compound is selected from any one of the following formulas I-1 to I-4:

[0018]

[0019] Wherein, L1, L2, L3, L4, R1, and R2 have the same defined ranges as those described in Formula I above.

[0020] In the present invention, L1, L2, L3, and L4 are each independently selected from any one of a single bond, a phenylene group, and a biphenylene group.

[0021] In the present invention, R1 is selected from any one of hydrogen, deuterium, halogen, phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted benzocarbazolyl, substituted or unsubstituted benzonaphthofuranyl, and substituted or unsubstituted benzonaphthothiophenyl.

[0022] Preferably, the substituents in the substituted biphenyl group, substituted terphenyl group, substituted naphthyl group, substituted phenanthrenyl group, substituted anthracenyl group, substituted pyridyl group, substituted dibenzofuranyl group, substituted dibenzothiophenyl group, substituted carbazolyl group, substituted dimethylfluorenyl group, substituted diphenylfluorenyl group, substituted spirobifluorenyl group, substituted benzocarbazolyl group, substituted benzonaphthofuranyl group and substituted benzonaphthothiophenyl group are selected from any one or a combination of at least two of deuterium, halogen, cyano, methyl, phenyl, naphthyl, dibenzofuranyl group, dibenzothiophenyl group or dimethylfluorenyl group.

[0023] Preferably, the dimethylfluorenyl group is selected from any one of the following structures:

[0024]

[0025] in, Indicates the attachment site of a group.

[0026] Preferably, the diphenylfluorenyl group is selected from any one of the following structures:

[0027]

[0028] in, Indicates the attachment site of a group.

[0029] Preferably, the carbazole group is selected from any one of the following structures:

[0030]

[0031] in, Indicates the attachment site of a group.

[0032] In the present invention, R2 is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl or dibenzothiophenyl.

[0033] Preferably, said R2 is selected from phenyl.

[0034] In the present invention, the organic compound includes any one of the following M1-M66:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040] In a second aspect, the present invention provides an organic electroluminescent material, which comprises the organic compound as described in the first aspect.

[0041] In a third aspect, the present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode, wherein the organic thin film layer comprises the organic compound described in the first aspect or the organic electroluminescent material described in the second aspect.

[0042] Preferably, the organic thin film layer includes any one of a hole injection layer, a hole transport layer, a luminescence auxiliary layer, a luminescent layer, a hole blocking layer, an electron buffer layer, an electron transport layer, an electron buffer layer or an electron injection layer, or a combination of at least two thereof.

[0043] Preferably, the hole transport layer comprises the organic compound as described in the first aspect.

[0044] Preferably, the light-emitting auxiliary layer comprises the organic compound as described in the first aspect.

[0045] In a fourth aspect, the present invention provides an electronic device, comprising the organic electroluminescent device according to the third aspect.

[0046] Preferably, the electronic device includes any one of an optical fiber, a lighting device, an electrophotographic photoreceptor, a photoelectric converter, an organic solar cell, a switching element, an organic light-emitting field-effect transistor, an image sensor or a dye laser.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] The organic compounds provided by the present invention can be used as hole transport layer and / or luminescence auxiliary layer materials, can effectively transport holes and block electrons, and improve the utilization rate of excitons; have suitable hole mobility, high Tg, good thermal stability, and the molecules have appropriate twisting and steric hindrance, making the material difficult to crystallize; can be used in the hole transport layer and / or luminescence auxiliary layer of organic light-emitting devices, reduce the device driving voltage, and improve the device luminescence efficiency and lifespan.

[0049] Explanation of terms

[0050] As used in the present invention, the term "organic electroluminescent compound" means a compound that can be used in an organic electroluminescent device and can be contained in any layer constituting the organic electroluminescent device as needed.

[0051] Definition of device terms

[0052] As used in the present invention, the term "organic electroluminescent material" refers to a material that can be used in an organic electroluminescent device and that may include at least one compound. If necessary, the organic electroluminescent material may be included in any layer constituting the organic electroluminescent device. For example, the organic electroluminescent material may be a hole injection material, a hole transport material, an electron blocking material, a luminescence auxiliary material, a light-emitting layer material (including a host material and a dopant material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, and the like.

[0053] The organic electroluminescent material disclosed in the present invention may include at least one compound represented by Formula I. Although not limited thereto, the compound having Formula I may be included in the hole transport layer, and / or the compound having the structure represented by Formula 1 may be included in the light-emitting auxiliary layer, and is not limited thereto.

[0054] Hereinafter, each layer of the organic electroluminescent device comprising the compound of formula I of the present invention will be described.

[0055] substrate

[0056] Organic EL devices are generally fabricated on a light-transmitting substrate that supports the organic EL device. The light-transmitting substrate preferably has a transmittance of 50% or more for light in the visible region of 400-700 nm, and is preferably a smooth substrate.

[0057] Examples of such light-transmitting substrates include glass plates and synthetic resin plates. Examples of glass plates include plates formed from soda-lime glass, barium-strontium-containing glass, lead glass, aluminum silicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of synthetic resin plates include plates made of polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone resin.

[0058] anode

[0059] The anode plays the role of injecting holes into the hole transport layer or the light-emitting layer, and it is effective to have a work function of 4 eV or more (preferably 4.45 eV or more). Specific examples of anode materials include carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, and alloys thereof, metal oxides such as tin oxide and indium oxide used in ITO substrates and NESA substrates, and organic conductive resins such as polythiophene or polypyrrole.

[0060] cathode

[0061] As the cathode, a cathode having a metal, alloy, conductive compound or mixture thereof with a small work function (less than 4 eV) can be used as an electrode material. As a specific example of such an electrode material, magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, lithium fluoride or the like and their alloys can be used, but they are not particularly limited. As the alloy, representative examples include magnesium / silver, magnesium / indium, lithium / aluminum or the like, but they are not particularly limited. The ratio of the alloy is controlled by the temperature, atmosphere, vacuum degree or the like of the evaporation source, and an appropriate ratio is selected. The anode and the cathode can also be formed by a layer structure of more than two layers as needed.

[0062] light-emitting layer

[0063] The light-emitting layer has the functions of carrier injection, carrier transport, and light emission. The light-emitting layer materials include host materials and guest materials. Guest materials include phosphorescent guest materials, fluorescent guest materials, TADF guest materials, etc.

[0064] Hole injection layer / hole transport layer

[0065] The hole injection layer / hole transport layer is a layer that helps inject holes into the light-emitting layer and transport the holes to the light-emitting area. It has a large hole mobility and an ionization energy that is usually as small as 5.7 eV or less. As such a hole injection layer / hole transport layer, it is preferred that the material transports holes to the light-emitting layer with a lower electric field strength. It is further preferred that the hole mobility is, for example, 10-4 cm2 / V·second or more when an electric field of 104-106 V / cm is applied. Examples of materials known as hole transport layer materials include bis(N-(1-naphthyl-n-phenyl))benzidine (α-NPD), N,N'-di(naphthyl-1-yl)-N,N'-biphenylbenzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), etc.

[0066] Light-emitting auxiliary layer

[0067] The light-emitting auxiliary layer is used to reduce the potential barrier for holes to be transferred to the light-emitting layer, and also helps to block electrons, preventing electrons from overflowing from the light-emitting layer to the hole transport layer, thereby improving the light-emitting efficiency.

[0068] electron buffer layer

[0069] The electron buffer layer helps to block holes in the light-emitting layer and also helps to transfer electrons to the light-emitting layer to promote the combination of electrons and holes in the light-emitting layer and improve the light-emitting efficiency.

[0070] Electron injection layer / electron transport layer

[0071] The electron injection layer / electron transport layer helps inject electrons into the light-emitting layer and transports electrons to the light-emitting region, and has high electron mobility. The adhesion-improving layer is an electron injection layer made of a material that has particularly good adhesion to the cathode.

[0072] Specific examples of the material used in the electron injection layer include LiF, Liq, Li2O, BaO, NaCl, and CsF, but are not particularly limited.

[0073] The functions 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.

[0074] To form each layer of the organic electroluminescent device of the present disclosure, a dry film forming method such as vacuum evaporation, sputtering, plasma, ion plating method, etc., or a wet film forming method such as inkjet printing, nozzle printing, slit coating, spin coating, dip coating, flow coating method, etc. can be used. The organic electroluminescent compound of the present disclosure can be formed into a film by a co-evaporation method or a mixture evaporation method.

[0075] The products are used in optoelectronics, medicine, biotechnology, optical fiber, lighting equipment, electronic photographic photoreceptors, photoelectric converters, organic solar cells, switching elements, organic light-emitting field-effect transistors, image sensors or dye lasers.

[0076] Definition of Substituent Terms

[0077] As used in the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0078] As used herein, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0079] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a group derived from a monocyclic hydrocarbon or a polycyclic hydrocarbon having 1 to 30 ring main chain carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0080] In the present invention, aryl and arylene groups include monocyclic, polycyclic or condensed ring aromatic groups, and the rings may be interrupted by short non-aromatic units and may contain spiro structures, including but not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0081] In the present invention, the heteroaryl and heteroarylene groups include monocyclic, polycyclic or condensed-ring heteroaryl groups, the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen and sulfur. Including but not limited to furyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof.

[0082] As used herein, the term "substituted" refers to a hydrogen atom in a compound being replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0083] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium, and tritium.

[0084] In the present invention, the definition of the group defines the range of the number of carbon atoms, and the number of carbon atoms is any integer within the defined range. For example, a C6-C60 aromatic group represents an aromatic group, and the number of carbon atoms can be any integer within the range of 6-60, such as 6, 8, 10, 15, 20, 30, 35, 40, 45, 50, 55 or 60.

[0085] In this disclosure, "combination" means that one or more members of an applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can conceive from the list. For example, an alkyl group and a deuterium group can be combined to form a partially or fully deuterated alkyl group; or a halogen, an alkyl group, and an aryl group can be combined to form a haloarylalkyl group. In some embodiments, the combination of substituents comprises a combination of 2-4 groups; in other embodiments, the combination of substituents comprises a combination of 2-3 groups; and in yet other embodiments, the combination of substituents comprises a combination of 2 groups. BRIEF DESCRIPTION OF THE DRAWINGS

[0086] Figure 1 Schematic diagram of the structure of an organic electroluminescent device;

[0087] Among them, 1 is the substrate, 2 is the anode, 3 is the hole injection layer, 4 is the hole transport layer, 5 is the luminescence auxiliary layer, 6 is the luminescent layer, 7 is the electron transport layer, 8 is the electron injection layer, and 9 is the cathode.

[0088] The simple layered structures illustrated in the accompanying drawings are provided by way of non-limiting examples, and it should be understood that the embodiments of the present disclosure can be used in conjunction with various other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be obtained by combining the layers described in different ways, or layers can be omitted entirely based on design, performance, and cost factors. Other layers not specifically described can also be included, and materials other than those specifically described can be used. Although many of the embodiments provided herein describe various materials as including a single material, it should be understood that combinations of materials can be used. In addition, the layers described can have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. DETAILED DESCRIPTION

[0089] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0090] The synthesis method of the organic compounds in the following examples is the Buchwald-Hartwig reaction; the testing instrument is an SQD2 quadrupole mass spectrometer with an APCI source.

[0091] Example 1

[0092] This embodiment provides an organic compound M1, and the preparation method of the organic compound M1 includes the following steps:

[0093]

[0094] Synthesis of intermediate 1-1: In a 250 mL three-necked flask, raw material 1 (10 mmol), raw material 2 (10 mmol) and 100 mL of toluene were added, followed by dropwise addition of sodium tert-butoxide (20 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.2 mmol) and (8% eq) S-phos (0.8 mmol), and the reaction was carried out at 110° C. for 1 h. After the reaction was completed, the temperature was lowered to room temperature, water (20 mL) was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (DCM / hexane) to obtain intermediate 1-1 (1.93 g, yield 46%).

[0095] Synthesis of compound M1: Under N2 protection, intermediate 1-1 (10 mmol), raw material 3 (10 mmol), sodium tert-butoxide (15 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.2 mmol), (8% eq) S-phos (0.8 mmol) and toluene 80 mL were added to a 250 mL two-necked flask, and then refluxed with stirring. After cooling to room temperature, the organic layer was extracted with ethyl acetate and H2O. The extracted organic layer was dried over MgSO4 and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (DCM / hexane), and then recrystallized and purified using a DCM / acetone mixed solvent to obtain compound M1 (5.55 g, yield 73%).

[0096] MS (APCI) m / z [M+H] + :762.67.

[0097] Example 2

[0098] This embodiment provides an organic compound M7, and the preparation method of the organic compound M7 includes the following steps:

[0099]

[0100] Synthesis of Intermediate 7-1: In a 250 mL three-necked flask, raw material 3 (10 mmol), raw material 4 (10 mmol), 60 mL of toluene, 20 mL of ethanol, and 20 mL of water were added. Tetrakistriphenylphosphine palladium (0.4 mmol) and potassium carbonate (20 mmol) were added and heated to 80°C for 5 h. After the reaction was completed, the mixture was cooled to room temperature and the organic layer was extracted with ethyl acetate and H2O. The extracted organic layer was dried over MgSO4 and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (DCM / hexane) to obtain Intermediate 7-1 (1.91 g, yield: 42%).

[0101] The synthesis of compound M7 was the same as that of compound 1, except that raw material 3 was replaced by an equal molar amount of intermediate 7-1, and intermediate 1-1 was replaced by an equal molar amount of raw material 5 to obtain compound M7 (4.39 g, yield 68%).

[0102] MS (APCI) m / z [M+H] +: 646.56.

[0103] Example 3

[0104] This embodiment provides an organic compound M37, and the preparation method of the organic compound M37 includes the following steps:

[0105]

[0106] The synthesis of intermediate 37-1 was the same as that of intermediate 1-1, except that raw material 2 was replaced with an equal molar amount of raw material 6 to obtain intermediate 37-1 (1.30 g, yield 43%);

[0107] The synthesis of compound M37 was the same as that of compound 1, except that intermediate 1-1 was replaced by an equal molar amount of 37-1 to obtain compound M37 (4.97 g, yield 77%).

[0108] MS (APCI) m / z [M+H] + :646.49.

[0109] Example 4

[0110] This embodiment provides an organic compound M42. The preparation method of the organic compound M42 includes the following steps:

[0111]

[0112] The synthesis of compound M42 was the same as that of compound M1, except that intermediate 1-1 was replaced by an equal molar amount of raw material 7 to obtain compound M42 (4.02 g, yield 65%).

[0113] MS (APCI) m / z [M+H] + :620.39.

[0114] Example 5

[0115] This embodiment provides an organic compound M49, and a preparation method of the organic compound M49 includes the following steps:

[0116]

[0117] The synthesis of intermediate 49-1 was the same as that of intermediate 1-1, except that the starting material 2 was replaced with an equal molar amount of starting material 8 to obtain intermediate 49-1 (1.57 g, yield 40%).

[0118] The synthesis of compound M49 was the same as that of compound 1, except that intermediate 1-1 was replaced by an equal molar amount of 49-1, and raw material 3 was replaced by an equal molar amount of 9 to obtain compound M49 (5.73 g, yield 78%).

[0119] MS (APCI) m / z [M+H] + :736.85.

[0120] Example 6

[0121] This embodiment provides an organic compound M50, and the preparation method of the organic compound M50 includes the following steps:

[0122]

[0123] The synthesis of compound M50 was the same as that of compound M1, except that intermediate 1-1 was replaced by an equal molar amount of raw material 10 to obtain compound M50 (6.52 g, yield 75%).

[0124] MS (APCI) m / z [M+H] + :870.74.

[0125] Example 7

[0126] This embodiment provides an organic compound M52, and the preparation method of the organic compound M52 includes the following steps:

[0127]

[0128] Synthesis of Intermediate 52-1: Add 45.9 mL of phenylmagnesium bromide (2.9 M in THF) to a 250 mL three-necked flask equipped with a magnetic rotor. Dissolve 10 g of adamantanone in 100 mL of tetrahydrofuran solution and add to a constant pressure dropping funnel. Replace the atmosphere with nitrogen three times. Under nitrogen protection, add the tetrahydrofuran solution of adamantanone dropwise. After the addition is complete, warm the mixture to room temperature for reaction. Monitor the reaction by TLC until the reaction of the raw materials is complete and then stop the reaction. After the reaction is completed, add an appropriate amount of saturated ammonium chloride aqueous solution to quench the reaction. Let the mixture stand in a separatory funnel to separate the layers. Collect the organic phase, extract the aqueous phase three times with dichloromethane, and combine the organic phases. Dry over anhydrous sodium sulfate. Purify by silica gel column chromatography (DCM / hexane) to obtain Intermediate 52-1 (12.8 g, yield 52%).

[0129] Synthesis of intermediate 52-2: In a 250 mL three-necked flask equipped with a magnetic rotor, intermediate 52-1 (12.8 g) and bromobenzene (8.8 g) were added, dissolved in 128 ml of dichloromethane, and replaced with nitrogen three times. Under nitrogen protection, 17.4 g of Eaton's reagent was added dropwise at room temperature. The reaction was monitored by TLC until the reaction of the raw materials was complete and then the reaction was stopped. After the reaction was completed, it was poured into saturated brine, allowed to stand with a separatory funnel, the organic phase was collected, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and dried over anhydrous sodium sulfate. It was purified by silica gel column chromatography (DCM / hexane) to obtain intermediate 52-3 (7 g, yield 55%).

[0130] The synthesis of intermediate 52-3 was the same as that of compound M1, except that intermediate 1-1 was replaced by an equal molar amount of raw material 13, and raw material 3 was replaced by an equal molar amount of intermediate 52-2 to obtain intermediate 52-3 (2.06 g, yield 44%).

[0131] The synthesis of compound M52 was the same as that of compound M1, except that intermediate 1-1 was replaced by an equal molar amount of intermediate 52-3 to obtain compound M52 (6.16 g, yield 76%).

[0132] MS (APCI) m / z [M+H] + : 812.35.

[0133] Example 8

[0134] This embodiment provides an organic compound M60, and a preparation method of the organic compound M60 includes the following steps:

[0135]

[0136] The synthesis of intermediate 60-1 was the same as that of compound M1, except that intermediate 1-1 was replaced by an equal molar amount of raw material 14, and raw material 3 was replaced by an equal molar amount of intermediate 52-2 to obtain intermediate 60-1 (2.85 g, yield 46%).

[0137] The synthesis of compound M60 was the same as that of compound M1, except that intermediate 1-1 was replaced by an equal molar amount of intermediate 60-1 to obtain compound M60 (6.82 g, yield 71%).

[0138] MS (APCI) m / z [M+H] + :962.31.

[0139] The synthesis of compounds M2-M6, M8-M36, M38-M41, M43-M48, M51, M53-M59, and M61-M66 is the same as that of M1, M7, M37, M42, M49, M50, M52, or M60.

[0140] Application Examples 1-8 and Comparative Application Example 1

[0141] The following application examples 1-8 and comparative application example 1 respectively provide an OLED, such as Figure 1 As shown, the organic light-emitting device includes a substrate (indium tin oxide (ITO) coated glass substrate) 1, an anode 2, a hole injection layer (HIL) 3, a hole transport layer 4 (HTL-1), a light-emitting auxiliary layer (HTL-2) 5, a light-emitting layer (EML) 6, an electron transport layer (ETL) 7, an electron injection layer (EIL) 8 and a cathode 9 stacked in sequence;

[0142] The materials used are as follows:

[0143]

[0144]

[0145] The preparation steps of OLED devices are as follows:

[0146] (1) Substrate cleaning:

[0147] The glass substrate 1 coated with an ITO transparent electrode was ultrasonically treated in an aqueous detergent (the composition and concentration of the aqueous detergent: 10 wt% ethylene glycol solvent, 1 wt% triethanolamine), rinsed in deionized water, ultrasonically degreased in an acetone-ethanol mixed solvent (volume ratio 1:1), baked in a clean environment until the water was completely removed, and then cleaned with ultraviolet light and ozone;

[0148] (2) Evaporation:

[0149] Place the glass substrate 1 with the anode 2 in a vacuum chamber and evacuate to 1×10 -6 to 2×10 -4 Pa, vacuum evaporating the hole injection layer 3 material on the above-mentioned anode layer film by co-evaporation, wherein the PD and NPB are adjusted according to the mass ratio, the total evaporation rate is 0.1nm / s, and the evaporation thickness is 10nm;

[0150] (3) depositing a hole transport layer 4 on the hole injection layer 3 at a deposition rate of 0.1 nm / s and a film thickness of 60 nm;

[0151] (4) evaporating a light-emitting auxiliary layer 5 on the hole transport layer 4 at a deposition rate of 0.1 nm / s and a deposition thickness of 20 nm;

[0152] (5) Vapor-depositing a light-emitting layer 6 on the light-emitting auxiliary layer 5 by vacuum evaporating the light-emitting host material and the guest material in a co-evaporation manner. The evaporation rate is adjusted according to the mass ratio of the host material to the guest material. The total evaporation rate is 0.1 nm / s, and the total film thickness is 30 nm.

[0153] (6) Vacuum-depositing an electron transport layer 7 on the light-emitting layer 6. The evaporation rate is adjusted according to the mass ratio of the compound ET to LiQ. The total evaporation rate is 0.1 nm / s, and the total evaporation film thickness is 30 nm.

[0154] (7) Vacuum-depositing an electron injection layer 8 on the electron transport layer 7 at a deposition rate of 0.05 nm / s and a total deposition thickness of 1 nm;

[0155] (8) A cathode 9 is evaporated on the electron injection layer 8. The total evaporation rate is 0.1 nm / s and the total evaporation film thickness is 100 nm.

[0156] The compositions of the OLED devices in Application Examples 1-8 and Comparative Application Example 1 are as follows:

[0157]

[0158]

[0159] Test Case

[0160] Device performance test:

[0161] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR 650 spectrum scanning luminance meter and a Keithley K 2400 digital source meter system;

[0162] The test conditions for device application examples 1-8 and comparative application example 1 are as follows:

[0163] Photoelectric characteristics test conditions: current density is 10mA / cm 2 ;

[0164] Life test: current density is 10mA / cm 2 , record the time (in hours) when the device brightness drops to 95% of the original brightness;

[0165] The test results are shown in Table 1 below:

[0166] Table 1

[0167]

[0168] As can be seen from the data in Table 1, the organic compounds provided by the present invention can be used in the hole transport layer and / or light-emitting auxiliary layer of an organic light-emitting device to reduce the device driving voltage and improve the device luminous efficiency and life.

[0169] The applicant states that while the above-described embodiments illustrate the process of the present invention, the present invention is not limited to the above-described process steps, nor does it imply that the present invention must rely on the above-described process steps for implementation. Those skilled in the art will appreciate that any improvements to the present invention, equivalent substitutions for the raw materials used, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. An organic compound, characterized in that The organic compound has the structure shown in the following formula I: Wherein, L1 and L2 are single bonds; L3 and L4 are each independently selected from any one of a single bond, a phenylene group or a biphenylene group; R1 is selected from any one of phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, and substituted or unsubstituted spirobifluorenyl; The substituents in the substituted biphenyl group, substituted terphenyl group, substituted naphthyl group, substituted phenanthrenyl group, substituted anthracenyl group, substituted dibenzofuranyl group, substituted dibenzothienyl group, substituted dimethylfluorenyl group, substituted diphenylfluorenyl group, and substituted spirobifluorenyl group are selected from any one of deuterium and methyl group, or a combination of at least two thereof; The R2 is selected from any one of hydrogen, deuterium, phenyl, biphenyl, and naphthyl; and n is selected from 1 or 2.

2. The organic compound according to claim 1, characterized in that The organic compound is selected from any one of the following formulas I-1 to I-4: Wherein, L1, L2, L3, L4, R1, and R2 have the same limited ranges as described in claim 1.

3. The organic compound according to claim 1, characterized in that The dimethylfluorenyl group is selected from any one of the following structures: in, Indicates the attachment site of a group.

4. The organic compound according to claim 1, characterized in that The diphenylfluorenyl group is selected from any one of the following structures: in, Indicates the attachment site of a group.

5. The organic compound according to claim 1, characterized in that The R2 is selected from phenyl.

6. The organic compound according to claim 1, characterized in that The organic compound includes any one of the following M1-M27, M30-M33, M36-M63, M65-M66:

7. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises the organic compound according to any one of claims 1 to 6.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic thin film layer located between the anode and the cathode, wherein the organic thin film layer comprises the organic compound according to any one of claims 1 to 6 or the organic electroluminescent material according to claim 7.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic thin film layer includes any one or a combination of at least two of a hole injection layer, a hole transport layer, a luminescence auxiliary layer, a luminescent layer, a hole blocking layer, an electron buffer layer, an electron transport layer, an electron buffer layer or an electron injection layer.

10. The organic electroluminescent device according to claim 9, characterized in that: The hole transport layer includes the organic compound according to claim 1 .

11. The organic electroluminescent device according to claim 9, characterized in that: The light-emitting auxiliary layer includes the organic compound according to claim 1 .

12. An electronic device, characterized in that: The electronic device comprises the organic electroluminescent device according to claim 8.

13. The electronic device according to claim 12, wherein: The electronic device includes any one of an optical fiber, a lighting device, an electrophotographic photoreceptor, a photoelectric converter, an organic solar cell, a switching element, an organic light-emitting field-effect transistor, an image sensor, or a dye laser.

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