CN112159361A - Electron transport material, organic electroluminescent device and display device - Google Patents

Electron transport material, organic electroluminescent device and display device Download PDF

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CN112159361A
CN112159361A CN202011227004.5A CN202011227004A CN112159361A CN 112159361 A CN112159361 A CN 112159361A CN 202011227004 A CN202011227004 A CN 202011227004A CN 112159361 A CN112159361 A CN 112159361A
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electron transport
reaction
organic electroluminescent
water
100mmol
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邢其锋
丰佩川
孙伟
胡灵峰
陈跃
陈雪波
马艳
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Yantai Jingshi Materials Genomic Engineering Research Institute
Yantai Xianhua Chem Tech Co ltd
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Yantai Jingshi Materials Genomic Engineering Research Institute
Yantai Xianhua Chem Tech Co ltd
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Abstract

The invention discloses an electron transport material with a general formula I, which can be used as an electron transport layer of an organic electroluminescent device in a display device. The electron transport material has a parent structure of a phenanthrene-substituted triazine-terphenyl system, has high bond energy among atoms, good thermal stability, is favorable for solid-state accumulation among molecules, has strong transition capability of electrons, and can be used as an electron transport layer material to 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.

Description

Electron transport material, organic electroluminescent device and display device
Technical Field
The invention relates to the technical field of light-emitting display, in particular to 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, a film can be formed on any substrate by an evaporation or spin coating method, and flexible display and large-area display can be realized; the optical properties, electrical properties, stability, etc. of the materials can be adjusted by changing the structure of the molecules, the choice of the materials has a large space, and in the most common OLED device structure, the following organic materials are generally 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. At present, as an important functional material, an electron transport material has a direct influence on the mobility of electrons, and ultimately influences the luminous efficiency of an OLED. However, the electron transport materials currently used in OLEDs have low electron transfer rates and poor energy level matching with adjacent layers, which severely limits the light emitting efficiency of OLEDs and the display function of OLED display devices.
Disclosure of Invention
The invention provides an electron transport material, an organic electroluminescent device and a display device, in order to improve the luminous efficiency and prolong the service life of the organic electroluminescent device.
The electron transport material has a structure shown as a formula (I):
Figure BDA0002763900880000021
wherein the content of the first and second substances,
Ar1、Ar2is selected from C6-C30Aryl or C3-C30The heteroaryl of (a), wherein each hydrogen atom of the aryl may be independently substituted by Ra;
L1-L3selected from chemical bonds, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
Z1-Z5selected from CR or N, R is selected from hydrogen, cyano, C6-C30Arylene group of (A) or (C)3-C30And adjacent R may be linked to form a ring;
Y1-Y10selected from CR 'or N, R' is selected from hydrogen, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a);
ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
Preferably, Ar is1、Ar2Selected from one of the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, 9-dimethylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothienyl, aza-dibenzofuranyl, aza-dibenzothienyl; l is1-L3A 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, or carbazole; r is selected from hydrogen, cyano, the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinquiOxazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, or carbazolyl; r' is selected from hydrogen, 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, or carbazolyl.
The invention also discloses a specific structure of the electron transport material shown in the formula A1-A50:
Figure BDA0002763900880000041
Figure BDA0002763900880000051
the electron transport material has a parent structure of a phenanthrene-substituted triazine-terphenyl system, has high bond energy among atoms, good thermal stability, strong transition capability of electrons, and can be used as an electron transport layer material to 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, and is beneficial to solid-state accumulation among molecules; the electron transport material is applied in an electron transport layer, has a proper energy level with the adjacent layers, is beneficial to the injection and the migration of electrons, can effectively reduce the take-off and landing voltage, has higher electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device; the electron transport material has a larger conjugate plane, is beneficial to molecular accumulation, shows good thermodynamic stability, and shows long service life in an organic electroluminescent device.
The present invention also provides an organic electroluminescent device comprising at least an anode electrode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode electrode, wherein the electron transport layer is at least one selected from the above-mentioned compounds, and in the present invention, there is no particular limitation in the kind and structure of the organic electroluminescent device as long as the electron transport material provided by the present invention can be used. The organic electroluminescent device of the present invention 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 element of the present invention may be a light-emitting element 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 element of the present invention may be a light-emitting element 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.
Drawings
Fig. 1 is a schematic structural diagram of a typical organic electroluminescent device of the organic electroluminescent device according to the present invention, which is shown from bottom to top: 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.
For convenience, the organic electroluminescent device of the present invention will be described below with reference to fig. 1, but this is not intended to limit the scope of the present invention in any way. It is understood that all organic electroluminescent devices capable of using the electron transport material of the present invention are within the scope of the present invention.
In the present invention, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, such as glass, polymer materials, glass with TFT elements, polymer materials, and the like, may be used.
In the present invention, 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 hole injection layer 3 in the present invention is not particularly limited, and may be made of 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 is added, and the type of the p-type dopant is not particularly limited, and various p-type dopants known in the art may be used, and for example, the following p-type dopants may be used:
Figure BDA0002763900880000071
in the present invention, the hole transport layer 4 is not particularly limited, and at least one of Hole Transport Materials (HTM) well known in the art may be selected, 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:
Figure BDA0002763900880000072
Figure BDA0002763900880000081
in the present invention, 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 include 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:
Figure BDA0002763900880000091
Figure BDA0002763900880000101
Figure BDA0002763900880000111
the light-emitting layer 5 preferably contains a phosphorescent dopant, and the dopant may be at least one selected from the following compounds RPD-1 to RPD-28, and the amount of the dopant is not particularly limited and may be an amount known to those skilled in the art.
Figure BDA0002763900880000112
Figure BDA0002763900880000121
In the present invention, the electron transport layer 6 comprises at least one of the electron transport materials of the present invention, and the electron transport layer 6 may also comprise a combination of at least one of the electron transport materials of the present invention with at least one of the following known electron transport materials ET-1 to ET-57:
Figure BDA0002763900880000122
Figure BDA0002763900880000131
Figure BDA0002763900880000141
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、Cs2CO3At least one of BaO, Na, Li, Ca and the like.
The cathode electrode 8 is not particularly limited and may be selected from, but not limited to, a magnesium silver mixture, LiF/Al, ITO, Al, and other metals, metal mixtures, oxides, and the like.
The method of preparing the organic electroluminescent device of the present invention is not particularly limited, and any method known in the art may be employed, for example:
(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) a hole injection layer 3 is vacuum evaporated on the reflecting anode electrode 2, the main material of the hole injection layer is HTM, and the hole injection layer contains P-type dopant (P-dopant) and has the thickness of 10-50 nm;
(3) vacuum evaporating a Hole Transport Material (HTM) as a hole transport layer 4 on the hole injection layer 3, wherein the thickness of the hole transport layer 4 is 80-150 nm;
(4) vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer contains a host material (GPH) and a guest material (RPD) and has a thickness of 20-50 nm;
(5) vacuum evaporation of an Electron Transport Material (ETM) as an electron transport layer 6 on the light emitting layer 5;
(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 third aspect of the present invention provides a display device comprising the above organic electroluminescent device, and the display device of the present invention includes, but is not limited to, a display, a television, a tablet computer, a mobile communication terminal, and the like.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Synthesis of electron transport materials
Example 1 Synthesis of A1
Into a reaction flask were charged 100mmol of 1, 4-dibromonaphthalene, 100mmol of 4-cyanophenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1, 4-dibromonaphthalene;
into a reaction flask, 100mmol of M1, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M2, wherein, Pd (dppf)2Cl2The addition amount of (A) is 1 mol% of M1;
into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of 2- (9, 9-dimethylfluorene) boronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M3, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene;
into a reaction flask were charged 100mmol of M2, 100mmol of M3, 41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh)3)4In an amount of M31mol％；
Into a reaction flask, 100mmol of M4, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M5, wherein, Pd (dppf)2Cl2The addition amount of (A) is 1 mol% of M4;
into a reaction flask were added 100mmol of 3-phenyl-5- (9-phenanthryl) -1-chlorotriazine, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A1, wherein Pd (PPh)3)4The adding amount of the (1) is 1mol percent of the 3-phenyl-5- (9-phenanthryl) -1-chlorotriazine;
the hydrogen spectrum of a1 is characterized as follows:
1H NMR(400MHz,Chloroform)9.08(s,1H),9.00(s,1H),8.84(s,2H),8.36(s,2H),8.17(s,1H),8.09(s,1H),7.91(d,J＝12.0Hz,4H),7.84(s,1H),7.83–7.72(m,8H),7.64–7.45(m,9H),7.34(d,J＝8.4Hz,3H),7.24–7.15(m,6H),7.06(d,J＝13.2Hz,3H),1.69(s,6H).
the reaction scheme is as follows:
Figure BDA0002763900880000171
example 2 Synthesis of A6
Into a reaction flask were charged 100mmol of 1, 4-dibromonaphthalene, 100mmol of 4-cyanophenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powderM1, wherein, Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1, 4-dibromonaphthalene;
into a reaction flask, 100mmol of M1, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M2, wherein, Pd (dppf)2Cl2The addition amount of (A) is 1 mol% of M1;
into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of 3-pyridineboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M3, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene;
into a reaction flask were charged 100mmol of M2, 100mmol of M3, 41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of M3;
into a reaction flask, 100mmol of M4, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M5, wherein, Pd (dppf)2Cl2The addition amount of (A) is 1 mol% of M4;
100mmol of 3-phenyl-5- (9-phenanthryl) are added to a reaction flask) 1-chlorotriazine, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A1, wherein Pd (PPh)3)4The adding amount of the (1) is 1mol percent of the 3-phenyl-5- (9-phenanthryl) -1-chlorotriazine;
the hydrogen spectrum of a6 is characterized as follows:
1H NMR(400MHz,Chloroform)9.24(s,1H),9.00(s,1H),8.97(d,J＝8.0Hz,1H),8.77(d,J＝10.0Hz,2H),8.49(s,1H),8.44–8.24(m,5H),8.20(s,1H),8.17(s,2H),8.04–7.72(m,7H),7.69(d,J＝10.0Hz,2H),7.63(d,J＝8.0Hz,2H),7.49(d,J＝12.0Hz,5H),7.33(s,1H).
the reaction scheme is as follows:
Figure BDA0002763900880000191
example 3 Synthesis of A11
Into a reaction flask were charged 100mmol of p-chlorobenzoic acid, 100mmol of 3-bromoxynil, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (PPh)3)4The addition amount of (a) is 1 mol% of 3-bromoxynil;
into a reaction flask, 100mmol of M1, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M2, wherein, Pd (dppf)2Cl2The addition amount of (A) is 1 mol% of M2;
into a reaction flask were charged 100mmol of 1, 4-dibromonaphthalene, 100mmol of M2, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M3, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1, 4-dibromonaphthalene;
into a reaction flask, 100mmol of M3, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein, Pd (dppf)2Cl2The addition amount of (A) is 1 mol% of M3;
into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M5, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene;
into a reaction flask were charged 100mmol of M4, 100mmol of M5, 41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M6, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of M5;
adding 100mmol of 9-bromo-10-phenylphenanthrene and 800ml of Tetrahydrofuran (THF) into a reaction bottle, dropwise adding 100mmol of n-butyllithium at-60 ℃, reacting for 1h, slowly heating to 0 ℃, adding 100mmol of 1, 3-dichloro-5-phenyltriazine in batches, stopping the reaction after the reaction is finished, adding water into the reactant, stirring, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder M7;
into a reaction flask were charged 100mmol of M6, 100mmol of M7, 41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A11, wherein Pd (PPh)3)4Was added in an amount of 1 mol% based on M7.
The hydrogen spectrum of a11 is characterized as follows:
1H NMR(400MHz,Chloroform)9.08(s,1H),9.00(s,1H),8.36(s,1H),8.13(d,J＝8.4Hz,2H),8.08-7.75(m,6H),7.69(d,J＝8.0Hz,4H),7.67–7.60(m,6H),7.59–7.43(m,8H),7.41-7.33(m,7H),7.26(d,J＝10.0Hz,4H).
the reaction scheme is as follows:
Figure BDA0002763900880000211
example 4 Synthesis of A14
Into a reaction flask were charged 100mmol of 1, 4-dibromobenzene, 100mmol of 4-cyanopyridine-3-boronic acid pinacol ester, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1, 4-dibromobenzene;
into a reaction flask, 100mmol of M1, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 ℃ for 12h, stopping the reaction after the reaction is finished, and cooling the reactantCooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M2, wherein, Pd (dppf)2Cl2The addition amount of (A) is 1 mol% of M1;
into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of 4-biphenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M3, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene;
into a reaction flask were charged 100mmol of M2, 100mmol of M3, 41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of M3;
into a reaction flask, 100mmol of M4, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M5, wherein, Pd (dppf)2Cl2The addition amount of (A) is 1 mol% of M4;
into a reaction flask were added 100mmol of 3-phenyl-5- (9-phenanthryl) -1-chlorotriazine, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A1, wherein Pd (PPh)3)4Is added in an amount ofIs 1mol percent of 3-phenyl-5- (9-phenanthryl) -1-chlorotriazine;
the hydrogen spectrum of a14 is characterized as follows:
1H NMR(400MHz,Chloroform)9.70(s,1H),9.08(s,1H),8.99(s,1H),8.84(s,1H),8.49–8.44(m,3H),8.36(s,1H),8.27(s,1H),8.10(d,J＝10.4Hz,3H),7.90(s,1H),7.69(d,J＝10.0Hz,4H),7.66(dd,J＝12.8,7.6Hz,8H),7.62–7.39(m,8H),.
the reaction scheme is as follows:
Figure BDA0002763900880000231
example 5 Synthesis of A19
Into a reaction flask were charged 100mmol of 3, 5-dicyano-bromobenzene, 120mmol of pinacol ester diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein, Pd (dppf)2Cl2The addition amount of (a) is 1 mol% of 3, 5-dicyano-bromobenzene;
into a reaction flask were charged 100mmol of 1, 4-dibromonaphthalene, 100mmol of M1, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M2, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1, 4-dibromonaphthalene;
into a reaction flask, 100mmol of M2, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtainWhite powder M3, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of M2;
into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of 1-naphthylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene;
into a reaction flask were charged 100mmol of M3, 100mmol of M4, 41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M5, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of M4;
adding 100mmol of 5-chloro-phenanthroline and 800ml of Tetrahydrofuran (THF) into a reaction bottle, dropwise adding 100mmol of n-butyllithium at-60 ℃, reacting for 1h, slowly heating to 0 ℃, adding 100mmol of 1, 3-dichloro-5-phenyl triazine in batches, stopping the reaction after the reaction is finished, adding water into a reactant, stirring, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder M6;
into a reaction flask were charged 100mmol of M5, 100mmol of M6, 41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A19, wherein Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
The hydrogen spectrum of a19 is characterized as follows:
1H NMR(400MHz,Chloroform)9.05(s,1H),9.03(d,J＝9.6Hz,2H),8.88(d,J＝10.0Hz,2H),8.50(s,1H),8.34(d,J＝10.0Hz,2H),8.14(s,1H),8.09(d,J＝12.0Hz,2H),7.89(s,1H),7.75(dd,J＝10.0,7.6Hz,5H),7.50(d,J＝8.8Hz,4H),7.39(d,J＝8.0Hz,4H),7.34(d,J＝8.0Hz,4H),7.27(s,1H).
the reaction scheme is as follows:
Figure BDA0002763900880000251
example 6 Synthesis of A21
Into a reaction flask were charged 100mmol of 1, 4-dibromonaphthalene, 100mmol of 4-cyanophenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1, 4-dibromonaphthalene;
into a reaction flask, 100mmol of M1, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M2, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of M1;
into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of 1-phenyl-2- (4-phenylboronic acid) -1H-benzimidazole, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M3, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene;
100mmol of M2, 100mmol of M3,41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of M3;
into a reaction flask, 100mmol of M4, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of dioxane were charged, and 1 mol% of Pd (dppf)2Cl2Reacting at 80 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M5, wherein Pd (PPh)3)4The addition amount of (A) is 1 mol% of M4;
adding 100mmol of 3-bromophenanthrene and 800ml of Tetrahydrofuran (THF) into a reaction bottle, dropwise adding 100mmol of n-butyllithium at-60 ℃, reacting for 1h, slowly heating to 0 ℃, adding 100mmol of 1, 3-dichloro-5-phenyl triazine in batches, stopping the reaction after the reaction is finished, adding water into the reactant, stirring, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder M6;
into a reaction flask were charged 100mmol of M5, 100mmol of M6, 41.4g potassium carbonate (300mmol), 800ml Tetrahydrofuran (THF), 200ml water and Pd (PPh)3)4Reacting at 60 deg.C for 12h, stopping reaction after reaction, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A21, wherein Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
The hydrogen spectrum of a21 is characterized as follows:
1H NMR(400MHz,Chloroform)8.85(s,1H),8.71–8.48(m,4H),8.34–8.29(m,3H),8.15(s,1H),8.09–7.70(m,8H),7.68(s,1H),7.65–7.54(m,6H),7.50(t,J＝12.0Hz,6H),7.38(s,2H),7.27(d,J＝12.0Hz,6H).
the reaction scheme is as follows:
Figure BDA0002763900880000271
preparation of organic electroluminescent device
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;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 10 DEG-5And (3) vacuum evaporating a hole injection layer on the anode layer film by using the Torr, wherein the material of the hole injection layer is HT-4 and a p-type dopant (p-dopant) with the mass ratio of 3%, the evaporation rate is 0.1nm/s, the evaporation film thickness is 10nm, and the material of the hole injection layer and the p-type dopant are as follows:
Figure BDA0002763900880000272
vacuum evaporating a hole transport material HT-5 material on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 80 nm;
a luminescent layer is evaporated on the hole transport layer in vacuum, the luminescent layer comprises a main material GHP-16 and a dye material RPD-1, evaporation is carried out by a multi-source co-evaporation method, wherein the evaporation rate of the main material GHP-16 is adjusted to be 0.1nm/s, the evaporation rate of the dye RPD-1 is 3% of the evaporation rate of the main material, and the total thickness of the evaporation film is 30 nm;
vacuum evaporation of an Electron Transport Layer (ETL) on the light emitting layer, the electron transport layer being the electron transport materials prepared in examples 1-6, respectively, and vacuum evaporation of LiF with a thickness of 0.5nm as an electron injection layer on the Electron Transport Layer (ETL), wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm; and finally, performing vacuum evaporation on the electron injection layer to form an aluminum layer with the thickness of 150nm as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate is 1nm/s, and the evaporation film thickness is 50 nm.
Comparative example 1
The electron transport material of the organic electroluminescent device is replaced by ET-2, and the rest is unchanged.
Comparative example 2
The electron transport material of the organic electroluminescent device is replaced by the substance with the following structure, and the rest is unchanged,
Figure BDA0002763900880000281
the organic electroluminescent devices of examples 1 to 6 and comparative example 1 were subjected to the following performance measurements:
measuring the driving voltage and current efficiency of the organic electroluminescent device and the lifetime of the device at the same brightness by using a digital source meter and a luminance meter, specifically, increasing the voltage at a rate of 0.1V per second, and measuring that the brightness of the organic electroluminescent device reaches 5000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT95 is as follows: 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. The results are shown in Table 1.
TABLE 1 organic electroluminescent device Properties
Required luminance (cd/m)2) Driving voltage/V Current efficiency (cd/A) Life (LT95)/h
Example 1 5000.00 4.1 41.3 285
Example 2 5000.00 4.0 42.0 270
Example 3 5000.00 4.0 42.1 275
Example 4 5000.00 3.9 41.6 280
Example 5 5000.00 4.0 42.4 275
Example 6 5000.00 3.9 42.8 280
Comparative example 1 5000.00 4.5 37.6 190
Comparative example 2 5000.00 4.2 39.5 255
As can be seen from table 1, the compounds a1, a6, a11, a14, a19 and a21 prepared by the method are used as electron transport materials for organic electroluminescent devices, can effectively reduce driving voltage, improve current efficiency and prolong device life, and are electron transport materials with good performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. An electron transport material having a structure according to formula i:
Figure FDA0002763900870000011
wherein the content of the first and second substances,
Ar1、Ar2is selected from C6-C30Aryl or C3-C30The heteroaryl of (a), wherein each hydrogen atom of the aryl may be independently substituted by Ra;
L1-L3selected from chemical bonds, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
Z1-Z5selected from CR or N, R is selected from hydrogen, cyano, C6-C30Arylene group of (A) or (C)3-C30And adjacent R may be linked to form a ring;
Y1-Y10selected from CR 'or N, R' is selected from hydrogen, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a);
ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
2. The electron transport material of claim 1, wherein Ar is Ar1、Ar2Selected from one of the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, 9-dimethylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothienyl, aza-dibenzofuranyl, aza-dibenzothienyl.
3. The electron transport material of claim 1, wherein L is1-L3A 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, or carbazole.
4. The electron transport material of claim 1, wherein R is selected from the group consisting of hydrogen, cyano, 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, or carbazolyl.
5. The electron transport material of claim 1, wherein R' is selected from hydrogen, the following 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, or carbazolyl.
6. The electron transport material of claim 1 having a structure as shown in formula a1-a 50:
Figure FDA0002763900870000031
Figure FDA0002763900870000041
7. an organic electroluminescent device comprising an anode electrode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode electrode, wherein the electron transport layer comprises at least one of the electron transport materials of any one of claims 1 to 6.
8. The organic electroluminescent device of claim 7, wherein the electron transport layer further comprises at least one transport material of the formula ET-1 to ET-57, wherein the structures of the formulae ET-1 to ET-57 are as follows,
Figure FDA0002763900870000042
Figure FDA0002763900870000051
Figure FDA0002763900870000061
Figure FDA0002763900870000071
9. a display device comprising the organic electroluminescent element according to claim 7 or 8.
CN202011227004.5A 2020-11-06 2020-11-06 Electron transport material, organic electroluminescent device and display device Pending CN112159361A (en)

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