CN113321641A - Compound, electron transport material, organic electroluminescent device and display device - Google Patents

Compound, electron transport material, organic electroluminescent device and display device Download PDF

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CN113321641A
CN113321641A CN202110500645.1A CN202110500645A CN113321641A CN 113321641 A CN113321641 A CN 113321641A CN 202110500645 A CN202110500645 A CN 202110500645A CN 113321641 A CN113321641 A CN 113321641A
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邢其锋
丰佩川
单鸿斌
马艳
胡灵峰
陈跃
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Yantai Xianhua Chem Tech Co ltd
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Abstract

The application provides a compound of general formula (I) which can be used in an electron transport material. The compound has a parent structure of a double-fluorene combined electron-absorbing fragment, has high bond energy among atoms, has good thermal stability, is favorable for solid-state accumulation among molecules, and has strong transition capability of electrons. When the organic electroluminescent material is used as an electron transport material, the driving voltage of the organic electroluminescent device is effectively reduced, the current efficiency of the organic electroluminescent device is improved, and the service life of the organic electroluminescent device is prolonged. The present application also provides an organic electroluminescent device and a display device comprising the compound of formula (I).
Figure DDA0003056072140000011

Description

Compound, electron transport material, organic electroluminescent device and display device
Technical Field
The application relates to the field of organic light-emitting display, in particular to a compound, an electron transport material, an organic electroluminescent device and a display device.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage dc driving, full curing, wide viewing angle, light weight, simple composition and process, etc., and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, and has a large viewing angle, low power, a response speed 1000 times that of the liquid crystal display, and a manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advance of the OLED technology in the two fields of lighting and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, and flexible display and large-area display can be realized by forming a film on any substrate by an evaporation or spin coating method; the optical property, the electrical property, the stability and the like of the material can be adjusted by changing the structure of the molecule, and the selection of the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. Among them, the electron transport material, as an important functional material, has a direct influence on the mobility of electrons and ultimately affects the light emitting efficiency of the OLED.
Disclosure of Invention
An object of embodiments of the present application is to provide a compound for an electron transport material.
In a first aspect, the present application provides a compound having the structure of formula (I):
Figure BDA0003056072120000021
wherein the content of the first and second substances,
R1and R2Each independently selected from C1-C6Alkyl of (C)5-C20Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of (A), R1And R2Wherein two adjacent groups can be connected to form a ring;
R3-R8each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)5-C20Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of (A), R3-R8Wherein two adjacent groups can be connected to form a ring;
X1-X5、Y1-Y5each independently selected from CR9Or N, R9Each independently selected from hydrogen, deuterium, cyano, C1-C6Alkyl of (C)1-C6Heteroalkyl group of (5), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of, adjacent to R9Can be connected to form a ring, X1-X5At least one of which is selected from N or R9CR being cyano9，Y1-Y5At least one of which is selected from N or R9CR being cyano9；
m and n are each independently selected from 0 or 1, at least one of said m and n being other than 0;
when m is 1, L1Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C30Arylene of, unsubstituted or substituted by Ra C3-C30The heteroarylene group of (a);
when m is 0, L1Selected from C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30The heteroaryl group of (a);
when n is 1, L2Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C30Arylene of, unsubstituted or substituted by Ra C3-C30The heteroarylene group of (a);
when n is 0, L2Selected from C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30The heteroaryl group of (a);
each heteroatom in the heteroalkyl, heteroaryl, or heteroarylene group is independently selected from O, S, N;
the substituents Ra of each group are each independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, naphthyl.
In a second aspect, the present application provides an electron transport material comprising at least one of the compounds provided herein.
In a third aspect, the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided herein.
A fourth aspect of the present application provides a display apparatus comprising the organic electroluminescent device provided herein.
The compound provided by the application has a parent structure of a linked electron-absorbing bifluorene fragment, has high bond energy among atoms, good thermal stability, favorability for solid-state accumulation among molecules and strong transition capability of electrons. When the organic electroluminescent device is used as an electron transport material, the organic electroluminescent device has a proper energy level with the adjacent layers, and is beneficial to the injection and migration of electrons, so that the driving voltage of the organic electroluminescent device is effectively reduced, the current efficiency of the organic electroluminescent device is improved, and the service life of the organic electroluminescent device is prolonged. The organic electroluminescent device comprises the compound as an electron transport material, so that the driving voltage of the electroluminescent device can be effectively reduced, the current efficiency of the organic electroluminescent device can be improved, and the service life of the organic electroluminescent device can be prolonged. The display device provided by the application comprises the organic electroluminescent device provided by the application, and has an excellent display effect.
Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
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In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be 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 one embodiment of the present application, and other embodiments can be obtained by those skilled in the art according to the drawings.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the description herein are intended to be within the scope of the present disclosure.
In a first aspect, the present application provides a compound having the structure of formula (I):
Figure BDA0003056072120000041
wherein the content of the first and second substances,
R1and R2Each independently selected from C1-C6Alkyl of (C)5-C20Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of (A), R1And R2Wherein two adjacent groups can be connected to form a ring;
R3-R8each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)5-C20Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of (A), R3-R8Wherein two adjacent groups can be connected to form a ring;
X1-X5、Y1-Y5each independently selected from CR9Or N, R9Each independently selected from hydrogen, deuterium, cyano, C1-C6Alkyl of (C)1-C6Heteroalkyl group of (5), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of, adjacent to R9Can be connected to form a ring, X1-X5At least one of which is selected from N or R9CR being cyano9，Y1-Y5At least one of which is selected from N or R9CR being cyano9；
m and n are each independently selected from 0 or 1, at least one of said m and n being other than 0;
when m is 1, L1Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C30Arylene of, unsubstituted or substituted by Ra C3-C30The heteroarylene group of (a);
when m is 0, L1Selected from C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30The heteroaryl group of (a);
when n is 1, L2Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C30Arylene of, unsubstituted or substituted by Ra C3-C30The heteroarylene group of (a);
when n is 0, L2Selected from C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30The heteroaryl group of (a);
each heteroatom in the heteroalkyl, heteroaryl, or heteroarylene group is independently selected from O, S, N;
the substituents Ra of each group are each independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, naphthyl.
The compound provided by the application has a parent structure of a linked electron-absorbing bifluorene fragment, has high bond energy among atoms, good thermal stability, favorability for solid-state accumulation among molecules and strong transition capability of electrons. In addition, the compound provided by the application has the advantages of simple and feasible preparation process and easily obtained raw materials, and is suitable for industrial production.
Preferably, R1And R2Each independently of the otherIs selected from C1-C6Alkyl of (C)5-C12Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a);
preferably, R3-R8Each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)5-C12Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a);
preferably, R9Each independently selected from hydrogen, deuterium, cyano, C1-C6Alkyl of (C)1-C3Heteroalkyl group of (5), C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a);
preferably, when m is 1, L1Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C18Arylene of, unsubstituted or substituted by Ra C3-C18The heteroarylene group of (a);
when m is 0, L1Selected from C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a);
when n is 1, L2Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C18Arylene of, unsubstituted or substituted by Ra C3-C18The heteroarylene group of (a);
when n is 0, L2Selected from C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a).
More preferably, R1And R2Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolineA group selected from the group consisting of an isoquinolyl group, a quinazolinyl group, a quinoxalinyl group, a cinnolinyl group, a naphthyridinyl group, a triazinyl group, a pyridopyrazinyl group, a furyl group, a benzofuryl group, a dibenzofuryl group, an aza-dibenzofuryl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an aza-dibenzothienyl group, a 9, 9-dimethylfluorenyl group, an arylamino group, and a carbazolyl group.
More preferably, R3-R8Each independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
More preferably, R9Each independently selected from hydrogen, deuterium, cyano, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
More preferably, when m is 1, L is1A subunit selected from the group consisting of a bond, unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzofuranThiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole;
when m is 0, L1Selected from the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl;
when n is 1, L2A subunit selected from the group consisting of a bond, unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole;
n is 0, L2Selected from the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
For example, the aforementioned compound is selected from any of the following structures a1-a 40:
Figure BDA0003056072120000071
Figure BDA0003056072120000081
in a second aspect, the present application provides an electron transport material comprising at least one of the compounds provided herein.
When the electron transport material is applied to the electron transport layer, the electron transport material has a proper energy level with the adjacent layers, and is beneficial to the injection and migration of electrons, so that the driving voltage of an organic electroluminescent device is effectively reduced, the current efficiency of the organic electroluminescent device is improved, and the service life of the organic electroluminescent device is prolonged.
A third aspect of the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided herein. Therefore, the organic electroluminescent device provided by the application has low driving voltage, high luminous efficiency and long service life.
In the present application, there is no particular limitation on the kind and structure of the organic electroluminescent device, and there may be various types and structures of organic electroluminescent devices known in the art as long as at least one of the electron transport materials provided herein may be used.
The organic electroluminescent device of the present application may be a light-emitting device having a top emission structure, and examples thereof include a light-emitting device comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a bottom emission structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially provided on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a double-sided light-emitting structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode are sequentially provided on a substrate.
In addition, an electron blocking layer may be provided between the hole transport layer and the light emitting layer, a hole blocking layer may be provided between the light emitting layer and the electron transport layer, and a light extraction layer may be provided on the transparent electrode on the light outgoing side. However, the structure of the organic electroluminescent device of the present application is not limited to the above-described specific structure, and the above-described layers may be omitted or added if necessary. The thickness of each layer is not particularly limited as long as the object of the present invention can be achieved. For example, the organic electroluminescent device may include an anode made of metal, a hole injection layer (5nm to 20nm), a hole transport layer (80nm to 140nm), an electron blocking layer (5nm to 20nm), a light emitting layer (150nm to 400nm), a hole blocking layer (5nm to 20nm), an electron transport layer (300nm to 800nm), an electron injection layer (5nm to 20nm), a transparent or semitransparent cathode, and a light extraction layer (50nm to 90nm) in this order on a substrate.
Fig. 1 shows a schematic diagram of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are sequentially disposed from bottom to top.
It is to be understood that fig. 1 schematically illustrates the structure of a typical organic electroluminescent device, and the present application is not limited to this structure, and the electron transport material of the present application may be used in any type of organic electroluminescent device.
In the organic electroluminescent device of the present application, various materials used for the layers in the prior art may be used for the layers, except that the electron transport layer contains the electron transport material provided herein.
For convenience, the organic electroluminescent device of the present application is described below with reference to fig. 1, but this is not meant to limit the scope of the present application in any way. It is understood that all organic electroluminescent devices capable of using the electron transport material of the present application are within the scope of the present application.
In the present application, the material of the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, for example, glass, polymer materials, glass with Thin Film Transistor (TFT) components, polymer materials, and the like, may be used.
In the present application, the material of the reflective anode electrode 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) known in the art2) The transparent conductive material such as zinc oxide (ZnO) or Low Temperature Polysilicon (LTPS) may be selected from metal materials such as silver and its alloy, aluminum and its alloy, organic conductive materials such as poly (3, 4-ethylenedioxythiophene) (PEDOT), and a multilayer structure of the above materials.
In the present application, the material of the hole injection layer 3 is not particularly limited, and a hole injection layer material known in the art, for example, a Hole Transport Material (HTM) is selected as the hole injection material.
In the present application, the hole injection layer 3 may further include a p-type dopant, the kind of the p-type dopant is not particularly limited, and various p-type dopants known in the art may be used, for example, the p-type dopant may be selected from at least one of the following p-1 to p-3 compounds:
Figure BDA0003056072120000101
in the present application, the amount of the p-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the material of the hole transport layer 4 is not particularly limited, and may be made using a Hole Transport Material (HTM) known in the art. The number of layers of the hole transport layer 4 is not particularly limited, and may be adjusted as needed as long as it satisfies the object of the present application, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.
For example, the material for the hole injection layer and the material for the hole transport layer may each be independently selected from, but not limited to, at least one of the following HT-1 to HT-31 compounds:
Figure BDA0003056072120000111
Figure BDA0003056072120000121
in the present application, the light emitting layer 5 may include a blue light emitting layer, a green light emitting layer, or a red light emitting layer, and the light emitting material in the light emitting layer 5 is not particularly limited, and various light emitting materials known to those skilled in the art may be used, for example, the light emitting material may include a host material and a guest material. In the present application, the amounts of the host material and the guest material are not particularly limited, and may be those known to those skilled in the art.
In the present application, the host material of the red light emitting layer is not particularly limited, and at least one of the host materials of the red light emitting layer known in the art may be used. For example, it may be selected from, but not limited to, at least one of the following RH-1 to RH-13 compounds, and GPH-1 to GPH-80 compounds:
Figure BDA0003056072120000131
Figure BDA0003056072120000141
Figure BDA0003056072120000151
Figure BDA0003056072120000161
in the present application, the host material of the green light emitting layer is not particularly limited, and at least one of the host materials of the green light emitting layer known in the art may be used. For example, it may be selected from, but not limited to, at least one of the aforementioned GPH-1 to GPH-80 compounds.
In the present application, the host material of the blue light emitting layer is not particularly limited, and at least one of the host materials of the blue light emitting layer known in the art may be used. For example, at least one compound selected from, but not limited to, the following BH-1 to BH-36 compounds:
Figure BDA0003056072120000162
Figure BDA0003056072120000171
in the present application, the guest material of the red light emitting layer is not particularly limited, and at least one of the guest materials of the red light emitting layer known in the art may be used. For example, at least one of the following RPD-1 to RPD-28 compounds may be selected, but is not limited to:
Figure BDA0003056072120000181
Figure BDA0003056072120000191
in the present application, the guest material of the green light emitting layer is not particularly limited, and at least one of the guest materials of the green light emitting layer known in the art may be used. For example, at least one of the following GD 01-GD 04 compounds may be selected, but is not limited to:
Figure BDA0003056072120000192
in the present application, the guest material of the blue light emitting layer is not particularly limited, and at least one of the guest materials of the blue light emitting layer known in the art may be used. For example, at least one of the following BD01 to BD04 compounds may be selected from, but not limited to:
Figure BDA0003056072120000193
in the present application, the electron transport layer 6 may contain at least one of the electron transport materials of the present application, and may also contain a combination of at least one of the electron transport materials of the present application and at least one of the following known electron transport materials.
For example, known electron transport materials may be selected from, but are not limited to, at least one of the following ET-1 to ET-57 compounds:
Figure BDA0003056072120000201
Figure BDA0003056072120000211
Figure BDA0003056072120000221
in the present application, the electron transport layer 6 may further include an n-type dopant, the kind of the n-type dopant is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:
Figure BDA0003056072120000222
in the present application, the amount of the n-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, and for example, may include, but are not limited to, LiQ, LiF, NaCl, CsF, Li in the prior art2O、Cs2CO3BaO, Na, Li, Ca and the likeAt least one of the materials.
In the present application, the material of the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, magnesium-silver mixture, magnesium-aluminum mixture, metal such as LiF/Al, ITO, Al, etc., metal mixture, oxide, etc.
The fourth aspect of the present application provides a display device comprising the organic electroluminescent device provided by the present application, having excellent display effect. The display device includes, but is not limited to, a display, a television, a mobile communication terminal, a tablet computer, and the like.
The method for preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be used, for example, the present application may be prepared by the following preparation method:
(1) cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top emission, respectively carrying out steps of medicinal washing, water washing, hairbrush, high-pressure water washing, air knife and the like in a cleaning machine, and then carrying out heat treatment;
(2) vacuum evaporating a hole injection material on the reflecting anode electrode 2 to form a hole injection layer 3, wherein the hole injection layer 3 contains a main body material and a p-type dopant;
(3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;
(4) a luminescent layer 5 is evaporated on the hole transport layer 4 in vacuum, wherein the luminescent layer 5 comprises a host material and a guest material;
(5) vacuum evaporating an electron transport material on the luminescent layer 5 to form an electron transport layer 6;
(6) vacuum evaporating an electron injection material on the electron transport layer 6 to form an electron injection layer 7;
(7) a cathode material is vacuum-deposited on the electron injection layer 7 as a cathode electrode 8.
The above description has been made only of the structure of a typical organic electroluminescent device and a method for manufacturing the same, and it should be understood that the present application is not limited to this structure. The electron transport material of the present application can be used for an organic electroluminescent device of any structure, and the organic electroluminescent device can be manufactured by any manufacturing method known in the art.
The method for synthesizing the compound of the present application is not particularly limited, and the synthesis can be carried out by any method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present application.
Synthetic examples
Synthesis example 1: synthesis of Compound A1
Figure BDA0003056072120000241
Into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1 mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4). The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 3-pyridyl-4-phenylboronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4The addition amount of (b) is 1 mol% of M3。
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
Into a reaction flask were added 100mmol of 4, 6-diphenyl-2- (4-phenylboronate), 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 1. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)δ9.24(s,1H),8.70(s,1H),8.34(d,J＝12.0Hz,5H),7.92(dd,J＝10.0,8.0Hz,5H),7.62–7.45(m,8H),7.34(s,1H),7.25(d,J＝7.6Hz,7H),1.69(s,6H).
Synthesis example 2: synthesis of compound A8:
Figure BDA0003056072120000251
into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 3, 5-dibromochlorobenzene, 100mmol of 3-pyridineboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 2 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4The amount of (A) added was 2 mol% based on 3, 5-dibromochlorobenzene.
100mmol of M4, 110mmol of pinacol diboron, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of dichloro [1,1' -bis (diphenylphosphino) ferrocene are introduced into a reaction flask]Palladium (Pd (dppf) Cl2). The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M4.
Into a reaction flask were charged 100mmol of M5, 100mmol of M3, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M6. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M6, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M7, wherein the TfO group in M7 is a triflate group.
100mmol of M7, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M8. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M7.
Into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 100mmol of M8, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder A8. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M8.
1H NMR(400MHz,Chloroform)δ9.24(s,1H),8.72(s,1H),8.61(d,J＝12.0Hz,2H),8.33(s,1H),8.18-8.03(m,4H),7.90(d,J＝8.0Hz,1H),7.80-7.59(m,6H),7.47(d,J＝8.8Hz,4H),7.30(t,J＝12.0Hz,4H),7.24(s,1H),1.69(s,6H).
Synthetic example 3: synthesis of compound a 12:
Figure BDA0003056072120000261
into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of cyclopentyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were added 100mmol of 4-phenyl-2-pyridineboronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
100mmol of M5, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M6. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M5.
Into a reaction flask were charged 100mmol of 2-chloro-4-phenylquinazoline, 100mmol of M6, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4. At 120 deg.CAnd reacting for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 12. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M6.
1H NMR(400MHz,Chloroform)δ8.91(s,1H),8.19(d,J＝12.0Hz,2H),8.13(s,1H),7.65(s,1H),7.58–7.38(m,6H),7.34-7.24(m,4H),1.90(s,2H),1.88–1.37(m,16H).
Synthetic example 4: synthesis of compound a 17:
Figure BDA0003056072120000281
into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
100mmol of M3, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. Stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, separating an organic phase,concentration gave a white solid, which was filtered and washed with water, and the resulting solid was purified by recrystallization from toluene to give white powder M4. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M3.
Into a reaction flask were charged 100mmol of 2-chloro-4-phenylquinazoline, 100mmol of M4, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Adding 100mmol of M5, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M6, wherein the TfO group in M6 is a triflate group.
100mmol of M6, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M7. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M6.
100mmol of 2-chloro-4-phenylbenzo [4,5 ] are added to a reaction flask]Thiophene [2,3-d ]]Pyrimidine, 100mmol of M7, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 17. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M7.
1H NMR(400MHz,Chloroform)δ8.45(s,1H),8.13(s,1H),7.98(d,J＝8.4Hz,3H),7.92–7.82(m,5H),7.80(d,J＝7.6Hz,4H),7.58–7.52(m,4H),7.49(s,1H),7.33(d,J＝12.4Hz,4H),7.24(s,1H),1.69(s,6H).
Synthesis example 5: synthesis of compound a 18:
Figure BDA0003056072120000291
into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
100mmol of M3, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M3.
100mmol of 4-cyanophenylboronic acid and 100mmol of 5-Bromo-2-chloropyridine, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 5-bromo-2-chloropyridine.
Into a reaction flask were charged 100mmol of M4, 100mmol of M5, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M6. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Adding 100mmol of M6, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M7, wherein the TfO group in M7 is a triflate group.
100mmol of M7, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M8. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M7.
Into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 100mmol of M8, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, and concentrating an organic phase to obtain whiteThe colored solid was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give white powder a 18. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M8.
1H NMR(400MHz,Chloroform)δ8.91(s,1H),8.53(s,1H),8.30(s,1H),8.02(d,J＝10.0Hz,3H),7.90(dd,J＝12.8,8.4Hz,5H),7.80(s,1H),7.72(t,J＝9.6Hz,3H),7.67(s,1H),7.59(s,1H),7.33(d,J＝8.4Hz,4H),7.24(s,1H),1.69(s,6H).
Synthetic example 6: synthesis of compound a 23:
Figure BDA0003056072120000311
into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
100mmol of M3, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, separating an organic phase, concentrating to obtain a white solid, filtering, washing with water, and obtainingThe obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M3.
100mmol of 2-chloro-4-phenylbenzo [4,5 ] are added to a reaction flask]Furan [2,3-d ]]Pyrimidine, 100mmol of M4, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Adding 100mmol of M5, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M6, wherein the TfO group in M6 is a triflate group.
100mmol of M6, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M7. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M6.
Into a reaction flask were added 100mmol of 2-chloro-5-phenylpyridine, 100mmol of M7, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 23. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M7.
1H NMR(400MHz,Chloroform)8.92(s,1H),8.36(s,1H),8.13–7.57(m,9H),7.65(s,1H),7.55–7.38(m,6H),7.29(dd,J＝12.4,9.6Hz,4H),1.69(s,6H).
Synthetic example 7: synthesis of compound a 28:
Figure BDA0003056072120000331
into a reaction flask were charged 100mmol of methyl 2-borate-3-naphthoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
100mmol of M3, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M3.
Into a reaction flask were charged 100mmol of 2-phenyl-5-chloropyridine, 100mmol of M4, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Adding 100mmol of M5, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M6, wherein the TfO group in M6 is a triflate group.
100mmol of M6, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M7. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M6.
Into a reaction flask were charged 100mmol of 2-chloro-4-phenylquinazoline, 100mmol of M7, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 28. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M7.
1H NMR(400MHz,Chloroform)δ8.90(s,1H),8.33(s,2H),8.21–8.11(m,3H),8.03(t,J＝7.6Hz,4H),7.97(s,1H),7.90(d,J＝8.0Hz,3H),7.89–7.68(m,5H),7.65(s,1H),7.57–7.51(m,4H),7.49(s,1H),,1.75(s,6H).
Other compounds of the present application can be synthesized by selecting suitable starting materials according to the idea of synthesis examples 1 to 7, and any other suitable methods and starting materials can be selected for synthesis.
Example 1
Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing in deionized water, carrying out ultrasonic oil removal in an acetone-ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
then, the glass substrate with the anode is placed in a vacuum chamber and is vacuumized to be less than 10 DEG-5In the torr, a hole injection layer is vacuum evaporated on the anode layer film, the material of the hole injection layer is a hole transport material HT-11 and a p-type dopant (p-1) with the mass ratio of 3%, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
and then, vacuum evaporating a hole transport material HT-5 on the hole injection layer to form the hole transport layer, wherein the evaporation rate is 0.1nm/s, the evaporation film thickness is 80nm, and the hole transport material HT-5 is as follows:
then, a light-emitting layer is evaporated on the hole transport layer in vacuum, the light-emitting layer comprises a host material GHP-16 and a guest material RPD-1, evaporation is carried out by a multi-source co-evaporation method, the evaporation rate of the host material GHP-16 is adjusted to be 0.1nm/s, the evaporation rate of the guest material RPD-1 is 3% of the evaporation rate of the host material GHP-16, and the total thickness of the evaporation film is 30 nm;
then, an electron transport material A1 is vacuum-evaporated on the luminescent layer to be used as an electron transport layer, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30 nm;
then, LiF with the thickness of 0.5nm is evaporated on the electron transport layer in vacuum to be used as an electron injection layer, and the evaporation rate is 0.1 nm/s;
and finally, evaporating Al with the thickness of 150nm on the electron injection layer to be used as a cathode, wherein the evaporation rate is 1 nm/s.
The organic electroluminescent device of the present embodiment emits red light.
Examples 2 to 7
The procedure was as in example 1 except that A1 was replaced with A8, A12, A17, A18, A23 and A28, respectively.
Example 8
The procedure is as in example 1, except that GPH-44 is used in place of GHP-16 and GD04 is used in place of RPD-1.
The organic electroluminescent device of the present embodiment emits green light.
Example 9
The procedure of example 1 was repeated, except that the compound BH-1 was used in place of GHP-16 and the compound BD01 was used in place of RPD-1.
The organic electroluminescent device of the present embodiment emits blue light.
Comparative example 1
The procedure was as in example 1, except that compound ET-2 was used in place of A1.
Comparative example 2
The procedure was as in example 8, except that compound ET-2 was used in place of A1.
Comparative example 3
The procedure was as in example 9, except that compound ET-2 was used in place of A1.
The performance test method of the organic electroluminescent device comprises the following steps:
the driving voltage, current efficiency and lifetime of the organic electroluminescent devices prepared in examples 1 to 9 and comparative examples 1 to 3 were measured at the same luminance using a digital source meter and a luminance meter, as follows:
< Driving Voltage and Current efficiency test >
(1) Red light device: the voltage was raised at a rate of 0.1V per second, as determined when the luminance of the organic electroluminescent device reached 5000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the luminance to the current density is the current efficiency.
(2) Green light device: the voltage was raised at a rate of 0.1V per second to determine that the luminance of the organic electroluminescent device reached 10000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the luminance to the current density is the current efficiency.
(3) Blue light device: the voltage was raised at a rate of 0.1V per second, as determined when the luminance of the organic electroluminescent device reached 1000cd/m2The voltage at the time of operation is the drive voltage,measuring the current density at the same time; the ratio of the luminance to the current density is the current efficiency.
< Life test of LT95 >
(1) Red light device: using a luminance meter at 5000cd/m2The luminance drop of the organic electroluminescent device was measured to be 4750cd/m by maintaining a constant current at luminance2Time in hours.
(2) Green light device: using a luminance meter at 10000cd/m2The luminance drop of the organic electroluminescent device was measured to be 9500cd/m by maintaining a constant current at luminance2Time in hours.
(3) Blue light device: using a luminance meter at 1000cd/m2The luminance drop of the organic electroluminescent device was measured to 950cd/m by maintaining a constant current at luminance2Time in hours.
Table 1 organic electroluminescent device performance results
Figure BDA0003056072120000371
As can be seen from the data in table 1, the use of the compounds a1, A8, a12, a17, a18, a23, a28 provided in the present application as electron transport materials in examples 1 to 9 enables lower driving voltages, higher current efficiencies, and longer life of LT95 for red, green, and blue light emitting devices at the same luminance as compared to the use of known materials in the prior art as electron transport materials in organic electroluminescent devices in comparative examples 1 to 3. Therefore, the compound is applied to an organic electroluminescent device as an electron transport material, and can effectively reduce the driving voltage of the organic electroluminescent device, improve the current efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (10)

1. A compound having the structure of formula (I):
Figure FDA0003056072110000011
wherein the content of the first and second substances,
R1and R2Each independently selected from C1-C6Alkyl of (C)5-C20Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of (A), R1And R2Wherein two adjacent groups can be connected to form a ring;
R3-R8each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)5-C20Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of (A), R3-R8Wherein two adjacent groups can be connected to form a ring;
X1-X5、Y1-Y5each independently selected from CR9Or N, R9Each independently selected from hydrogen, deuterium, cyano, C1-C6Alkyl of (C)1-C6Heteroalkyl group of (5), C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30Heteroaryl of, adjacent to R9Can be connected to form a ring, X1-X5At least one of which is selected from N or R9CR being cyano9，Y1-Y5At least one of which is selected from N or R9CR being cyano9；
m and n are each independently selected from 0 or 1, at least one of said m and n being other than 0;
when m is 1, L1Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C30Arylene ofC substituted or substituted by Ra3-C30The heteroarylene group of (a);
when m is 0, L1Selected from C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30The heteroaryl group of (a);
when n is 1, L2Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C30Arylene of, unsubstituted or substituted by Ra C3-C30The heteroarylene group of (a);
when n is 0, L2Selected from C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra3-C30The heteroaryl group of (a);
each heteroatom in the heteroalkyl, heteroaryl, or heteroarylene group is independently selected from O, S, N;
the substituents Ra of each group are each independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, naphthyl.
2. The compound of claim 1, wherein,
R1and R2Each independently selected from C1-C6Alkyl of (C)5-C12Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a);
R3-R8each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)5-C12Cycloalkyl of (3), C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a);
R9each independently selected from hydrogen, deuterium, cyano, C1-C6Alkyl of (C)1-C3Heteroalkyl group of (5), C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a);
when m is 1, L1Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C18Arylene of, unsubstituted or substituted by Ra C3-C18The heteroarylene group of (a);
when m is 0, L1Selected from C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a);
when n is 1, L2Selected from the group consisting of a bond, C unsubstituted or substituted by Ra6-C18Arylene of, unsubstituted or substituted by Ra C3-C18The heteroarylene group of (a);
when n is 0, L2Selected from C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra3-C18The heteroaryl group of (a).
3. The compound of claim 1, wherein R is1And R2Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
4. The compound of claim 1, wherein R is3-R8Each independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinylA quinoxaline group, a cinnolinyl group, a naphthyridine group, a triazine group, a pyridopyrazinyl group, a furyl group, a benzofuryl group, a dibenzofuryl group, an aza-dibenzofuryl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an aza-dibenzothienyl group, a 9, 9-dimethylfluorenyl group, an arylamine group, a carbazolyl group.
5. The compound of claim 1, wherein R is9Each independently selected from hydrogen, deuterium, cyano, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
6. The compound of claim 1, wherein,
when m is 1, the L1A subunit selected from the group consisting of a bond, unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole;
when m is 0, L1Selected from the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, phenanthrenyl, quinolyl, pyridyl, furyl, benzofuranyl, pyridyl, furyl, and the like,Aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamine, carbazolyl;
when n is 1, L is2A subunit selected from the group consisting of a bond, unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole;
n is 0, L2Selected from the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
7. The compound according to claim 1, wherein said compound is selected from any one of the following structures a1-a 40:
Figure FDA0003056072110000041
Figure FDA0003056072110000051
8. an electron transport material comprising at least one of the compounds of any one of claims 1-7.
9. An organic electroluminescent device comprising at least one of the electron transport materials of claim 8.
10. A display device comprising the organic electroluminescent device according to claim 9.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013081416A1 (en) * 2011-12-01 2013-06-06 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN112094170A (en) * 2020-09-29 2020-12-18 苏州久显新材料有限公司 Fluorene compound and light emitting device thereof
CN112125861A (en) * 2020-09-01 2020-12-25 烟台显华化工科技有限公司 Compound, electron transport material and organic electroluminescent device
CN112125892A (en) * 2020-09-01 2020-12-25 烟台显华化工科技有限公司 Compound, electron transport material and organic electroluminescent device
CN112538056A (en) * 2019-09-20 2021-03-23 南京高光半导体材料有限公司 Electron transport material and organic electroluminescent device containing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013081416A1 (en) * 2011-12-01 2013-06-06 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN112538056A (en) * 2019-09-20 2021-03-23 南京高光半导体材料有限公司 Electron transport material and organic electroluminescent device containing same
CN112125861A (en) * 2020-09-01 2020-12-25 烟台显华化工科技有限公司 Compound, electron transport material and organic electroluminescent device
CN112125892A (en) * 2020-09-01 2020-12-25 烟台显华化工科技有限公司 Compound, electron transport material and organic electroluminescent device
CN112094170A (en) * 2020-09-29 2020-12-18 苏州久显新材料有限公司 Fluorene compound and light emitting device thereof

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