CN114907179A - Anthracene derivative, and organic electroluminescent material, light-emitting device and consumer product using the same - Google Patents

Anthracene derivative, and organic electroluminescent material, light-emitting device and consumer product using the same Download PDF

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CN114907179A
CN114907179A CN202210659236.0A CN202210659236A CN114907179A CN 114907179 A CN114907179 A CN 114907179A CN 202210659236 A CN202210659236 A CN 202210659236A CN 114907179 A CN114907179 A CN 114907179A
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organic electroluminescent
anthracene derivative
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aromatic
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CN114907179B (en
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曹建华
姜卫东
张九敏
姜坤
李程辉
刘殿君
唐伟
唐怡杰
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Shanghai 800 Million Spacetime Advanced Material Co ltd
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Abstract

The invention relates to an anthracene derivative, an organic electroluminescent material, a light-emitting device and a consumer product, wherein the anthracene derivative is a novel organic electroluminescent compound with a large steric hindrance non-planar structure formed by anthracene and fluorene, the fluorene and spirobifluorene anthracene derivative increases molecular steric hindrance, prevents the generation of an organic intermolecular excitation-excitation compound, improves internal quantum efficiency, and has shorter light-emitting wavelength compared with the existing compound, so that the efficiency and the service life of an organic electroluminescent device containing the compound are improved; in addition, the compound improves the solubility of the solution, thereby solving the problems of the productivity and the cost of the process of the conventional blue light material.

Description

Anthracene derivative, and organic electroluminescent material, light-emitting device and consumer product using the same
Technical Field
The invention belongs to the technical field of organic electroluminescence, and particularly relates to an anthracene derivative, an organic electroluminescent material using the anthracene derivative, a light-emitting device using the anthracene derivative and a consumer product using the anthracene derivative.
Background
Most of the materials used in organic electroluminescent devices are pure organic materials or organometallic complexes in which organic materials and metals form complexes, and are classified into hole injection materials, hole transport materials, luminescent materials, electron transport materials, electron injection materials, and the like according to their applications. Here, an organic substance having relatively low ionization energy is mainly used as the hole injecting substance or the hole transporting substance, and an organic substance having relatively high electronegativity is mainly used as the electron injecting substance or the electron transporting substance. Further, it is preferable that the substance used as the light-emission assisting layer satisfies the following characteristics:
first, the material used in the organic electroluminescent element needs to have good thermal stability because joule heat is generated due to charge transfer in the organic electroluminescent element, and the glass transition temperature of the material generally used as the hole transport layer is low at present, and thus crystallization occurs when the organic electroluminescent element is driven at low temperature, which causes a phenomenon of lowering the light emission efficiency. Second, in order to reduce the driving voltage, it is necessary to design the organic matter adjacent to the cathode and the anode to have a small charge injection barrier and a high charge mobility. Third, since there is always an energy barrier at the interface between the electrode and the organic layer and at the interface between the organic layer and the organic layer, and some charges are inevitably accumulated, it is necessary to use a substance having excellent electrochemical stability.
The light-emitting layer is composed of two materials, i.e., a host and a dopant, and the dopant is required to have high quantum efficiency, and the host is required to have a larger energy gap than the dopant so that energy transfer to the dopant is likely to occur. Displays used for televisions, mobile devices, and the like realize full color based on three primary colors of red, green, and blue, and the light-emitting layers are respectively composed of a red main light-emitting body/dopant, a green main light-emitting body/dopant, and a blue main light-emitting body/dopant. The existing blue light material still has the problems of low luminous quantum efficiency and poor color purity. The main reason for this is that blue light comes from the transition between energy levels with wider energy gap, and organic compounds with wide forbidden band have certain difficulty in molecular design, and secondly, the blue light material system has stronger pi-pi bond interaction and very strong charge transfer characteristics, so that more radiationless relaxation channels exist in the wide band gap, the fluorescence quenching between molecules is intensified, and the quantum yield of the blue light system is reduced.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides an anthracene derivative, and an organic electroluminescent material, a light emitting device, and a consumer product using the same, wherein the anthracene derivative emits light in a blue to deep blue color with high luminous efficiency.
In a first object of the present invention, an anthracene derivative is provided.
In a second aspect of the present invention, there is provided an organic electroluminescent material.
In a third aspect of the present invention, there is provided an organic electroluminescent device.
A fourth object of the invention is to provide a consumer product.
In order to achieve the purpose, the invention adopts the following technical scheme:
an anthracene derivative, wherein the structural general formula of the anthracene derivative is shown as a formula (I) or a formula (II):
Figure BDA0003687680660000011
wherein, X 1 To X 8 Each independently represents N or CR 3 ；
R 1 、R 2 、R 3 At each occurrence, each is selected, identically or differently, from hydrogen, deuterium, with C 1 -C 40 Straight chain alkyl of (2) having C 1 -C 40 Linear heteroalkyl group of (A) having C 3 -C 40 A branched or cyclic alkyl group having C 3 -C 40 A branched or cyclic heteroalkyl group of (A) having C 2 -C 40 Alkenyl or alkynyl groups of (a), an aromatic or aromatic ring system having 5 to 80, preferably 6 to 60 carbon atoms or a heteroaromatic or heteroaromatic ring system having 2 to 60 carbon atoms, or two or more adjacent groups may be optionally cyclized or fused to each other to form a ring;
Ar 1 、Ar 2 、Ar 3 、Ar 4 each independently selected from hydrogen, deuterium, an aromatic or aromatic ring system having 6 to 60 carbon atoms, or an aromatic or aromatic ring system having 2 to 60 carbon atomsA heteroaromatic or heteroaromatic ring system of (a); ar (Ar) 3 And Ar 4 May be linked to each other by a single bond, a bridging group of O, S, N, or C to form a ring; or Ar in the formula (II) 1 And Ar 3 Or Ar 4 The rings are connected to each other by a single bond, O, S, N, or a bridging group of C.
Aryl in the sense of the present invention contains 6 to 60 carbon atoms; heteroaryl in the sense of the present invention contains 2 to 60 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5, said heteroatom preferably being selected from N, O or S. Aryl or heteroaryl herein is considered to mean a simple aromatic ring, i.e. benzene, naphthalene, etc., or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatic rings, such as biphenyl, which are connected to one another by single bonds, are, in contrast, not referred to as aryl or heteroaryl, but as aromatic or heteroaromatic ring systems.
An aromatic or heteroaromatic ring system in the sense of the present invention is intended to be taken to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be linked by a non-aromatic unit, for example C, N, O or an S atom. Thus, for example, as well as systems in which two or more aryl groups are linked by, for example, short alkyl groups, systems such as fluorene, 9' -spirobifluorene, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also to be understood as meaning aromatic or heteroaromatic ring systems in the sense of the present invention.
The alkyl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. As non-limiting examples thereof, there are methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl and the like. Heteroalkyl means a hydrogen atom or-CH on an alkyl group 2 -substituted by at least one heteroatom selected from halogen, cyano, N, O, S or silicon, as non-limiting examples difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, cyano, ethylcyano, methoxymethyl, methoxyethyl, trimethylsilyl, triisopropylsilyl and the like.
The alkenyl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. As non-limiting examples thereof, there are vinyl, allyl, isopropenyl, 2-butenyl, and the like.
The alkynyl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. As non-limiting examples thereof, there are ethynyl, 2-propynyl and the like.
In general, the cycloalkyl group, cycloalkenyl group according to the present invention means a monovalent functional group obtained by removing one hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. As non-limiting examples thereof, there may be mentioned cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, and the like, wherein one or more-CH groups 2 The radicals may be replaced by the radicals mentioned above; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms, or cyano groups.
The heterocycloalkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having a nuclear number of 3 to 40. In this case, more than one carbon, preferably 1 to 3 carbons, in the ring is substituted with a heteroatom such as N, O or S. As non-limiting examples thereof, there are tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine and the like.
Alkoxy as used herein means RO - The monovalent functional group represented by R is an alkyl group having 1 to 40 carbon atoms and may have a linear, branched or cyclic structure. Non-limiting examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentyloxy, cyclopentyloxy, cyclohexyloxy, and the like.
Aryloxy as used in the present invention means R' O - The monovalent functional group is represented by R' which is an aryl group having 6 to 60 carbon atoms. As non-limiting examples of such aryloxy groupsAnd phenoxy, naphthoxy, biphenyloxy, etc.
The aromatic or heteroaromatic, in each case aromatic or heteroaromatic, ring atoms according to the invention may also be replaced by the abovementioned R 1 Radical-substituted aromatic or heteroaromatic ring systems, in particular radicals derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,
Figure BDA0003687680660000021
Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-indenocarbazole, cis-or trans-indolocarbazole, triindene, isotridendene, spirotriindene, spiroisotridendene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo [5, 6 ] indole, perylene, anthracene, phenanthrene, perylene]Quinoline, benzo [6, 7 ]]Quinoline, benzo [7, 8 ]]Quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxaloimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroixazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diaza-thracene, 2, 7-diaza, 2, 3-diaza-pyrene, 1, 6-diaza-pyrene, 1, 8-diaza-pyrene, 4, 5, 9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescent red ring, naphthyridine, azacarbazole, benzocarbazine, carboline, phenanthroline, 1, 2, 3-triazole, 1, 2, 4-triazole, benzotriazole, 1, 2, 3-oxadiazole, 1, 2, 4-oxadiazole, 1, 2, 5-oxadiazole, 1, 3, 4-oxadiazole, 1, 2, 3-thiadiazole, 1, 2, 4-thiadiazole, 1, 2, 5-thiadiazole, 1, 3, 4-thiadiazole, 1, 3, 5-triazine, 1, 2, 4-triazine, 1, 2, 3-triazine, tetrazole, 1, 2, 4, 5-tetrazine, 1, 2, 3, 4-tetrazine, 1, 2, 3, 5-tetrazine, purine, pteridine, 2, 3, 5-tetrazine, purine, pteridine, and their pharmaceutically acceptable salts,Indolizines and benzothiadiazoles or groups derived from combinations of these systems.
Further, said X 1 ～X 8 Each is N or CH; r 1 、R 2 Is hydrogen; ar (Ar) 1 、Ar 2 Each independently selected from the group consisting of hydrogen, deuterium, an aromatic or aromatic ring system having 6 to 60 carbon atoms, or a heteroaromatic or heteroaromatic ring system having 2 to 60 carbon atoms; ar (Ar) 3 、Ar 4 Each independently selected from the group consisting of aromatic or aromatic ring systems having 6 to 60 carbon atoms.
Further, the heteroaromatic or heteroaromatic ring system is a group consisting of groups shown in II-1 to II-17 and an aromatic ring or aromatic ring system, and the specific structures of II-1 to II-17 are as follows:
Figure BDA0003687680660000031
wherein Z is 1 、Z 2 Each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 represents an oxygen atom or a sulfur atom;
Figure BDA0003687680660000033
represents a bond between a substituent and the main structure.
The substituent group in the invention is selected from hydrogen, deuterium, halogen, hydroxyl, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group or carboxylate thereof, sulfonic group or sulfonate thereof, phosphoric group or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, C 6 -C 60 Aryl radical, C 6 -C 60 Aryloxy radical, C 6 -C 60 An arylsulfonyl group, or C 2 -C 60 Heterocyclic aryl groups.
As used herein, "a combination thereof" or "group" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art would be able to envision from the applicable list. For example, alkyl groups and deuterium atoms may be combined to form partially or fully deuterated alkyl groups; halogen and alkyl groups may be combined to form haloalkyl substituents, such as trifluoromethyl and the like; and halogen, alkyl, and aryl groups may be combined to form haloaralkyl groups.
Further, the anthracene derivative is one of the following structures CJHB 950-CJHB 1087:
Figure BDA0003687680660000032
Figure BDA0003687680660000041
Figure BDA0003687680660000051
Figure BDA0003687680660000061
Figure BDA0003687680660000071
Figure BDA0003687680660000081
Figure BDA0003687680660000091
Figure BDA0003687680660000101
Figure BDA0003687680660000111
wherein, T 2 -:
Figure BDA0003687680660000112
and-represent a connecting bond.
An organic electroluminescent material comprising said anthracene derivative.
The organic electroluminescent material may be formed using the compound of the present invention alone, or may contain other compounds at the same time.
The compound of the present invention contained in the organic electroluminescent material of the present invention can be used as, but not limited to, a light emitting layer material, a carrier transport layer material or a photorefractive layer material.
An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer interposed between the first electrode and the second electrode, the organic layer comprising the anthracene derivative provided by the present invention.
The organic electroluminescent device includes a cathode, an anode, and at least one light emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent device described herein may include one light emitting layer, or it may include a plurality of light emitting layers. I.e. a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. A system having three light-emitting layers, which can exhibit blue, green and red light emission, is preferred. If more than one light-emitting layer is present, at least one of these layers comprises, according to the invention, a compound according to the invention.
Further, the organic electroluminescent device according to the invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer is directly adjacent to the hole injection layer or anode and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
In the other layers of the organic electroluminescent arrangement according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent arrangements in which one or more layers are applied by means of the sublimation method, with a vacuum sublimation apparatus having a vacuum of less than 10 -5 Pa, preferably less than 10 -6 Pa is applied by vapor deposition. However, the initial pressure may also be even moreLow, e.g. less than 10 -7 Pa。
Preference is likewise given to organic electroluminescent devices in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10 -5 The material is applied under a pressure between Pa and 1 Pa. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
Preference is furthermore given to organic electroluminescent arrangements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution of a compound of formula I. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
These methods are generally known to those skilled in the art, and they can apply them to an organic electroluminescent element comprising the compound according to the present invention without inventive work.
The invention therefore also relates to a method for producing an organic electroluminescent arrangement according to the invention by applying at least one layer by means of a sublimation method and/or by means of an organic vapor deposition method or by means of carrier gas sublimation and/or by spin coating or by means of a printing method from solution.
Furthermore, the present invention relates to pharmaceutical compositions comprising at least one compound of the invention as indicated above. The same preferences as indicated above for the organic electroluminescent arrangement apply to the compounds according to the invention. In particular, the compounds may furthermore preferably comprise further compounds. The processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires the preparation of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchytone, 1, 2, 3, 5-tetramethylbenzene, 1, 2, 4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, 4-methylanisole, toluene, xylene, acetone, xylene, or mixtures of the like, Cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or a mixture of these solvents.
Further, the organic layer is selected from one or more of an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer and a light emitting layer.
Further, the electron transporting layer and the light-emitting layer each contain the anthracene derivative of the present invention.
Further, the light-emitting layer comprises a dopant and a light-emitting main body, wherein the dopant comprises anthracene, naphthalene, anthracene, pyrene, perylene, phenanthrene, fluoranthene, perylene, phenanthrene, anthracene,
Figure BDA0003687680660000121
Benzanthracene, fluorene, spirofluorene, pentacene, and derivatives thereof; the light-emitting host comprises the anthracene derivative of the present invention.
Furthermore, the mass ratio of the dopant to the luminescent main body is 1: 99-50: 50.
A consumer product made of the organic electroluminescent device comprises the organic electroluminescent device provided by the invention.
The consumer product according to the invention may be one of the following products: a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior lighting and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet computer, a phablet, a Personal Digital Assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay at a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall containing multiple displays tiled together, a theater or stadium screen, a phototherapy device, and a sign.
Unless otherwise specified, all starting materials for use in the present invention are commercially available and any range recited herein includes any endpoints and any numerical values therebetween and any subranges therebetween.
Compared with the prior art, the invention has the beneficial effects that:
the anthracene derivative has a novel organic electroluminescent compound with a large steric hindrance non-planar structure formed by anthracene and fluorene, the fluorene or spirobifluorene anthracene derivative increases molecular steric hindrance, prevents the generation of an excitation-excitation compound between organic molecules, improves internal quantum efficiency, and has shorter light-emitting wavelength compared with the existing compound, so that the efficiency and the service life of an organic electroluminescent device containing the compound are improved; the compound improves the solubility in a solution to solve the problems of productivity and cost of the conventional blue light emitting material in the process, and can be used for producing a light emitting layer not in the deposition process but in the solution process in the conventional process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 shows a schematic diagram of an organic light emitting device 100. The illustrations are not necessarily drawn to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the described layers.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device includes a substrate 201, an anode 202, a hole injection 203, a hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 may be prepared by sequentially depositing the described layers. Since the most common OLED devices have one light emitting layer, while device 200 has a first light emitting layer and a second light emitting layer, the light emitting peak shapes of the first light emitting layer and the second light emitting layer may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of device 200, materials similar to those described with respect to device 100 may be used. Fig. 2 provides one example of how some layers may be added from the structure of device 100.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
In the present invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are available from published commercial sources unless otherwise specified, and the percentages are by mass unless otherwise specified. The novel series of organic compounds provided by the present invention, all reactions of which are carried out under well-known suitable conditions, are involved in simple organic preparations, for example, the preparation of phenylboronic acid derivatives can be synthesized by skilled operative skills and are not described in detail in the present invention.
The following examples are provided for testing the performance of OLED materials and devices using the following test apparatus and method:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C;
and (3) life test: LTS-1004AC life test equipment was used.
Example 1
Preparation of intermediate a 1:
the preparation method of the intermediate A1 comprises the following steps:
the first step is as follows: preparation of Compound Int-1
Figure BDA0003687680660000131
Under the protection of nitrogen, 50.0mmol of 4-bromo-9, 9-dimethyl spirobifluorene is dissolved in 100mL of dry tetrahydrofuran, the temperature is reduced to 0 ℃, 50.0mmol of potassium tert-butoxide is added, the temperature is further reduced to-78 ℃, 20.8mL of 2.5M N-butyllithium N-hexane solution is added dropwise, the mixture is stirred and reacted for 10 minutes, 55.0mmol of 2-benzyl bromochloride solution is added dropwise and dissolved in THF, the mixture is heated to room temperature and stirred and reacted for 2 hours, 50mL of 2N dilute hydrochloric acid aqueous solution is added, ethyl acetate is used for extraction, an organic phase is collected, dried and filtered, the filtrate is concentrated under reduced pressure and dried, and is separated and purified by a silica gel column, so that an intermediate Int-1 is obtained, and the yield: 84 percent.
The second step is that: preparation of Compound Int-2
Figure BDA0003687680660000141
Dissolving 50.0mmol of the intermediate Int-1 prepared in the first step in 120mL of dry THF, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 22.0mL of 2.5M N-butyllithium N-hexane solution, stirring for reaction for 20 minutes, dropwise adding 75.0mmol of benzonitrile, heating to room temperature, stirring for reaction for 1 hour, adding 50mL of 2N dilute hydrochloric acid aqueous solution, separating an organic phase, extracting the aqueous phase with dichloromethane, collecting the organic phase, drying and filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain Int-2, a yellow solid, wherein the yield is as follows: 87 percent.
The third step: preparation of Compound Int-3
Figure BDA0003687680660000142
Under the protection of nitrogen, 40.0mmol of intermediate Int-2 is dissolved in 80mL of glacial acetic acid, 0.2mol of 33% acetic acid bromide solution is added, the mixture is stirred at room temperature for 1 hour, and the mixture is decompressed, concentrated and dried, and is separated and purified by a silica gel column to obtain intermediate Int-3, and the yield is as follows: 85 percent.
The fourth step: preparation of Compound A1
Figure BDA0003687680660000143
20.0mmol of intermediate Int-3 is dissolved in 100mL of dichloromethane, the temperature is reduced to 0 ℃ by ice water bath, 2.0mmol of p-toluenesulfonic acid is added, 22.0mmol of NBS is added in batches, the mixture is stirred for reaction for 2 hours, 50mL of 10% sodium bicarbonate aqueous solution is added, an organic phase is separated, the organic phase is washed by water, the organic phase is collected, dried and filtered, filtrate is concentrated under reduced pressure to be dry, and the dry product is separated and purified by a silica gel column, so that the intermediate A1 is obtained, and the yield is 96%.
Referring to the above synthesis, the products shown in table 1 were prepared.
TABLE 1 correspondence table of reactants and synthesis products
Figure BDA0003687680660000144
Figure BDA0003687680660000151
Figure BDA0003687680660000161
Figure BDA0003687680660000171
Figure BDA0003687680660000181
Figure BDA0003687680660000191
Example 2
Preparation of compound CJHB 960:
Figure BDA0003687680660000192
15.0mmol of intermediate A6 was mixed with 60mL of toluene, 18.0mmol of phenylboronic acid, 54.0mmol of anhydrous sodium carbonate and 173.0mg of Pd (PPh) were added under nitrogen protection 3 ) 4 Adding 30mL of ethanol and 30mL of water into the catalyst, heating to reflux, stirring, reacting for 12 hours, cooling to room temperature, filtering, washing a filter cake with water and ethanol, and separating and purifying by using a silica gel column to obtain a yellow solid CJHB960, wherein the yield is as follows: 86%, MS (MALDI-TOF): m/z 695.2677[ M + H ]] + 。
Referring to the above synthesis, the products shown in table 2 were prepared.
TABLE 2 correspondence table of reactants and synthesized products and yields
Figure BDA0003687680660000193
Figure BDA0003687680660000201
Figure BDA0003687680660000211
Figure BDA0003687680660000221
Figure BDA0003687680660000231
Figure BDA0003687680660000241
Figure BDA0003687680660000251
Figure BDA0003687680660000261
Wherein, T 2 -:
Figure BDA0003687680660000262
example 3
An OLED device, as shown in fig. 1, is prepared by a method comprising the steps of:
1) the glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to 1 × 10 -5 ～9×10 -3 Pa, depositing silver on the ITO film as an anode to a thickness of
Figure BDA0003687680660000263
Continuing to respectively vapor-deposit compounds DNTPD and F4TCNQ as hole injection layers, wherein F4TCNQ is 3% of DNTPD mass, and the vapor-deposition film thickness is
Figure BDA0003687680660000264
Continuously depositing NPD on the hole injection layer film to form a hole transport layer, wherein the deposition film has a thickness of
Figure BDA0003687680660000265
3) Continuously evaporating a layer of compound HT202 on the hole transport layer as an electron blocking layer, wherein the thickness of the evaporated film is
Figure BDA0003687680660000266
4) Continuously evaporating a layer of anthracene derivative shown in formula I and BD025 of the invention on the electron blocking layer to form an organic light emitting layer, wherein BD025 is a doping material and the anthracene derivative shown in formula (I) is a host material, the doping concentration of the compound shown in formula (I) in BD025 is 10%, and the thickness of the evaporation film is set to be equal to that of the organic light emitting layer
Figure BDA0003687680660000267
5) Evaporating a layer of compounds LiQ and ET210 on the light-emitting layer as a deviceAn electron transport layer, wherein the mass ratio of LiQ to ET210 is 1: 1, and the thickness of the evaporation film is
Figure BDA0003687680660000268
6) Continuously evaporating a layer of compound LiF on the electron transport layer to form an electron injection layer of the device, wherein the thickness of the evaporated film is
Figure BDA0003687680660000269
Finally, depositing magnesium and silver as cathode layer of element on the electron injection layer at a mass ratio of 1: 10 and a thickness of deposited film
Figure BDA00036876806600002610
The structure of the compound used in example 3 above is as follows:
Figure BDA00036876806600002611
comparative example 1
The same procedure as in example 3 was followed, except that compound B01 was used in place of the anthracene derivative represented by the formula (I). The structure of compound B01 is:
Figure BDA0003687680660000271
comparative example 2
The same procedure as in example 3 was followed, except that compound B02 was used in place of the anthracene derivative represented by the formula (I). The structure of compound B02 is:
Figure BDA0003687680660000272
comparative example 3
The same procedure as in example 3 was followed, except that compound B03 was used in place of the anthracene derivative represented by the formula (I). The structure of compound B03 is:
Figure BDA0003687680660000273
the driving voltage and current efficiency of the organic electroluminescent elements prepared in example 3 and comparative example 1, comparative example 2 and comparative example 3 and the lifetime of the elements were measured at the same luminance using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent element reached 1000cd/m 2 The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the LT 90% lifetime test is as follows: using a luminance meter at 1000cd/m 2 The luminance decay of the organic electroluminescent element was measured to 900cd/m while maintaining a constant current at luminance 2 Time in hours. All results are summarized in table 3, and all results are reported as relative values normalized to the results of comparative example 1.
TABLE 3 test results of the performance of each element
Figure BDA0003687680660000274
As can be seen from table 3, the compound of the present invention, as a blue light material, obtained a blue organic electroluminescent device, and the device had a reduced driving voltage, an improved current efficiency, and a good improvement in LT 90% lifetime.
The compound B01 in comparative example 1, the compound B02 in comparative example 2, and the compound B03 in comparative example 3 are different from the compounds of the present invention in that dimethylfluorene or dimethylsilylheterofluorene has a weak plane conjugation ability, an imbalance in the transport of holes and electrons, which is stronger in the hole accepting ability than in the electron accepting ability, and this imbalance in transport affects the formation of excitons in the light emitting layer, resulting in high voltage, low efficiency, and reduced lifetime. The compound has a spirofluorene structure, is an orthogonal structure, has great steric hindrance, and reduces the formation of fluorescent molecular excimers of anthracene derivatives, so that the compound has excellent performance on molecular film formation and charge transmission, the charge transmission in the element is more balanced, and the element performance is improved.
The organic electroluminescent device of the present invention can be applied to wall-mounted televisions, flat panel displays, flat light emitters for illumination and the like, light sources for back lights of copying machines, printers, liquid crystal displays, measuring instruments and the like, display panels, sign lamps and the like.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. An anthracene derivative, characterized in that the structural general formula of the anthracene derivative is shown as formula (I) or formula (II):
Figure FDA0003687680650000011
wherein X 1 To X 8 Each independently represents N or CR 3 ；
R 1 、R 2 、R 3 At each occurrence, each identically or differently selected from hydrogen, deuterium, with C 1 -C 40 Straight chain alkyl of (2) having C 1 -C 40 Linear heteroalkyl group of (A) having C 3 -C 40 A branched or cyclic alkyl group having C 3 -C 40 A branched or cyclic heteroalkyl group of (A) having C 2 -C 40 Alkenyl or alkynyl groups of (a), an aromatic or aromatic ring system having 5 to 80, preferably 6 to 60 carbon atoms or a heteroaromatic or heteroaromatic ring system having 2 to 60 carbon atoms, or two or more adjacent groups may be optionally cyclized or fused to each other to form a ring;
Ar 1 、Ar 2 、Ar 3 、Ar 4 each independently selected from the group consisting of hydrogen, deuterium, an aromatic or aromatic ring system having 6 to 60 carbon atoms, or a heteroaromatic or heteroaromatic ring system having 2 to 60 carbon atoms; ar (Ar) 3 And Ar 4 May be linked to each other by a single bond, a bridging group of O, S, N, or C to form a ring; or Ar in the formula (II) 1 And Ar 3 Or Ar 4 The rings are connected to each other by a single bond, O, S, N, or a bridging group of C.
2. The anthracene derivative according to claim 1, wherein X is 1 ～X 8 Each is N or CH; r 1 、R 2 Is hydrogen; ar (Ar) 1 、Ar 2 Each independently selected from the group consisting of hydrogen, deuterium, an aromatic or aromatic ring system having 6 to 60 carbon atoms, or a heteroaromatic or heteroaromatic ring system having 2 to 60 carbon atoms; ar (Ar) 3 、Ar 4 Each independently selected from the group consisting of aromatic or aromatic ring systems having 6 to 60 carbon atoms.
3. The anthracene derivative according to claim 1, wherein the heteroaromatic or heteroaromatic ring system is selected from the group consisting of groups II-1 to II-17 and aromatic rings or aromatic ring systems, wherein II-1 to II-17 have the following specific structures:
Figure FDA0003687680650000021
wherein Z is 1 、Z 2 Each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 represents an oxygen atom or a sulfur atom;
Figure FDA0003687680650000022
represents a bond between a substituent and the main structure.
4. The anthracene derivative according to any one of claims 1 to 3, wherein the anthracene derivative has a CJHB950 to CJHB1087 structure selected from one of the following structures:
Figure FDA0003687680650000031
Figure FDA0003687680650000041
Figure FDA0003687680650000051
Figure FDA0003687680650000061
Figure FDA0003687680650000071
Figure FDA0003687680650000081
Figure FDA0003687680650000091
Figure FDA0003687680650000101
wherein, T 2 -O-, S-or one of the following structures:
Figure FDA0003687680650000102
and-represent a connecting bond.
5. An organic electroluminescent material, characterized in that the organic electroluminescent material comprises the anthracene derivative according to any one of claims 1 to 4.
6. An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises the anthracene derivative according to any one of claims 1 to 4.
7. The organic electroluminescent device according to claim 6, wherein the organic layer is selected from one or more of an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer and a light emitting layer;
preferably, the electron transport layer and the light-emitting layer contain the anthracene derivative.
8. The organic electroluminescent device according to claim 7, wherein the organic electroluminescent device is characterized in thatThe luminescent layer comprises a dopant and a luminescent main body, wherein the dopant comprises anthracene, naphthalene, anthracene, pyrene, perylene, phenanthrene, fluoranthene,
Figure FDA0003687680650000111
Benzanthracene, fluorene, spirofluorene, pentacene, and derivatives thereof; the luminescent host comprises the anthracene derivative.
9. The organic electroluminescent device according to claim 8, wherein the mass ratio of the dopant to the luminescent host is 1: 99-50: 50.
10. a consumer product comprising the organic electroluminescent device according to any one of claims 6 to 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4332096A1 (en) * 2022-08-29 2024-03-06 Canon Kabushiki Kaisha Organic compound and organic light-emitting element

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190013191A (en) * 2017-08-01 2019-02-11 성균관대학교산학협력단 Organic luminescent compound, producing method of the same and organic electroluminescent device including the same
CN112794804A (en) * 2019-11-14 2021-05-14 石家庄诚志永华显示材料有限公司 Spirofluorene derivative and application thereof
CN113429302A (en) * 2021-08-27 2021-09-24 北京八亿时空液晶科技股份有限公司 Naphthofluorene derivative, luminescent material, luminescent element and consumer product

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190013191A (en) * 2017-08-01 2019-02-11 성균관대학교산학협력단 Organic luminescent compound, producing method of the same and organic electroluminescent device including the same
CN112794804A (en) * 2019-11-14 2021-05-14 石家庄诚志永华显示材料有限公司 Spirofluorene derivative and application thereof
CN113429302A (en) * 2021-08-27 2021-09-24 北京八亿时空液晶科技股份有限公司 Naphthofluorene derivative, luminescent material, luminescent element and consumer product

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4332096A1 (en) * 2022-08-29 2024-03-06 Canon Kabushiki Kaisha Organic compound and organic light-emitting element

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