CN111635355B - Compound, hole transport material and organic electroluminescent device - Google Patents

Compound, hole transport material and organic electroluminescent device Download PDF

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CN111635355B
CN111635355B CN202010518276.4A CN202010518276A CN111635355B CN 111635355 B CN111635355 B CN 111635355B CN 202010518276 A CN202010518276 A CN 202010518276A CN 111635355 B CN111635355 B CN 111635355B
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organic electroluminescent
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hole transport
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CN111635355A (en
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邢其锋
丰佩川
单鸿斌
孙伟
胡灵峰
陈跃
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Yantai Xianhua Chem Tech Co ltd
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Abstract

The embodiment of the invention provides a compound of a general formula (I), which can be used for a hole transport material. The compound has a parent structure connected with a multi-element condensed heterocyclic aromatic amine, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, has strong hole transition capability, and can effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency and prolong the service life when being used as a hole transport layer material. The application also provides an organic electroluminescent device and a display device comprising the compound of the general formula (I).

Description

Compound, hole transport material and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic light-emitting display, in particular to a hole transport material and an organic electroluminescent device containing the hole 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, hole transport materials are used as an important functional material, which has a direct effect on the mobility of holes and ultimately affects the luminous efficiency of an OLED. However, the hole transport rate achieved by the hole transport materials applied to the OLED at present is low, and the energy level matching performance with the adjacent layers is poor, so that the luminous efficiency of the OLED and the display function of the OLED display device are severely restricted.
Disclosure of Invention
The embodiment of the invention aims to provide a hole 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 Aryl or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
l is selected from chemical bond, C 6 -C 30 Arylene or C of (2) 3 -C 30 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
R 1 -R 4 each independently selected from hydrogen, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 30 Aryl, C 3 -C 30 Heteroaryl, amine groups, the hydrogen atoms on the aryl, heteroaryl and amine groups each independently being substituted by Ra, the R 1 -R 4 Can be linked to form a ring;
x and Y are each independently selected from O, S, CR 5 R 6 、NR 7 ，R 5 And R is 6 Each independently selected from C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 30 Aryl or C 3 -C 30 Heteroaryl, R 7 Selected from C 6 -C 30 Aryl or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
Z 1 -Z 8 each independently selected from CR 8 Or N, R 8 Selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 30 Aryl or C 3 -C 30 Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently can be substituted with Ra, the Z 1 -Z 8 Any one of which is connected with the general formula (I) through a chemical bond;
the heteroatoms of the heteroaryl or 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 a hole 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 hole 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 the multi-element fused heterocyclic aromatic amine connection, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, and has strong hole transition capability. When the material is used as a hole transport material, the material has proper energy level with adjacent layers, is favorable for injection and migration of holes, can effectively reduce the landing voltage, has higher hole migration rate, and can realize good luminous efficiency in an organic electroluminescent device. The organic electroluminescent device comprises the compound as a hole 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 clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. 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,
ar1 and Ar2 are each independently selected from the group consisting of C6-C30 aryl or C3-C30 heteroaryl, each of which hydrogen atoms on the aryl and heteroaryl groups may be independently substituted with Ra;
l is selected from a bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group, each of which independently may be substituted with Ra;
R1-R4 are each independently selected from hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, amine groups, the hydrogen atoms on the aryl, heteroaryl and amine groups each independently being substituted with Ra, two adjacent groups of R1-R4 being capable of being joined to form a ring;
x and Y are each independently selected from O, S, CR R6, NR7, R5 and R6 are each independently selected from C1-C10 alkyl, C3-C6 cycloalkyl, C6-C30 aryl or C3-C30 heteroaryl, R7 is selected from C6-C30 aryl or C3-C30 heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
Z1-Z8 are each independently selected from CR8 or N, R8 is selected from hydrogen, deuterium, C1-C10 alkyl, C3-C6 cycloalkyl, C6-C30 aryl or C3-C30 heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra, any of said Z1-Z8 being attached to formula (I) by a chemical bond;
the heteroatoms of the heteroaryl or heteroarylene are each independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
Preferably, ar1 and Ar2 are each independently selected from the group consisting of C6-C25 aryl and C3-C12 heteroaryl, each of which hydrogen atoms on the aryl and heteroaryl groups may be independently substituted with Ra;
preferably, L is selected from a bond, a C6-C18 arylene group, or a C3-C12 heteroarylene group, each of which independently may be substituted with Ra;
preferably, R1-R4 are each independently selected from hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, C3-C12 heteroaryl, amine groups, the hydrogen atoms on the aryl, heteroaryl and amine groups each independently being substituted with Ra;
preferably, R5 and R6 are each independently selected from C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl or C3-C12 heteroaryl, each hydrogen atom on said aryl and heteroaryl independently being optionally substituted by Ra;
preferably, R7 is selected from C6-C18 aryl or C3-C18 heteroaryl, each of which independently of the other hydrogen atoms on the aryl and heteroaryl may be substituted by Ra;
preferably, R8 is selected from hydrogen, deuterium, C1-C10 alkyl, C3-C6 cycloalkyl, C6-C12 aryl or C3-C12 heteroaryl, each hydrogen atom on said aryl and heteroaryl independently being substituted by Ra.
More preferably, each of Ar1 and Ar2 is independently selected from the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, said L is 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 -R 4 、R 8 Each independently selected from hydrogen, methyl, ethyl, cyclopentyl, cyclohexyl, 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 R 5 And R is 6 Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, 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 process is carried out,the R is 7 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.
For example, the compound of formula (I) is selected from the following compounds:
a second aspect of the present application provides a hole 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 hole transport material of the present application may be used in 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 hole transport material has a parent structure connected by a multi-element condensed heterocyclic aromatic amine, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, has strong hole transition capability, can effectively reduce the driving voltage of an organic electroluminescent device when used as a hole transport layer material, improves the current efficiency of the organic electroluminescent device, and prolongs the service life of the organic electroluminescent device.
The derivative of the diversified fused heterocycle is applied to a hole transport layer, has a proper energy level with adjacent layers, is favorable for hole injection and migration, can effectively reduce the starting voltage, and meanwhile has a higher hole migration rate, so that good luminous efficiency can be realized in a device. The compound provided by the invention 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 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 hole transport materials provided herein as a hole transport layer. In the present application, the kind and structure of the organic electroluminescent device are not particularly limited as long as the hole 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 hole transport layer contains the hole 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 hole 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 material of 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:
the hole transport layer 4 comprises at least one of the hole transport materials of the present application, and the hole transport layer 4 may also comprise a combination of at least one of the hole transport materials of the present application with at least one of the following known Hole Transport Materials (HTM).
For example, the known Hole Transport Material (HTM) 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 (GPH) and a light emitting dye (RPD). The host material may be selected from at least one of the following GPH-1 to GPH-80 compounds:
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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 may be selected from 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 on the reflective anode electrode 2, wherein a main material of the hole injection layer is HTM, and the hole injection layer comprises P-type dopant (P-dopant);
(3) Vacuum evaporating a hole transport material on the hole injection layer 3 as a hole transport layer 4;
(4) Vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer comprises a host material and a guest material;
(5) Vacuum vapor-depositing an electron transport material as an electron transport layer 6 on the light emitting layer 5, wherein an n-type dopant (n-dopant) is contained; (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 reaction flask was charged 100mmol of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene, 120mmol of pinacol diboronate, 41.4g of potassium carbonate (300 mmol), 800ml of N, N-Dimethylformamide (DMF) and 1mol% of Pd (dppf) Cl are added 2 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, filtration was carried out, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (dppf) Cl 2 Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene 1mol%.
Into a reaction flask were charged 100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 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, the reaction mixture was cooled to room temperature, water was added, filtration was carried out, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd (PPh) 3 ) 4 The amount of (C) added was 1mol% based on M1.
In a single flask were added 175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene, heated to reflux, reacted for 8h and monitored for disappearance of starting material by Thin Layer Chromatography (TLC). Column chromatography, separation of intermediate M3.
Into the reaction flask were added 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, and 1mol% of cuprous iodide and 1mol% of 1, 10-phenanthroline. 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 yellow powder M4. Wherein the addition amount of the cuprous iodide and the 1, 10-phenanthroline is 1mol% of M3.
Into the reaction flask were charged 100mmol of M4, 100mmol of 4-benzidine-2- (9, 9-dimethylfluorene), 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). 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 yellow powder A1. Wherein, the addition amount of Pd (dba) is 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ8.45(s,1H),7.96-7.90(m,3H),7.88(t,J＝8.4Hz,3H),7.87–7.70(m,6H),7.64–7.53(m,8H),7.49(d,J＝8.0Hz,3H),7.43–7.29(m,5H),7.24-7.10(m,4H),1.69(s,6H)。
Synthesis of A5:
into a reaction flask was charged 100mmol of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene, 120mmol of pinacol diboronate, 40g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl are 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 M1. Wherein Pd (dppf) Cl 2 Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene 1mol%.
Into a reaction flask were charged 100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 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 M2. Wherein Pd (PPh) 3 ) 4 The amount of (C) added was 1mol% based on M1.
In a single flask was added 175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene, heated to reflux and reacted for 8h, TLC monitored the disappearance of starting material. Column chromatography, separation of intermediate M3.
Into the reaction flask were added 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, and 1mol% of cuprous iodide and 1mol% of 1, 10-phenanthroline. 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 yellow powder M4. Wherein the addition amount of the cuprous iodide and the 1, 10-phenanthroline is 1mol% of M3.
To the reaction flask were added 100mmol of M4, 100mmol of 4-benzidine-2- (N-phenylcarbazole), 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). 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 yellow powder A5. Wherein, the addition amount of Pd (dba) is 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ8.43-8.29(m,3H),7.96(s,1H),7.86(s,1H),7.81–7.70(m,4H),7.70–7.53(m,11H),7.49(d,J＝8.0Hz,4H),7.43–7.34(m,7H),7.31(s,1H),7.19(d,J＝10.0Hz,4H),6.40(s,1H)。
Synthesis of a 12:
into a reaction flask was charged 100mmol of 5-bromo-7, 7-dimethyl-7H-benzo [ c ]]Fluorene, 120mmol of pinacol diboronate, 40g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% Pd (dppf) Cl were 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 M1. Wherein Pd (dppf) Cl 2 Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene 1mol%.
Into a reaction flask were charged 100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 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 M2. Wherein Pd (PPh) 3 ) 4 The amount of (C) added was 1mol% based on M1.
In a single flask was added 175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene, heated to reflux, reacted for 8h and TLC monitored for disappearance of starting material. Column chromatography, separation of intermediate M3.
Into the reaction flask were added 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, and 1mol% of cuprous iodide and 1mol% of 1, 10-phenanthroline. 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 yellow powder M4. Wherein the addition amount of the cuprous iodide and the 1, 10-phenanthroline is 1mol% of M3.
Into the reaction flask were charged 100mmol of M4, 100mmol of 2-benzidine-2- (9, 9-dimethylfluorene), 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). 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 yellow powder a12. Wherein, the addition amount of Pd (dba) is 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ8.24-8.10(m,4H),8.05–7.85(m,3H),7.78-7.69(m,5H),7.62(s,1H),7.58(d,J＝8.4Hz,3H),7.50(dd,J＝13.2,9.6Hz,6H),7.45–7.32(m,4H),7.26(d,J＝12.6Hz,2H),7.14(s,1H),7.08(s,2H),6.40(s,1H),1.75(s,6H),1.69(s,6H)。
Synthesis of a 13:
into the reaction flask were added 100mmol of 5-bromobenzo [ b ] naphtho [1,2-d ] carbazole, 120mmol of iodobenzene, 40g of potassium carbonate (300 mmol), 800ml of DMF, and 1mol% of cuprous iodide and 1mol% of 1, 10-phenanthroline. The reaction was carried out at 120℃for 12h. After the reaction was completed, 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 yellow powder M1. Wherein, the addition of the cuprous iodide and the 1, 10-phenanthroline is 1mol percent of 5-bromobenzo [ b ] naphtho [1,2-d ] carbazole.
Into a reaction flask were charged 100mmol of M1, 120mmol of pinacol biborate, 41.4g 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 M2. Wherein Pd (dppf) Cl 2 Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene 1mol%.
Into a reaction flask were charged 100mmol of M2, 100mmol of 2-iodo-5-bromonitrobenzene, 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 M2.
In a single flask was added 175.8mmol of M3, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene, heated to reflux and reacted for 8h, TLC monitored the disappearance of starting material. Column chromatography, isolation of intermediate M4.
100mmol of M4, 120mmol of iodobenzene, 40g of potassium carbonate (300 mmol) and 800ml of DMF are added into a reaction bottle, and 1mol% of cuprous iodide and 1mol% of 1, 10-phenanthroline are added. 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 yellow powder M5. Wherein the addition amount of the cuprous iodide and the 1, 10-phenanthroline is 1mol% of M4.
Into the reaction flask were charged 100mmol of M4, 100mmol of bis 2- (9, 9-dimethylfluorene) amine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% Pd (dba). 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 yellow powder a13. Wherein, the addition amount of Pd (dba) is 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ8.55(d,J＝8.0Hz,3H),7.96(s,1H),7.92–7.79(m,5H),7.72(s,1H),7.69–7.55(m,10H),7.51(d,J＝10.0Hz,4H),7.42(s,1H),7.34-7.11(m,9H),6.40(s,1H),1.69(s,12H)。
Synthesis of a 14:
into a reaction flask was charged 100mmol of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene, 120mmol of pinacol diboronate, 40g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl are 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 M1. Wherein Pd (dppf) Cl 2 Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene 1mol%.
Into a reaction flask were charged 100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 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 M2. Wherein Pd (PPh) 3 ) 4 The amount of (C) added was 1mol% based on M1.
In a single flask was added 175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene, heated to reflux and reacted for 8h, TLC monitored the disappearance of starting material. Column chromatography, separation of intermediate M3.
Into the reaction flask were added 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, and 1mol% of cuprous iodide and 1mol% of 1, 10-phenanthroline. 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 yellow powder M4. Wherein the addition amount of the cuprous iodide and the 1, 10-phenanthroline is 1mol% of M3.
Into the reaction flask were charged 100mmol of M4, 100mmol of N- ([ 1,1' -biphenyl ] -4-yl) benzofuran [2,3-b ] pyridin-7-amine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). 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 yellow powder a14. Wherein, the addition amount of Pd (dba) is 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ8.42(s,1H),8.03(s,1H),7.97(d,J＝10.0Hz,3H),7.74(d,J＝8.8Hz,4H),7.64–7.52(m,6H),7.49(d,J＝8.0Hz,4H),7.43–7.35(m,6H),7.31(d,J＝7.6Hz,3H),7.26(s,1H),6.40(s,1H)。
Synthesis of a 15:
into a reaction flask was charged 100mmol of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene, 120mmol of pinacol diboronate, 41.4g of potassium carbonate (300 mmol), 800ml of N, N-Dimethylformamide (DMF) and 1mol% of Pd (dppf) Cl are added 2 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, filtration was carried out, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (dppf) Cl 2 Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene 1mol%.
Into a reaction flask were charged 100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 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, the reaction mixture was cooled to room temperature, water was added, filtration was carried out, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd (PPh) 3 ) 4 The amount of (C) added was 1mol% based on M1.
In a single flask were added 175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene, heated to reflux, reacted for 8h and monitored for disappearance of starting material by Thin Layer Chromatography (TLC). Column chromatography, separation of intermediate M3.
Into the reaction flask were added 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, and 1mol% of cuprous iodide and 1mol% of 1, 10-phenanthroline. 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 yellow powder M4. Wherein the addition amount of the cuprous iodide and the 1, 10-phenanthroline is 1mol% of M3.
Into the reaction flask were charged 100mmol of M4, 100mmol of 3-dibenzothiophene-2- (9, 9-dimethylfluorene), 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). 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 yellow powder a15. Wherein, the addition amount of Pd (dba) is 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ8.54(s,1H),8.45(s,1H),8.16–7.88(m,3H),7.88–7.67(m,5H),7.68(s,1H),7.68(s,1H),7.64–7.52(m,5H),7.40(dd,J＝10.4,7.6Hz,5H),7.27(d,J＝8.4Hz,6H),7.24-7.03(m,4H),6.40(s,1H),1.69(s,6H)。
Synthesis of a 23:
into the reaction flask were added 100mmol of dinaphtho [2,1-b:1',2' -d ] furan, 400ml of dichloromethane, and 100mmol of NBS. Stirring and reacting for 12h at normal temperature. 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 M1.
Into a reaction flask were charged 100mmol of M1, 120mmol of pinacol biborate, 40g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% ofPd(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 M2. Wherein Pd (dppf) Cl 2 Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d]Thiophene 1mol%.
Into a reaction flask were charged 100mmol of M2, 100mmol of 2-iodo-5-bromonitrobenzene, 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 M2.
In a single flask was added 175.8mmol of M4, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene, heated to reflux and reacted for 8h, TLC monitored the disappearance of starting material. Column chromatography, isolation of intermediate M4.
100mmol of M4, 120mmol of 3-iodobiphenyl, 40g of potassium carbonate (300 mmol) and 800ml of DMF are added into a reaction flask, and 1mol% of cuprous iodide and 1mol% of 1, 10-phenanthroline are added. 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 yellow powder M5. Wherein the addition amount of the cuprous iodide and the 1, 10-phenanthroline is 1mol% of M4.
Into the reaction flask were charged 100mmol of M5, 100mmol of 2-benzidine-2- (9, 9-dimethylfluorene), 40g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). 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 yellow powder a23. Wherein, the addition amount of Pd (dba) is 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.21(s,1H),7.97(d,J＝12.0Hz,2H),7.81(s,1H),7.70(d,J＝10.0Hz,5H),7.64–7.50(m,12H),7.36(d,J＝13.6Hz,6H),7.29-7.14(m,10H),6.40(s,1H),1.69(s,6H)。
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, a hole transport material A1 is vacuum-evaporated on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, the evaporation film thickness is 80nm, and the hole transport layer is formed by 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 is vacuum evaporated over the light emitting layer, the electron transport layer comprising an electron transport material ET42. Wherein, the vapor deposition rate is 0.1nm/s, the vapor deposition film thickness is 30nm, and the selected electron transport material ET42 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 7
The procedure of example 1 was repeated except that A5, A12, A13, A14, A15 and A23 were used in place of A1. See in particular table 1.
Comparative example 1
The procedure of example 1 was repeated except that HT-27 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 5 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 device 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 life test 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, A5, A12, A13, A14, A15 and A23 prepared by the method are used for hole transport materials of organic electroluminescent devices, can effectively reduce driving voltage, improve current efficiency, prolong service life of the devices, and are hole 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 (5)

1. A compound of formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
Ar 1 selected from phenyl, biphenyl, pyridyl, 9-dimethylfluorenyl, dibenzofuranyl, naphthyl, ar 1 The hydrogen atoms on may each independently be substituted with phenyl;
Ar 2 selected from biphenyl, 9-dimethylfluorenyl, spirofluorenyl;
l is a bond;
R 1 -R 4 selected from hydrogen;
x is selected from O, S, CR 5 R 6 ，R 5 And R is 6 Selected from methyl;
y is selected from O, S, CR 9 R 10 、NR 7 ，R 9 And R is 10 Each independently selected from methyl or phenyl, R 7 Selected from phenyl;
Z 1 -Z 8 each independently selected from CR 8 Or N, R 8 Selected from hydrogen.
2. The compound according to claim 1, wherein the compound is selected from the group consisting of:
3. a hole transport material comprising at least one of the compounds of claim 1 or 2.
4. An organic electroluminescent device comprising at least one of the hole transport materials of claim 3.
5. A display device comprising the organic electroluminescent device of claim 4.
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