CN116023370A

CN116023370A - Aromatic ring-linked electricity-absorbing biphenyl oxazole compound and application thereof

Info

Publication number: CN116023370A
Application number: CN202111230662.4A
Authority: CN
Inventors: 邢其锋; 丰佩川; 杜金华; 马艳; 胡灵峰; 陈跃; 陈义丽
Original assignee: Yantai Xianhua Chem Tech Co ltd
Current assignee: Yantai Xianhua Chem Tech Co ltd
Priority date: 2021-10-22
Filing date: 2021-10-22
Publication date: 2023-04-28

Abstract

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

Description

Aromatic ring-linked electricity-absorbing biphenyl oxazole compound and application thereof

Technical Field

The application relates to the technical field of organic light-emitting display, in particular to an aromatic ring-linked electricity-absorbing biphenyl oxazole compound and application thereof.

Background

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. Has important significance for the domestic material to break through the patent barrier. 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. Among them, an electron transport material, which is an important functional material, has a direct influence on the mobility of electrons and ultimately affects the light emitting efficiency of the OLED by affecting the exciton recombination by matching with the hole layer. The electron transfer rate achieved by the electron transport material applied to the OLED at present is obviously lower than that of the hole layer material applied to the OLED, the energy level matching performance of the electron transport material and the adjacent layer is poor, and the luminous efficiency of the OLED and the display function of the OLED display device are severely restricted. The present invention is directed to developing higher mobility electron transport materials that match high mobility hole transport materials to achieve higher luminous efficiency.

Disclosure of Invention

The application aims to provide an aromatic ring-linked electricity-absorbing biphenyl oxazole compound which is used as an electron transmission material so as to improve the working efficiency and prolong the service life of an organic electroluminescent device.

In a first aspect the present application provides a compound of formula (I):

wherein, the liquid crystal display device comprises a liquid crystal display device,

ar and Ar ¹ 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;

Ar ² selected from the following groups:

wherein R is selected from C1-C6 alkyl or cycloalkyl, and m is selected from 0-3; Z1-Z5 are each independently selected from N or CR1, R1 is selected from hydrogen, C6-C30 aryl or C3-C30 heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently being optionally substituted by Ra;

X ¹ -X ³ each independently selected from CH or N, and X ¹ -X ³ At least two of which are selected from N;

l is selected from chemical bond, C ₆ -C ₃₀ Arylene or C of (2) ₃ -C ₃₀ Is a heteroarylene group, and hydrogen atoms on the arylene and heteroarylene groupsEach of the subunits independently may be substituted with Ra, adjacent Ra being capable of linking to form a ring;

the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S or N;

the substituents Ra of each group are each independently selected from deuterium, halogen, nitro, cyano, C ₁ -C ₄ Alkyl, phenyl, biphenyl, terphenyl, naphthyl or pyridyl.

A second aspect of the present application provides an electron transport material comprising at least one of the compounds provided herein.

A third aspect of the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided herein.

A fourth aspect of the present application provides a display device comprising the organic electroluminescent device provided herein.

The compound provided by the application has the parent structure of the benzoxazole linkage electric absorption fragment, has high bond energy among atoms, good thermal stability, is favorable for solid state accumulation among molecules, and has strong electron transition capability. When the organic electroluminescent material is used as an electron transport material, the organic electroluminescent material has a matched energy level with adjacent layers, is favorable for electron injection and migration, can effectively reduce driving voltage, has higher electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device. The organic electroluminescent device comprises the compound as an electron transport material, so that the driving voltage 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, not all of the above-described advantages need be achieved simultaneously in practicing any one of the products or methods of the present application.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following description will briefly introduce the drawings that are required to be used in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only one embodiment of the present application, and other embodiments may be obtained according to these drawings to those skilled in the art.

Fig. 1 is a schematic structural view of a typical organic electroluminescent device.

Detailed Description

For the purposes of making the objects, technical solutions, and advantages of the present application more apparent, the present application will be further described in detail below by referring to the accompanying drawings and examples. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments obtained by those skilled in the art based on the embodiments herein fall within the scope of the protection of the present application.

In a first aspect the present application provides a compound of formula (I):

Ar ² selected from the following groups:

l is selected from chemical bond, C ₆ -C ₃₀ Arylene or C of (2) ₃ -C ₃₀ Sub-group of (2)Heteroaryl, the hydrogen atoms on the arylene and heteroarylene each independently may be substituted with Ra, adjacent Ra being capable of linking to form a ring;

The compound provided by the application has the parent structure of the benzoxazole linkage electric absorption fragment, has high bond energy among atoms, good thermal stability, is favorable for solid state accumulation among molecules, and has strong electron transition capability. Meanwhile, the energy level of the structure is regulated through the oxazole segment, and the structure is more matched with the adjacent layer, so that the structure can be used as an electron transport layer material to effectively reduce the driving voltage of the organic electroluminescent device, improve the current efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device. Meanwhile, the preparation process of the derivative of the benzoxazole electricity-absorbing fragment is simple and feasible, raw materials are easy to obtain, and the method is suitable for industrial production.

Preferably Ar and Ar ¹ Each independently selected from C ₆ -C ₁₈ Aryl or C of (2) ₃ -C ₁₈ The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;

preferably Ar ² Selected from the following groups:

wherein R is selected from C1-C6 alkyl or cycloalkyl, and m is selected from 0-3; Z1-Z5 are each independently selected from N or CR1;

preferably, R1 is selected from hydrogen, C ₆ -C ₁₈ Aryl or C of (2) ₃ -C ₁₈ The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;

preferably, L is selected from the group consisting of a bond, C ₆ -C ₁₈ Arylene of (2)Or C ₃ -C ₁₈ The hydrogen atoms on the arylene and heteroarylene groups may each independently be substituted with Ra, adjacent Ra being capable of linking to form a ring.

More preferably Ar and Ar ¹ Each independently selected from the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.

More preferably, said R1 is selected from hydrogen, 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.

More preferably, R is selected from methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl.

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, benzofuran, dibenzofuran, aza-dibenzofuran, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene.

For example, the compound of formula (I) is selected from the following compounds:

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A second aspect of the present application provides an electron transport material comprising at least one of the compounds provided herein. When the electron transport material is applied to an electron transport layer, the electron transport material has a matched energy level with adjacent layers, is favorable for electron injection and migration, can effectively reduce driving voltage, has higher electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device. The electron transport material provided by the application also has a larger conjugate plane, is favorable for molecular accumulation, shows good thermodynamic stability, and shows long service life in an organic electroluminescent device.

A third aspect of the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided herein as an electron transport layer. Therefore, the organic electroluminescent device provided by the application can effectively reduce the driving voltage, improve the luminous efficiency and prolong the service life of the organic electroluminescent device.

In the present application, the kind and structure of the organic electroluminescent device are not particularly limited, and various types and structures of organic electroluminescent devices known in the art may be used as long as at least one of the electron transporting materials 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.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer, a hole blocking layer may be provided between the light emitting layer and the electron transport layer, and a light extraction layer may be provided on the transparent electrode on the light emitting side. However, the structure of the organic electroluminescent device of the present application is not limited to the above-described specific structure, and each of the above-described layers may be omitted or added if necessary. The thickness of each layer is not particularly limited as long as the object of the present application can be achieved. For example, the organic electroluminescent device may include an anode made of metal, a hole injection layer (5 nm to 20 nm), a hole transport layer (80 nm to 140 nm), an electron blocking layer (5 nm to 20 nm), a light emitting layer (150 nm to 400 nm), a hole blocking layer (5 nm to 20 nm), an electron transport layer (300 nm to 800 nm), an electron injection layer (5 nm to 20 nm), a transparent or semitransparent cathode, and a light extraction layer (50 nm to 90 nm) in this order on a substrate.

Fig. 1 shows a schematic view of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are disposed in this order from bottom to top.

It will be appreciated that fig. 1 schematically illustrates only one typical organic electroluminescent device structure, and the present application is not limited to this structure, and the electron transport material of the present application may be used for any type of organic electroluminescent device.

In the organic electroluminescent device of the present application, various materials used for the layer in the prior art may be used for the other layers, except that the electron transport layer contains the electron transport material provided in the present application.

For convenience, the organic electroluminescent device of the present application will be described below with reference to fig. 1, but this is not meant to limit the scope of protection of the present application in any way. It is understood that all organic electroluminescent devices capable of using the electron transport materials of the present application are within the scope of the present application.

In the present application, the material of 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 Thin Film Transistor (TFT) element, 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 Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) ₂ ) The transparent conductive material such as zinc oxide (ZnO) and Low Temperature Polysilicon (LTPS) can be selected from metal materials such as silver and alloys thereof, aluminum and alloys thereof, organic conductive materials such as poly (3, 4-ethylenedioxythiophene) (PEDOT), and multilayer structures of the above materials.

In the present application, the material of the hole injection layer 3 is not particularly limited, and a hole transport material known in the art or a hole injection material known in the art may be selected. As the hole injecting material, for example, at least one of known Hole Transporting Materials (HTM) is selected.

In this application, the hole injection layer 3 may further include a p-type dopant, the kind of which is not particularly limited, and various p-type dopants known in the art may be used, for example, the p-type dopant may be selected from at least one of the following compounds:

in the present application, the amount of the p-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.

In the present application, the hole transport layer 4 is not particularly limited, and may be made using a Hole Transport Material (HTM) known in the art. For example, the material for the hole injection layer host and the material for the hole transport layer may be selected from, but not limited to, at least one of the following HT-1 to HT-31 compounds:

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In the present application, the light emitting material in the light emitting layer 5 is not particularly limited, and various light emitting materials known to those skilled in the art may be used, for example, the light emitting material may include a host material and a guest material. In the present application, the amounts of the host material and the guest material are not particularly limited, and may be those known to those skilled in the art.

In this application, the light emitting layer 5 may include a green light emitting layer, a red light emitting layer, or a blue light emitting layer, and in this application, a host material of the light emitting layer is not particularly limited, and at least one of light emitting layer host materials known in the art may be used. For example, the green light emitting layer host material may be selected from, but is not limited to, at least one of the following GPH-1 to GPH-80 compounds:

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in the present application, the host material of the red light emitting layer is not particularly limited, and at least one of the host materials of the red light emitting layer known in the art may be used. For example, it may be selected from, but not limited to, the above GPH-1 to GPH-80 compounds, and at least one of the following RH-1 to RH-13 compounds:

in the present application, the host material of the blue light emitting layer is not particularly limited, and at least one of the host materials of the blue light emitting layer known in the art may be used. For example, at least one of the following BH-1 to BH-36 compounds may be selected, but not limited to:

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In the present application, the guest material of the red light emitting layer is not particularly limited, and at least one of the guest materials of the red light emitting layer known in the art may be used. For example, at least one of the following RPD-1 to RPD-28 compounds may be selected, but is not limited to:

in the present application, the guest material of the green light emitting layer is not particularly limited, and at least one of the guest materials of the green light emitting layer known in the art may be used. For example, at least one of the following GD01 to GD04 compounds may be selected, but not limited to:

in the present application, the guest material of the blue light emitting layer is not particularly limited, and at least one of blue light emitting layer guest materials known in the art may be used. For example, at least one of the following BD01 to BD04 compounds may be selected, but is not limited to:

in the present application, the electron transport layer 6 may contain at least one of the electron transport materials of the present application, or may contain a combination of at least one of the electron transport materials of the present application and at least one of the following known electron transport materials. For example, known electron transport materials may be selected from, but are not limited to, at least one of the following ET-1 to ET-57 compounds:

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In the present application, the electron transport layer 6 may further include n-type dopants, the kind of which is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:

in the present application, the amount of the n-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.

In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, 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 material of the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, metals such as magnesium-silver mixture, magnesium-aluminum mixture, liF/Al, ITO, al, metal mixtures, oxides, and the like.

A fourth aspect of the present application provides a display device including the organic electroluminescent device provided herein, having an excellent display effect. 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 material on the reflective anode electrode 2 to form a hole injection layer 3, wherein the hole injection layer 3 comprises a main body material and a p-type 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 5 comprises a host material and a guest material;

(5) Vacuum evaporating an electron transport material on the light-emitting layer 5 as an electron transport layer 6;

(6) Vacuum evaporating an electron injection material on the electron transport layer 6 as an electron injection layer 7;

(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 compound A1:

into a reaction flask were charged 100mmol of 9-phenanthreneboronic acid, 100mmol of cyprodinil, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The addition amount of (2) is 1mol% of that of the cyprodinil.

Into a reaction flask were charged 100mmol of 4-chlorobenzeneboronic acid, 100mmol of M1, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M2. Wherein Pd is% PPh ₃ ) ₄ The amount of (C) added was 1mol% based on M1.

Into a reaction flask were charged 100mmol of M2, 110mmol of pinacol biborate, 29.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dichloro [1,1' -bis (diphenylphosphino) ferrocene]Palladium (Pd (dppf) Cl) ₂ ). The reaction was carried out at 100℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was separated, and a white solid was obtained by concentration, filtration and washing with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (dppf) Cl ₂ The amount of (2) added was 1mol% of M2.

Into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M3, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder A1. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M3.

¹ H NMR(400MHz,Chloroform)δ9.08(s,1H),8.84(s,1H),8.30(s,1H),8.24(d,J＝12.4Hz,2H),8.18(d,J＝8.0Hz,2H),7.87–7.80(m,5H),7.75(d,J＝10.0Hz,4H),7.68–7.50(m,6H).

Synthesis of compound A4:

into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of 2, 4-dichloro-6-phenylpyrimidine, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of (2), 4-dichloro-6-phenylpyrimidine added was 1mol%.

Into a reaction flask were charged 100mmol of 4-chlorobenzeneboronic acid, 100mmol of M1, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M2. Wherein Pd (PPh) ₃ ) ₄ The amount of (C) added was 1mol% based on M1.

Into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. Stopping the reaction after the reaction is completed, cooling the reactant to room temperature, adding water, concentrating the organic phaseA white solid was obtained, which was filtered and washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M3, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder A4. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M3.

¹ H NMR(400MHz,Chloroform)δ8.18(s,1H),8.11(d,J＝8.8Hz,2H),7.98–7.86(m,5H),7.83–7.75(m,3H),7.72–7.57(m,4H),7.55-7.49(m,3H),7.38(d,J＝7.2Hz,4H),7.33–7.26(m,3H),1.69(s,6H).

Synthesis of compound A6:

into a reaction flask were charged 100mmol of 3-pyridineboronic acid, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of the catalyst to be added was 1mol% of 3-pyridineboronic acid.

Into a reaction flask were charged 100mmol of M1, 110mmol of pinacol biborate, 29.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dichloro [1,1' -bis (diphenylphosphino) ferrocene]Palladium (Pd (dppf) Cl) ₂ ). The reaction was carried out at 100℃for 12h. Stopping the reaction after the reaction is completed, cooling the reactant to room temperature, adding water, separating the organic phase, concentrating A white solid was obtained, which was filtered and washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein Pd (dppf) Cl ₂ The amount of (C) added was 1mol% based on M1.

Into a reaction flask were charged 100mmol of 2, 4-dichloro-6-phenyltriazine, 100mmol of M2, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M3. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% based on 2, 4-dichloro-6-phenyltriazine.

Into a reaction flask were charged 100mmol of 4-chlorobenzeneboronic acid, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) ₃ ) ₄ The amount of (C) added was 3mol% based on M3.

Into a reaction flask were charged 100mmol of M4, 110mmol of pinacol biborate, 29.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dichloro [1,1' -bis (diphenylphosphino) ferrocene]Palladium (Pd (dppf) Cl) ₂ ). The reaction was carried out at 100℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, the organic phase was separated, and a white solid was obtained by concentration, filtration and washing with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd (dppf) Cl ₂ The amount of (2) added was 1mol% of M4.

Into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of 3-pyridineboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). Reaction at 60℃12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder M6. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M5, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder A6. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M5.

¹ H NMR(400MHz,Chloroform)δ9.24(s,1H),8.72(d,J＝10.0Hz,2H),8.34(d,J＝10.0Hz,2H),7.96(s,1H),7.88(d,J＝10.4Hz,4H),7.79(d,J＝8.0Hz,4H),7.48(d,J＝12.0Hz,4H),7.43-7.25(m,6H).

Synthesis of compound a 10:

into a reaction flask were charged 100mmol of p-tert-butylphenylboronic acid, 100mmol of 2, 4-dichloro-6-phenyltriazine, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% based on 2, 4-dichloro-6-phenyltriazine.

Into a reaction flask were charged 100mmol of 4-chlorobenzeneboronic acid, 100mmol of M1, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). At the position ofThe reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M2. Wherein Pd (PPh) ₃ ) ₄ The amount of (C) added was 1mol% based on M1.

Into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M3, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder a10. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M3.

¹ H NMR(400MHz,Chloroform)δ8.42(d,J＝8.0Hz,2H),8.19–7.94(m,3H),7.84–7.75(m,6H),7.58-7.50(m,4H),7.36(d,J＝7.6Hz,4H),7.25(d,J＝7.6Hz,4H),1.69(s,6H),1.33(s,9H).

Synthesis of compound a 11:

into a reaction flask were charged 100mmol of 2-spirobifluorene boric acid, 100mmol of 2, 4-dichloro-6-phenylpyrimidine, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of (2), 4-dichloro-6-phenylpyrimidine added was 1mol%.

Into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of phenylboronic acid, 41.4g of carbonic acidPotassium (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water were added, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M3, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder a11. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M3.

¹ H NMR(400MHz,Chloroform)δ8.23(s,1H),8.21–8.04(m,3H),7.98(s,1H),7.95–7.89(m,5H),7.84(d,J＝7.6Hz,6H),7.75–7.68(m,5H),7.65–7.47(m,7H),7.34(s,1H),7.24(t,J＝7.2Hz,4H).

Synthesis of compound a 13:

into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask was charged 100mmol of 1-bromo-4Naphthalene boric acid, 100mmol of M1, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M2. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 1-bromo-4-naphthaleneboric acid.

Into a reaction flask were charged 100mmol of M3, 100mmol of 4, 6-diphenyl-2-chlorotriazine, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder a13. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M3.

¹ H NMR(400MHz,Chloroform)δ8.95(s,1H),8.36(s,2H),7.84–7.75(m,6H),7.72–7.56(m,6H),7.50-7.40(m,4H),7.34-7.16(m,5H).

Synthesis of compound a 15:

into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of phenylboron Acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water are added, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M1, 110mmol of pinacol biborate, 29.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dichloro [1,1' -bis (diphenylphosphino) ferrocene]Palladium (Pd (dppf) Cl) ₂ ). The reaction was carried out at 100℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, an organic phase is separated, the white solid is obtained by concentration, filtration and water washing, and the obtained solid is recrystallized and purified by toluene to obtain white powder M2. Wherein Pd (dppf) Cl ₂ The amount of (C) added was 1mol% based on M1.

Into a reaction flask were charged 100mmol of 1-bromo-4-chlorodibenzofuran, 100mmol of M2, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M3. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 1-bromo-4-chlorodibenzofuran.

Into a reaction flask were charged 100mmol of M3, 110mmol of pinacol biborate, 29.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dichloro [1,1' -bis (diphenylphosphine) ferrocene]Palladium (Pd (dppf) Cl) ₂ ). The reaction was carried out at 100℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, the organic phase was separated, and a white solid was obtained by concentration, filtration and washing with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (dp)pf)Cl ₂ The amount of (2) added was 1mol% of M3.

Into a reaction flask were charged 100mmol of 2-bromotriphenylene, 110mmol of pinacol biborate, 29.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dichloro [1,1' -bis (diphenylphosphine) ferrocene]Palladium (Pd (dppf) Cl) ₂ ). The reaction was carried out at 100℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, the organic phase was separated, and a white solid was obtained by concentration, filtration and washing with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd (dppf) Cl ₂ The amount of (2) added was 1mol% based on 2-bromotriphenylene.

Into a reaction flask were charged 100mmol of 2, 4-dichloro-6-phenyltriazine, 100mmol of M5, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder M6. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% based on 2, 4-dichloro-6-phenyltriazine.

Into a reaction flask were charged 100mmol of M4, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder a15. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M4.

¹ H NMR(400MHz,Chloroform)δ9.40(s,1H),8.38–8.23(m,3H),8.15–8.03(m,4H),7.98-7.90(m,4H),7.85–7.74(m,5H),7.64(t,J＝7.6Hz,4H),7.56–7.43(m,6H),7.39-7.31(m,3H).

Synthesis of compound a 16:

into a reaction flask were charged 100mmol of 3-bromo-5-chloroiodobenzene, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of the catalyst to be added was 1mol% of 3-bromo-5-chloroiodobenzene.

Into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of 4-pyridineboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M3. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M2, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. Stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, concentrating the organic phase to obtain white solid, filtering and washing the white solid to obtainThe solid obtained was purified by recrystallization from toluene to give white powder M4. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M2.

Into a reaction flask were charged 100mmol of 9-phenanthreneboronic acid, 100mmol of 2, 4-dichloro-6-phenylpyrimidine, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder M6. Wherein Pd (PPh) ₃ ) ₄ The addition amount of (2) is 1mol% of that of the cyprodinil.

Into a reaction flask were charged 100mmol of M5, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder a16. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M5.

¹ H NMR(400MHz,Chloroform)δ9.08(s,1H),8.84(s,1H),8.34(t,J＝7.6Hz,3H),8.22(d,J＝6.8Hz,2H),8.17(s,2H),7.99(d,J＝10.0Hz,4H),7.69(d,J＝8.8Hz,4H),7.60(t,J＝10.0Hz,6H),7.43–7.32(m,7H).

Synthesis of compound a 22:

into a reaction flask were charged 100mmol of 2, 6-dimethylbenzeneboronic acid, 100mmol of 2, 4-dichloro-6-phenyltriazine, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% based on 2, 4-dichloro-6-phenyltriazine.

Into a reaction flask were charged 100mmol of 3-pyridineboronic acid, 100mmol of m-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. Stopping the reaction after the reaction is completed, cooling the reactant to room temperature, adding waterThe organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization from toluene to give white powder M4. Wherein Pd (PPh) ₃ ) ₄ The amount of the catalyst to be added was 1mol% of 3-pyridineboronic acid.

Into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of M5, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder M6. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M3, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder a22. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M3.

¹ H NMR(400MHz,Chloroform)δ9.24(s,1H),8.70(s,1H),8.34(d,J＝12.0Hz,3H),8.16(d,J＝11.2Hz,2H),7.87(s,1H),7.79(d,J＝10.0Hz,2H),7.70-7.61(m,4H),7.52(d,J＝8.0Hz,3H),7.40–7.22(m,6H),2.58(s,6H).

Synthesis of compound a 23:

into a reaction flask were charged 100mmol of 3-dibenzothiophene boric acid, 100mmol of 2, 4-dichloro-6-phenyltriazine, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% based on 2, 4-dichloro-6-phenyltriazine.

Into a reaction flask were charged 100mmol of 1-bromo-4-naphthalene boric acid, 100mmol of M1, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M2. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 1-bromo-4-naphthaleneboric acid.

Into a reaction flask were charged 100mmol of M2, 100mmol of p-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M3. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M2.

Into a reaction flask were charged 100mmol of M3, 110mmol of pinacol biborate, 29.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dioxaneChloro [1,1' -bis (diphenylphosphine) ferrocene]Palladium (Pd (dppf) Cl) ₂ ). The reaction was carried out at 100℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, the organic phase was separated, and a white solid was obtained by concentration, filtration and washing with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (dppf) Cl ₂ The amount of (2) added was 1mol% of M3.

Into a reaction flask were charged 100mmol of 2, 6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). The reaction was carried out at 60℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M5. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of 2, 6-dichlorobenzoxazole.

Into a reaction flask were charged 100mmol of M4, 100mmol of M5, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) ₃ ) ₄ . The reaction was carried out at 60℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder a23. Wherein Pd (PPh) ₃ ) ₄ The amount of (2) added was 1mol% of M4.

¹ H NMR(400MHz,Chloroform)δ9.00(s,1H),8.95-8.76(m,4H),8.36-8.18(m,4H),7.98(d,J＝10.0Hz,2H),7.88–7.75(m,3H),7.72–7.60(m,7H),7.56-7.40(m,5H),7.33(d,J＝8.0Hz,4H).

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, the anode is arrangedIs placed in a vacuum cavity, vacuumized to be 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 a hole transport material HT-11 and 3% of p-type dopant (p-1) by mass, the evaporation rate is 0.1nm/s, the thickness of the evaporation film is 10nm, and the materials HT-11 and the p-type dopant of the hole injection layer are as follows:

then, vacuum evaporation of a hole transport material HT-5 as a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, the evaporation film thickness is 80nm, and the hole transport layer is made of the following materials:

then, a light-emitting layer is vacuum-evaporated on the hole transmission layer, the light-emitting layer comprises a host material GHP-16 and a guest 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 guest material RPD-1 is 3% of the evaporation rate of the host material GHP-16, the total thickness of evaporation is 30nm, and the host material and the guest material are respectively the following materials:

then, an electron transport material A1 was vacuum-deposited as an electron transport layer on the light-emitting layer at a deposition rate of 0.1nm/s and a deposition film thickness of 30nm, and the electron transport material A1 was selected as follows:

Then, liF with the thickness of 0.5nm is vacuum evaporated on the electron transport layer to be used as an electron injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 10nm;

then, an aluminum 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.

The organic electroluminescent device of the present embodiment emits red light.

Example 2-example 10

The procedure of example 1 was repeated except that A4, A6, A10, A11, A13, A15, A16, A22 and A23 were used in place of A1. See in particular table 1.

Example 11

The procedure of example 1 was repeated except that GPH-44 was used in place of GHP-16 and GD04 was used in place of RPD-1.

The organic electroluminescent device of the present embodiment emits green light.

Example 12

The procedure of example 1 was repeated except that GHP-16 was replaced with BH-1 and RPD-1 was replaced with BD 01.

The organic electroluminescent device of the present embodiment emits blue light.

Comparative example 1

The procedure of example 1 was repeated except that ET-2 was used instead of A1.

Comparative example 2

The procedure of example 1 was repeated except that R-1 was used in place of A1.

Comparative example 3

The procedure of example 11 was repeated except that the compound ET-2 was used in place of A1.

Comparative example 4

The procedure of example 12 was repeated except that the compound ET-2 was used in place of A1.

The performance test method of the organic electroluminescent device comprises the following steps:

the driving voltage, current efficiency and lifetime of the organic electroluminescent devices prepared in examples 1 to 12 and comparative examples 1 to 4 were measured using a digital source meter and a luminance meter at the same luminance, and the specific procedures are as follows:

< test of drive Voltage and Current efficiency >

(1) Red light device: increasing the voltage at a rate of 0.1V per second, and measuring that the brightness of the organic electroluminescent device reaches 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.

(2) Green light device: increasing the voltage at a rate of 0.1V per second, and determining that the brightness of the organic electroluminescent device reaches 10000cd/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.

(3) Blue light device: increasing the voltage at a rate of 0.1V per second, and determining that the brightness of the organic electroluminescent device reaches 1000cd/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.

< lifetime test of LT95 >

(1) Red light device: 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.

(2) Green light device: using a luminance meter at 10000cd/m ² Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 9500cd/m ² Time in hours.

(3) Blue light device: at 1000cd/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 950cd/m ² Time in hours.

TABLE 1 organic electroluminescent device Performance results

As can be seen from the data of table 1, the compounds A1, A4, A6, a10, a11, a13, a15, a16, a22, a23 provided herein are used as electron transport materials for organic electroluminescent devices in examples 1 to 12, and can provide lower driving voltages, higher luminous efficiency, and longer LT95 lifetime for red, green, and blue light emitting devices at the same luminance as compared to the case of using the known materials in the prior art as electron transport materials for organic electroluminescent devices in comparative examples 1 to 4. Therefore, the compound is used as an electron transport material of the organic electroluminescent device, can effectively reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency and prolong the service life of the organic electroluminescent device, and is an electron transport material with good performance.

The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modifications, equivalent substitutions, improvements, etc. that are within the spirit and principles of the present application are intended to be included within the scope of the present application.

Claims

1. A compound of formula (I):

Ar ² selected from the following groups:

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, adjacent Ra being capable of linking to form a ring;

2. The compound according to claim 1, wherein,

ar and Ar ¹ Each independently selected from C ₆ -C ₁₈ Aryl or C of (2) ₃ -C ₁₈ The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;

Ar ² selected from the following groups:

wherein R is selected from C1-C6 alkyl or cycloalkyl, and m is selected from 0-3; Z1-Z5 are each independently selected from N or CR1, R1 is selected from hydrogen, C ₆ -C ₁₈ Aryl or C of (2) ₃ -C ₁₈ 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 ₁₈ Arylene or C of (2) ₃ -C ₁₈ The hydrogen atoms on the arylene and heteroarylene groups may each independently be substituted with Ra, adjacent Ra being capable of linking to form a ring.

3. The compound of claim 1, wherein Ar and Ar ¹ Each independently selected from the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.

4. The compound of claim 1, wherein R1 is selected from hydrogen, unsubstituted or Ra substituted groups: 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.

5. The compound of claim 1, wherein R is selected from methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl.

6. The compound of claim 1, wherein L is selected from a bond, a subunit of the following compounds that is unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, benzofuran, dibenzofuran, aza-dibenzofuran, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene.

7. The compound of claim 1, selected from the following compounds:

/>

8. an electron transport material comprising at least one of the compounds of any of claims 1-7.

9. An organic electroluminescent device comprising at least one of the electron transport materials of claim 8.

10. A display device comprising the organic electroluminescent device of claim 9.