CN111635415B - Compound, electron transport material and organic electroluminescent device - Google Patents

Compound, electron transport material and organic electroluminescent device Download PDF

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CN111635415B
CN111635415B CN202010519053.XA CN202010519053A CN111635415B CN 111635415 B CN111635415 B CN 111635415B CN 202010519053 A CN202010519053 A CN 202010519053A CN 111635415 B CN111635415 B CN 111635415B
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organic electroluminescent
reaction
electroluminescent device
electron transport
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CN111635415A (en
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邢其锋
丰佩川
李玉彬
孙伟
胡灵峰
陈跃
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Yantai Xianhua Chem Tech Co ltd
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Abstract

The present application provides a compound of formula (I) which can be used in electron transport materials. The compound has a parent structure of diversified fused heterocycle, has high bond energy among atoms, good thermal stability, favorability for solid accumulation among molecules and strong electron transition capability, and can effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency and prolong the service life of the organic electroluminescent device when being used as an electron transport material. The application also provides an organic electroluminescent device and a display device comprising the compound of the general formula (I).

Description

Compound, electron transport material and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic light-emitting display, in particular to an electron transport material and an organic electroluminescent device containing the electron transport material.
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 (OLED) has the advantages of self-luminescence, low voltage DC drive, full solidification, wide viewing angle, light weight, simple composition and process, etc., compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle and low power, the response speed can reach 1000 times of the liquid crystal display, and the manufacturing cost is 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 advancement of OLED technology in the two fields of illumination 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 usually the result of the optimized collocation 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, film can be formed on any substrate by a vapor deposition or spin coating method, and flexible display and large-area display can be realized; 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 material has a large space to select. In the most common OLED device structures, the following classes of organic materials are typically included: a hole injection material, a hole transport material, an electron transport material, a light emitting material (dye or doped guest material) of each color, a corresponding host material, and the like. Currently, an electron transport material is an important functional material, which has a direct effect on the mobility of electrons and ultimately affects the luminous efficiency of an OLED. However, the electron transfer rate achieved by the electron transport materials currently applied to the OLED is low, and the energy level matching with the adjacent layers is poor, which severely restricts the light emitting efficiency of the OLED and the display function of the OLED display device.
Disclosure of Invention
The embodiment of the invention aims to provide an electron transport material so as to improve the luminous efficiency of an organic electroluminescent device and prolong the service life of the organic electroluminescent device.
In a first aspect the present invention provides a compound of formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
Ar 1 and Ar is a group 2 Each independently selected from C 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
L 1 and L 2 Each independently selected from chemical bonds, C 6 -C 30 Arylene group or C of (C) 3 -C 30 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
x is selected from O, S, CR 1 R 2 ，R 1 And R is 2 Each independently selected from C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 30 Aromatic groups or C 3 -C 30 Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently can be substituted with Ra, the R 1 And R is 2 Can be linked to form a ring;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
A second aspect of the present application provides an electron transport material comprising at least one of the compounds provided herein.
A third aspect of 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 device comprising the organic electroluminescent device provided herein.
The compound provided by the application has a parent structure of diversified fused heterocycles, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, and has strong electron transition capability. When the material is used as an electron transport material, the material has proper energy level with adjacent layers, is favorable for electron injection and migration, can effectively reduce the landing voltage, has higher electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device. The organic electroluminescent device comprises the compound as an electron transport material, so that the voltage at the take-off and landing can be effectively reduced, the luminous efficiency is improved, and the service life of the organic electroluminescent device is prolonged. The display device provided by the application has excellent display effect. Of course, it is not necessary for any one product or method of practicing the invention to achieve all of the advantages set forth above at the same time.
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, and it is apparent that the drawings in the following description are only one embodiment of the present invention, and other embodiments can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In a first aspect the present invention provides a compound of formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
Ar 1 and Ar is a group 2 Each independently selected from C 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
L 1 and L 2 Each independently selected from chemical bonds, C 6 -C 30 Arylene group or C of (C) 3 -C 30 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
x is selected from O, S, CR 1 R 2 ，R 1 And R is 2 Each independently selected from C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 30 Aromatic groups or C 3 -C 30 Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently can be substituted with Ra, the R 1 And R is 2 Can be linked to form a ring;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
Preferably Ar 1 And Ar is a group 2 Each independently selected from C 6 -C 18 Aromatic groups or C of (2) 3 -C 18 The hydrogen atoms on the aryl and heteroaryl groupsEach independently may be substituted with Ra;
preferably L 1 And L 2 Each independently selected from chemical bonds, C 6 -C 18 Arylene group or C of (C) 3 -C 18 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
preferably, R 1 And R is 2 Each independently selected from C 3 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 18 Aromatic groups or C of (2) 3 -C 18 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra.
More preferably, the Ar 1 And Ar is a group 2 Each independently selected from the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, the L 1 And L 2 Each independently selected from the group consisting of a bond, a subunit of the following compounds 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.
More preferably, the R 1 And R is 2 Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, and triphenylenePhenyl, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
For example, the compound of formula (I) is selected from the following compounds:
a second aspect of the present application provides an electron transport material comprising at least one of the compounds described above.
Fig. 1 shows a schematic view 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 disposed in this order from bottom to top.
It will be appreciated that fig. 1 schematically illustrates only one typical organic electroluminescent device structure, and the present application is not limited to this structure, and the electron transport material of the present application may be used for any type of organic electroluminescent device. For example, the organic electroluminescent device may further include an electron blocking layer, a hole blocking layer, a light extraction layer, and the like. In practical applications, these layers may be added or omitted as the case may be.
The compound adopted by the electron transport material has a parent structure of diversified condensed heterocycles, has high bond energy among atoms, good thermal stability, is favorable for solid state accumulation among molecules, has strong electron transition capability, and can effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device when used as an electron transport layer material.
The derivative of the diversified fused heterocycle is applied to an electron transport layer, has a proper energy level with adjacent layers, is favorable for electron injection and migration, can effectively reduce the landing voltage, has a higher electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device. The compound provided by the application has a larger conjugate plane, is favorable for molecular accumulation, shows good thermodynamic stability, and shows long service life in an organic electroluminescent device.
Meanwhile, the preparation process of the derivative of the multi-element condensed heterocyclic ring is simple and feasible, raw materials are easy to obtain, and the derivative is suitable for industrial production.
A third aspect of the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided herein as an electron transport layer. In the present application, the kind and structure of the organic electroluminescent device are not particularly limited as long as the electron transport material provided in the present application can 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 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 semitransparent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a bottom light emitting structure, and examples thereof include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode structure in this order 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 examples thereof include a transparent or semitransparent 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 semitransparent cathode structure sequentially formed on a substrate.
In the organic electroluminescent device of the present application, any material used for the layer in the prior art may be used for the other layers, except that the electron transport layer contains the electron transport material provided in the present application.
For convenience, the organic electroluminescent device of the present application will be described below with reference to fig. 1, but this is not meant to limit the scope of protection of the present application in any way. It is understood that all organic electroluminescent devices capable of using the electron transport materials of the present application are within the scope of the present invention.
In the present application, the substrate 1 is not particularly limited, and a conventional substrate used in the organic electroluminescent device in the related art, for example, glass, polymer material, glass with TFT devices, polymer material, and the like can be used.
In the present application, the reflective anode electrode 2 is not particularly limited, and may be selected from transparent conductive materials such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO 2), zinc oxide (ZnO), metal materials such as silver and alloys thereof, aluminum and alloys thereof, organic conductive materials such as PEDOT (poly 3, 4-ethylenedioxythiophene), and multilayer structures of the above materials, and the like, which are known in the related art. In the present application, the hole injection layer 3 is not particularly limited, and may be formed using a hole injection layer material known in the art, for example, a Hole Transport Material (HTM) is selected as a host material, and a p-type dopant, the kind of which is not particularly limited, may be used, and various p-type dopants known in the art, for example, the following p-type dopants may be used:
in the present application, the hole transport layer 4 is not particularly limited, and at least one of Hole Transport Materials (HTM) known in the art may be used.
For example, the material for the hole injection layer host and the material for the hole transport layer may be selected from at least one of the following HT-1 to HT-32 compounds:
in the present application, the light emitting material in the light emitting layer 5 is not particularly limited, and any light emitting material known to those skilled in the art may be used, for example, the light emitting material may contain a host material and a light emitting dye. The host material may be selected from at least one of the following GPH-1 to GPH-80 compounds:
in a preferred embodiment of the present application, the light-emitting layer 5 employs a phosphorescent electroluminescence technique. The light emitting layer 5 thereof contains a phosphorescent dopant which may be selected from at least one of the following RPD-1 to RPD-28 compounds. The amount of the dopant is not particularly limited and may be an amount well known to those skilled in the art.
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In the present application, the electron transport layer 6 comprises at least one of the electron transport materials of the present application, the electron transport layer 6 may also comprise a combination of at least one of the electron transport materials of the present application with at least one of the following known electron transport materials ET-1 to ET-57:
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in the present application, the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, for example, may include, but not limited to, liQ, liF, naCl, csF, li in the prior art 2 O、Cs 2 CO 3 At least one of materials such as BaO, na, li, ca.
In the present application, the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, metals such as magnesium silver mixture, liF/Al, ITO, al, metal mixtures, oxides, and the like.
A fourth aspect of the present application provides a display device comprising the organic electroluminescent device provided herein. Including but not limited to displays, televisions, tablet computers, mobile communication terminals, etc.
The method of preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be employed, for example, the present application may be prepared using the following preparation method:
(1) Cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top light emission, respectively performing steps of medicine washing, water washing, hairbrushes, high-pressure water washing, air knives and the like in a cleaning machine, and then performing heating treatment;
(2) Vacuum evaporating a hole injection layer 3 on the reflective anode electrode 2, wherein the main material of the hole injection layer is HTM, and the hole injection layer contains P-type dopant (P-dopant) with the thickness of 10-50nm;
(3) Vacuum evaporating a Hole Transport Material (HTM) on the hole injection layer 3 as a hole transport layer 4, wherein the thickness is 80-150nm;
(4) Vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer comprises a host material (GPH) and a guest material (RPD) and has the thickness of 20-50nm;
(5) Vacuum evaporating an Electron Transport Material (ETM) as an electron transport layer 6 on the light emitting layer 5;
(6) Vacuum evaporating electron injection material selected from LiQ, liF, naCl, csF, li as electron injection layer 7 on electron transport layer 6 2 O、Cs 2 CO 3 One or a combination of a plurality of materials such as BaO, na, li, ca;
(7) A cathode material is vacuum-evaporated on the electron injection layer 7 as a cathode electrode 8.
Only the structure of a typical organic electroluminescent device and a method of manufacturing the same are described above, and it should be understood that the present application is not limited to such a structure. The electron transport material of the present application may be used for an organic electroluminescent device of any structure, and the organic electroluminescent device may be prepared using any preparation method known in the art.
The method for synthesizing the compounds of the present application is not particularly limited, and may be synthesized 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 of A1:
into a 10L three-necked flask, 1000mmol of 2, 4-dichlorobenzo [4,5] thiophene [3,2-d ] pyrimidine (2000 ml) of methylene chloride) was charged, and the solution was stirred. The temperature was controlled below 10 ℃, 416ml of triethylamine (3000 mmol) was poured in, the temperature was controlled below 10 ℃, 93.75g of hydrazine hydrate (1500 mmol) was added dropwise, then the temperature was naturally raised to room temperature, the reaction was carried out for 1h, and the completion of the reaction was monitored by Thin Layer Chromatography (TLC). 4000ml of pure water was added, stirred for 30 minutes, suction-filtered, and the obtained solid was added to a 4000ml beaker containing 2000ml of pure water, stirred for 10 minutes, suction-filtered, and dried to obtain a white solid M1.
Into a reaction flask were charged 100mmol of 2-chloro-4, 6-diphenyltriazine, 100mmol of 4-boric acid benzoyl, 40g of potassium carbonate (300 mmol), 800ml of N, N-Dimethylformamide (DMF) and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 2-chloro-4, 6-diphenyltriazine.
In a single flask was added 175.8mmol of M1, 159.8mmol of intermediate M2 and 1000ml of ethanol, and after stirring until the solution was clear, stirring was continued for 30 minutes, TLC monitored for disappearance of starting material. 57g of iodobenzene diacetic acid (175.8 mmol) was added in portions, followed by stirring for 1 hour, the solid gradually precipitated, after completion of the TLC monitoring reaction, the filter cake was filtered, and the filter cake was rinsed with ethanol, and the filtrate was washed to colorless clear liquid, to obtain brown solid M3.
Into a reaction flask were charged 100mmol of M3, 100mmol of phenylboronic acid, 40g of potassium carbonate (300 mmol), 800ml of DMF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)δ8.36-8.28(m,4H),7.96-7.86(m,3H),7.78-7.64(m,7H),7.50-7.41(m,5H),7.32(d,J＝10.0Hz,4H)。
Synthesis of A4:
1000mmol of 2, 4-dichlorobenzo [4,5] furan [3,2-d ] pyrimidine, 2000ml of dichloromethane and stirring to dissolve the solution were placed in a 10L three-necked flask. The temperature was controlled to below 10 ℃, 416ml of triethylamine (3000 mmol) was poured in, the temperature was controlled to below 10 ℃, 93.75g of hydrazine hydrate (1500 mmol) was added dropwise, the temperature was naturally raised to room temperature, and the reaction was allowed to proceed for 1 hour, and Thin Layer Chromatography (TLC) was monitored to complete the reaction. 4000ml of pure water was added, stirred for 30 minutes, suction-filtered, and the obtained solid was added to a 4000ml beaker containing 2000ml of pure water, stirred for 10 minutes, suction-filtered, and dried to obtain a white solid M1.
In a single vial was added 175.8mmol of M1, 159.8mmol of 2-aldehyde-9, 9-dimethylfluorene and 1000ml of ethanol, and after stirring until the solution was clear, stirring was continued for 30 minutes, TLC monitored for disappearance of starting material. 57g of iodobenzene diacetic acid (175.8 mmol) was added in portions, followed by stirring for 1 hour, the solid gradually precipitated, after completion of the TLC monitoring reaction, the filter cake was filtered, and the filter cake was rinsed with ethanol, and the filtrate was washed to colorless clear liquid, to obtain brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of 4, 6-diphenyl-2- (3-phenylboronate), 40g of potassium carbonate (300 mmol), 800ml of DMF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)δ8.37(d,J＝10.0Hz,2H),8.11(d,J＝8.0Hz,1H),7.89(d,J＝8.0Hz,2H),7.74(d,J＝10.0Hz,2H),7.68(s,1H),7.65-7.55(m,9H),7.52(d,J＝8.4Hz,3H),7.35(d,J＝8.0Hz,2H),7.23(d,J＝8.4Hz,3H),1.69(s,6H)。
Synthesis of A7:
1000mmol of 2, 4-dichlorobenzo [4,5] furan [3,2-d ] pyrimidine, 2000ml of dichloromethane and stirring to dissolve the solution were placed in a 10L three-necked flask. Pouring 416ml of triethylamine (3000 mmol) into the reaction kettle, controlling the temperature to be lower than 10 ℃, dropwise adding 93.75g of hydrazine hydrate (1500 mmol) into the reaction kettle, naturally heating the reaction kettle to room temperature, reacting the reaction kettle for 1 hour, and monitoring the completion of the reaction by Thin Layer Chromatography (TLC). 4000ml of pure water was added, stirred for 30 minutes, suction-filtered, and the obtained solid was added to a 4000ml beaker containing 2000ml of pure water, stirred for 10 minutes, suction-filtered, and dried to obtain a white solid M1.
In a single flask was added 175.8mmol of M1, 159.8mmol of benzaldehyde and 1000ml of ethanol, and after stirring until the solution was clear, stirring was continued for 30 minutes and TLC monitored for disappearance of starting material. 57g of iodobenzene diacetic acid (175.8 mmol) was added in portions, followed by stirring for 1 hour, the solid gradually precipitated, after completion of the TLC monitoring reaction, the filter cake was filtered, and the filter cake was rinsed with ethanol, and the filtrate was washed to colorless clear liquid, to obtain brown solid M2.
Into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 100mmol of 3-bromophenylboric acid, 40g of potassium carbonate (300 mmol), 800ml of DMF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 2-chloro-3-phenylquinoxaline.
Into a reaction flask were charged 100mmol of M3, 150mmol of pinacol biborate, 40g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl 2 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of M2, 100mmol of M4, 40g of potassium carbonate (300 mmol), 800ml of DMF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A7. Wherein, the liquid crystal display device comprises a liquid crystal display device,Pd(PPh 3 ) 4 the amount of (2) added was 1mol% of M2.
1 H NMR(400MHz,Chloroform)δ8.49(d,J＝10.0Hz,2H),8.33-8.28(m,2H),8.03(s,1H),7.80-7.74(m,4H),7.67(t,J＝12.0Hz,3H),7.59-7.50(m,6H),7.34(d,J＝10.0Hz,4H)。
Synthesis of a 11:
1000mmol of 2, 4-dichlorobenzo [4,5] furan [3,2-d ] pyrimidine, 2000ml of dichloromethane and the solution were placed in a 10L three-necked flask, followed by stirring. Pouring 416ml of triethylamine (3000 mmol) into the reaction kettle, controlling the temperature to be lower than 10 ℃, dropwise adding 93.75g of hydrazine hydrate (1500 mmol) into the reaction kettle, naturally heating the reaction kettle to room temperature, reacting the reaction kettle for 1 hour, and monitoring the completion of the reaction by Thin Layer Chromatography (TLC). Adding 4000ml of pure water, stirring for 30 minutes, and then carrying out suction filtration; the obtained solid was added to a 4000ml beaker containing 2000ml of pure water, stirred for 10 minutes, suction-filtered and dried to obtain a white solid M1.
In a single flask was added 175.8mmol of M1, 159.8mmol of benzaldehyde and 1000ml of ethanol, and after stirring until the solution was clear, stirring was continued for 30 minutes and TLC monitored for disappearance of starting material. 57g of iodobenzene diacetic acid (175.8 mmol) was added in portions, followed by stirring for 1 hour, the solid gradually precipitated, after completion of the TLC monitoring reaction, the filter cake was filtered, and the filter cake was rinsed with ethanol, and the filtrate was washed to colorless clear liquid, to obtain brown solid M2.
Into a reaction flask were charged 100mmol of 2-spirobifluorene boric acid, 100mmol of m-bromoiodobenzene, 40g of potassium carbonate (300 mmol), 800ml of DMF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The addition amount of (2) was 1mol% of m-bromoiodobenzene.
Into a reaction flask were charged 100mmol of M3, 150mmol of pinacol biborate, 40g of potassium carbonate (300 mmol), 800ml of DMF, and 1mol% Pd (dppf) Cl is added 2 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of M2, 100mmol of M4, 40g of potassium carbonate (300 mmol), 800ml of DMF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a11. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
1 H NMR(CDCl3,400MHz)δ8.30(d,J＝7.6Hz,2H),8.18(d,J＝9.6Hz,3H),8.02(s,1H),7.98–7.76(m,3H),7.69(d,J＝10.0Hz,3H),7.61(d,J＝7.2Hz,4H),7.50(s,1H),7.37–7.27(m,7H),7.24(d,J＝8.0Hz,4H)。
Synthesis of a 25:
105mmol of 2-bromo-2-chloro-biphenyl, 500ml of THF, were placed in a 1L three-necked flask, cooled to-78℃and 100mmol of butyllithium were added dropwise, and the flask was kept for 1h. 100mmol of 2, 4-dichlorobenzofluoreno-pyrimidine is added, the temperature is naturally raised, the reaction is completed for 12 hours, water is added into the reaction solution, the ethyl acetate is used for extraction, and the organic phase is concentrated and dried. Intermediate M1 is obtained.
100mmol of intermediate M1 was added to the reaction flask, 200ml of trifluoromethanesulfonic acid was added thereto, and the mixture was refluxed under heating and reacted for 12 hours. After the reaction, adding the mixture into water, precipitating solid, and filtering to obtain an intermediate M2.
1000mmol of M2 and 2000ml of methylene chloride were put into a 10L three-necked flask, and the solution was stirred. Pouring 416ml of triethylamine (3000 mmol) into the reaction kettle, controlling the temperature to be lower than 10 ℃, dropwise adding 75.09g of hydrazine hydrate (1500 mmol) into the reaction kettle, naturally heating the reaction kettle to room temperature, reacting the reaction kettle for 1 hour, and monitoring the completion of the reaction by Thin Layer Chromatography (TLC). Adding 4000ml of pure water, stirring for 30 minutes, and then carrying out suction filtration; the obtained solid was added to a 4000ml beaker containing 2000ml of pure water, stirred for 10 minutes, suction-filtered and dried to obtain a white solid M3.
Into a reaction flask were charged 100mmol of p-aldehyde phenylboronic acid, 100mmol of 2-chloro-4-phenylquinazoline, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% based on 2-chloro-4-phenylquinazoline.
In a single vial was added 175.8mmol of M3, 159.8mmol of M4 and 1000ml of ethanol, and after stirring until the solution was clear, stirring was continued for 30 minutes, TLC monitored for disappearance of starting material. 57g of iodobenzene diacetic acid (175.8 mmol) was added in portions, followed by stirring for 1 hour, the solid gradually precipitated, after completion of the TLC monitoring reaction, the filter cake was filtered, and the filter cake was rinsed with ethanol, and the filtrate was washed to colorless clear liquid, to obtain brown solid M5.
Into a reaction flask were charged 100mmol of M5, 100mmol of 2-dibenzothiophene boronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a25. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
1 H NMR(CDCl3,400MHz)δ8.45(s,1H),8.21(s,1H),8.13(s,1H),8.16–7.88(m,6H),7.86(s,1H),7.80(d,J＝7.6Hz,4H),7.75(s,1H),7.63(d,J＝12.0Hz,4H),7.55(d,J＝8.8Hz,3H),7.49(s,1H),7.43(s,1H),7.41–7.29(m,8H),7.26(d,J＝13.6Hz,3H)。
Example 1
Ultrasonic treating the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in an acetone-ethanol mixed solvent, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
then placing the above-mentioned glass substrate with anode in vacuum cavity, vacuumizing to less than 10 -5 And vacuum evaporation of a hole injection layer on the anode layer film, wherein the hole injection layer is made of HT-11 and 3% of p-type dopant (p-dopant) by mass ratio, the evaporation rate is 0.1nm/s, the thickness of the evaporation film is 10nm, and the hole injection layer is made of the following materials:
then, vacuum evaporation of a hole transport material HT-5 as a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, the evaporation film thickness is 80nm, and the hole transport layer is made of the following materials:
then, a luminescent layer is vacuum-evaporated on the hole transmission layer, the luminescent layer comprises a host material GHP-16 and a dye material RPD-1, evaporation is carried out by utilizing a multi-source co-evaporation method, wherein the evaporation rate of the host material GHP-16 is regulated to be 0.1nm/s, the evaporation rate of the dye RPD-1 is 3% of the evaporation rate of the host material, the total film thickness of the evaporation is 30nm, and the host material and the guest material are respectively the following materials:
then, an electron transport layer including an electron transport material A1 is vacuum-deposited over the light-emitting layer. Wherein, the vapor deposition rate is 0.1nm/s, the vapor deposition film thickness is 30nm, and the selected electron transport material A1 has the following formula:
then, liF with the thickness of 0.5nm is vacuum evaporated on an Electron Transport Layer (ETL) as an electron injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 10nm;
then, an Al layer having a thickness of 150nm was vacuum-deposited on the electron injection layer as a cathode electrode of the organic electroluminescent device, wherein the deposition rate was 1nm/s and the deposition film thickness was 50nm.
Examples 2 to 5
The procedure of example 1 was repeated except that A4, A7, A11 and A25 were used in place of A1. See in particular table 1.
Comparative example 1
The procedure of example 1 was repeated except that R1 was used instead of A1.
The organic electroluminescent device prepared by the above procedure was subjected to the following performance measurement:
the driving voltage and current efficiency and the lifetime of the organic electroluminescent devices prepared in examples 1 to 7 and comparative example 1 were measured using a digital source meter and a luminance meter under the same luminance, specifically, the voltage was increased at a rate of 0.1V per second, and the luminance of the organic electroluminescent devices was measured to be 5000cd/m 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; the lifetime test of LT95 is as follows: at 5000cd/m using a luminance meter 2 Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 4750cd/m 2 Time in hours.
TABLE 1 organic electroluminescent device Performance results
As can be seen from Table 1, the compounds A1, A4, A7, A11 and A25 prepared by the method are used for the electron transport material of the organic electroluminescent device, can effectively reduce the driving voltage, improve the current efficiency, prolong the service life of the device, and are electron transport materials with good performance.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.

Claims (3)

1. An electron transport material, wherein the electron transport material is selected from the following compounds:
2. an organic electroluminescent device comprising at least one of the electron transport materials of claim 1.
3. A display device comprising the organic electroluminescent device of claim 2.
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