CN117327099A - Phenanthroline substituted compound and application thereof - Google Patents

Abstract

This application provides a compound of formula (I). The compound has a parent structure of a bis-phenanthroline substituted fragment, a large conjugated plane, and high bond energy between atoms. It is used as an electron transport material or charge generation. The material has a suitable energy level between adjacent levels, which is conducive to the injection and migration of electrons, can effectively reduce the driving voltage of organic electroluminescent devices, and has a high electron migration rate, thereby improving organic electroluminescence. device luminous efficiency. Applying this compound as an electron transport material or charge generation material in an organic electroluminescent device can reduce the driving voltage of the organic electroluminescent device, improve its luminous efficiency, and extend its service life.

Description

A phenanthroline substituted compound and its application

Technical Field

The present application relates to the technical field of organic light-emitting display, and in particular to a phenanthroline substituted compound and its application.

Background Art

Electroluminescence (EL) refers to the phenomenon that luminescent materials emit light under the action of electric field, stimulated by current and voltage. It is a luminescence process that directly converts electrical energy into light energy. Organic electroluminescent displays (hereinafter referred to as OLEDs) have a series of advantages such as autonomous luminescence, low-voltage DC drive, full curing, wide viewing angle, light weight, simple composition and process. Compared with liquid crystal displays, OLEDs do not require backlight, have a large viewing angle, low power consumption, and a response speed that can reach 1,000 times that of liquid crystal displays, but their manufacturing cost is lower than that of liquid crystal displays with the same resolution. Therefore, organic electroluminescent devices have a very broad application prospect.

With the continuous advancement of OLED technology in the two major fields of lighting and display, people are paying more attention to the research on high-efficiency organic materials that affect the performance of OLED devices. An organic electroluminescent device with high efficiency and long life is usually the result of an optimized combination of device structure and various organic materials. This provides great opportunities and challenges for chemists to design and develop functional materials of various structures.

Compared with inorganic light-emitting materials, organic electroluminescent materials have many advantages, such as good processing performance, can be formed into films on any substrate by evaporation or spin coating, can realize flexible display and large-area display, can adjust the optical properties, electrical properties and stability of materials by changing the molecular structure, etc., and there is a lot of room for material selection. In the most common OLED device structure, the following types of organic materials are usually included: hole injection materials, hole transport materials, electron transport materials, charge generation materials, and luminescent materials (including host materials and guest materials). At present, electron transport materials or charge generation materials, as an important functional material, have a direct impact on the mobility of electrons and ultimately affect the luminous efficiency of OLEDs. However, the current commercial electron transport materials or charge generation materials have the problem of low mobility, so it is necessary to develop materials with higher mobility.

Summary of the invention

The purpose of the present application is to provide a compound which, when used as an electron transport material or a charge generating material, can improve the working efficiency and extend the service life of an organic electroluminescent device.

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

in,

^Q1 and ^Q2 are each independently selected from:

The hydrogen atoms on Q ¹ may be independently substituted by R ₁ , wherein R ₁ is selected from C ₁ -C ₄ alkyl, C ₆ -C ₃₀ aryl which is unsubstituted or substituted by Rc, C ₃ -C ₃₀ heteroaryl which is unsubstituted or substituted by Rc;

The hydrogen atoms on Q ² may be independently substituted by R ₂ , wherein R ₂ is selected from C ₁ -C ₄ alkyl, C ₆ -C ₃₀ aryl which is unsubstituted or substituted by Rc, C ₃ -C ₃₀ heteroaryl which is unsubstituted or substituted by Rc;

^L1 and ^L2 are each independently selected from a chemical bond, a _C6 - _C30 arylene group which is unsubstituted or substituted by Rc, and _{a C3-C30 heteroarylene} group which is unsubstituted or substituted by Rc;

M is selected from

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

The substituents Rc of the respective groups are each independently selected from deuterium, halogen, nitro, cyano, C ₁ -C ₄ alkyl, phenyl, biphenyl, terphenyl or naphthyl.

The second aspect of the present application provides an electron transport material, which comprises at least one of the compounds provided in the first aspect of the present application.

The third aspect of the present application provides a charge generating material, which comprises at least one of the compounds provided in the first aspect of the present application.

The fourth aspect of the present application provides an organic electroluminescent device, which comprises at least one of the electron transport material provided in the second aspect of the present application or the charge generation material provided in the third aspect of the present application.

The fifth aspect of the present application provides a display device, which includes the organic electroluminescent device provided by the fourth aspect of the present application.

The compound provided by the present application has a parent structure of a diphenanthroline substituted fragment, has a larger conjugated plane, and has a high bond energy between atoms, which is conducive to solid-state accumulation between molecules, thereby showing good thermal stability. When used as an electron transport material, it has a suitable energy level with adjacent levels, which is conducive to the injection and migration of electrons, and can effectively reduce the driving voltage of the organic electroluminescent device, while having a higher electron migration rate, thereby improving the luminous efficiency of the organic electroluminescent device and extending the service life of the organic electroluminescent device. When used as a charge generating material, the efficiency of charge generation can be improved, especially for the charge generating layer containing metal Li or Yb, the compound of the present application can form a good complexation with the above-mentioned metal to improve the efficiency of charge generation, thereby effectively enhancing the luminous efficiency of the organic electroluminescent device and reducing the driving voltage of the organic electroluminescent device. The organic electroluminescent device of the present application includes the compound of the present application as an electron transport material or a charge generating material, which can effectively reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency of the organic electroluminescent device, and extend the service life of the organic electroluminescent device. The display device provided by the present application has an excellent display effect.

Of course, implementing any product or method of the present application does not necessarily require achieving all of the advantages described above at the same time.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly illustrate the technical solutions in the present application or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other embodiments can also be obtained based on these drawings.

FIG1 is a schematic diagram of the structure of a typical organic electroluminescent device;

FIG. 2 is a schematic diagram of the structure of another typical organic electroluminescent device.

DETAILED DESCRIPTION

The following will be combined with the drawings in this application to clearly and completely describe the technical solutions in this application. Obviously, the described embodiments are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field based on this application belong to the scope of protection of this application.

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

in,

^Q1 and ^Q2 are each independently selected from:

The hydrogen atoms on Q ¹ may be independently substituted by R ₁ , wherein R ₁ is selected from C ₁ -C ₄ alkyl, C ₆ -C ₃₀ aryl which is unsubstituted or substituted by Rc, C ₃ -C ₃₀ heteroaryl which is unsubstituted or substituted by Rc;

The hydrogen atoms on Q ² may be independently substituted by R ₂ , wherein R ₂ is selected from C ₁ -C ₄ alkyl, C ₆ -C ₃₀ aryl which is unsubstituted or substituted by Rc, C ₃ -C ₃₀ heteroaryl which is unsubstituted or substituted by Rc;

^L1 and ^L2 are each independently selected from a chemical bond, a _C6 - _C30 arylene group which is unsubstituted or substituted by Rc, and _{a C3-C30 heteroarylene} group which is unsubstituted or substituted by Rc;

M is selected from

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

The substituents Rc of the respective groups are each independently selected from deuterium, halogen, nitro, cyano, C ₁ -C ₄ alkyl, phenyl, biphenyl, terphenyl or naphthyl.

Preferably, R ₁ and R ₂ are each independently selected from C ₁ -C ₄ alkyl, C ₆ -C ₁₈ aryl which is unsubstituted or substituted by Rc, and C ₃ -C ₁₈ heteroaryl which is unsubstituted or substituted by Rc.

Preferably, L ¹ and L ² are each independently selected from a chemical bond, a C ₆ -C ₁₈ arylene group which is unsubstituted or substituted by Rc, and a C ₃ -C ₁₈ heteroarylene group which is unsubstituted or substituted by Rc.

More preferably, R ₁ and R ₂ are each independently selected from methyl, ethyl, isopropyl, tert-butyl, the following groups which are unsubstituted or substituted by Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazine, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl.

More preferably, ^L1 and ^L2 are each independently selected from the subunits of the following compounds which are chemically bonded, unsubstituted or substituted with Rc: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thiophene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9,9-dimethylfluorene, and spirofluorene.

For example, the compound of formula (I) can be selected from the compounds shown in the following A1 to A33:

The compound of formula (I) provided in the present application has high bond energy between atoms, good thermal stability, and is conducive to solid-state stacking between molecules. In addition, the preparation process of the compound of formula (I) provided in the present application is simple and easy, and the raw materials are easily available, which is suitable for industrial production.

The second aspect of the present application provides an electron transport material, which comprises at least one of the compounds provided in the first aspect of the present application.

The third aspect of the present application provides a charge generating material, which comprises at least one of the compounds provided in the first aspect of the present application.

When the compound of the present application is used as an electron transport material or a charge generating material, it has a matching energy level between adjacent layers, which is conducive to the injection and migration of electrons, and can effectively reduce the driving voltage of the organic electroluminescent device. At the same time, it has a high electron migration rate, thereby improving the luminous efficiency of the organic electroluminescent device and extending the service life of the organic electroluminescent device. The compound provided by the present application also has a large conjugated plane, which is conducive to molecular stacking and shows good thermodynamic stability. Use in an organic electroluminescent device can extend its service life.

The fourth aspect of the present application provides an organic electroluminescent device, which comprises at least one of the electron transport material provided in the second aspect of the present application or the charge generating material provided in the third aspect of the present application. Therefore, the organic electroluminescent device provided in the present application has a low driving voltage, a high luminous efficiency and a long service life.

In the present application, there is no particular limitation on the type and structure of the organic electroluminescent device, and it can be an organic electroluminescent device of different types and structures known in the art, as long as at least one of the electron transport materials or charge generation materials provided in the present application can be used.

In some embodiments of the present application, the organic electroluminescent device of the present application may be a light-emitting device with a top-emitting structure, which may include, in sequence, 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 semi-transparent cathode on a substrate.

The organic electroluminescent device of the present application may also be a light-emitting device with a bottom emission structure, which may include a transparent or semi-transparent 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 sequence on a substrate.

The organic electroluminescent device of the present application may also be a light-emitting device with a double-sided light-emitting structure, which may include a transparent or semi-transparent 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 semi-transparent cathode structure in sequence on a substrate.

In addition, the organic electroluminescent device of the present application may also have an electron blocking layer between the hole transport layer and the light-emitting layer, a hole blocking layer 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-mentioned specific structure, and the above-mentioned layers may be omitted or increased if necessary. The present application has no particular restrictions on the thickness of the above-mentioned layers, as long as the purpose of the present application can be achieved. For example, the organic electroluminescent device may include an anode (100nm to 150nm) made of metal, a hole injection layer (5nm to 20nm), a hole transport layer (80nm to 140nm), an electron blocking layer (5nm to 20nm), a light-emitting layer (20nm to 45nm), a hole blocking layer (5nm to 20nm), an electron transport layer (30nm to 40nm), an electron injection layer (3nm to 10nm), a transparent or semi-transparent cathode (100nm to 160nm) and a light extraction layer (50nm to 90nm) on a substrate in sequence. For example, FIG1 shows a schematic diagram of a typical organic electroluminescent device, in which, from bottom to top, a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are arranged in sequence.

In other embodiments of the present application, the organic electroluminescent device of the present application may be a light-emitting device with a top-emitting structure, which may include, in sequence, an anode, a first hole injection layer, a first light-emitting unit, a charge generation layer, a second hole injection layer, a second light-emitting unit, an electron injection layer, and a transparent or semi-transparent cathode on a substrate.

The organic electroluminescent device of the present application may also be a light-emitting device with a bottom-emitting structure, which may include a transparent or semi-transparent anode, a first hole injection layer, a first light-emitting unit, a charge generation layer, a second hole injection layer, a second light-emitting unit, an electron injection layer and a cathode structure in sequence on a substrate.

The organic electroluminescent device of the present application may also be a light-emitting device with a double-sided light-emitting structure, which may include a transparent or semi-transparent anode, a first hole injection layer, a first light-emitting unit, a charge generation layer, a second hole injection layer, a second light-emitting unit, an electron injection layer and a transparent or semi-transparent cathode structure on a substrate in sequence. The first light-emitting unit includes a first hole transport layer, a first light-emitting layer and a first electron transport layer arranged in sequence, and the second light-emitting unit includes a second hole transport layer, a second light-emitting layer and a second electron transport layer arranged in sequence.

For example, an organic electroluminescent device may include, on a substrate, in sequence, an anode (100 nm to 150 nm) made of metal, a first hole injection layer (5 nm to 20 nm), a first hole transport layer (80 nm to 140 nm), a first light-emitting layer (20 nm to 45 nm), a first electron transport layer (30 nm to 40 nm), a charge generation layer (5 nm to 20 nm), a second hole injection layer (5 nm to 20 nm), a second hole transport layer (80 nm to 140 nm), a second light-emitting layer (20 nm to 45 nm), a second electron transport layer (30 nm to 40 nm), an electron injection layer (3 nm to 10 nm), a cathode (100 nm to 160 nm), and a light extraction layer (50 nm to 90 nm). By way of example, FIG2 shows a schematic diagram of another typical organic electroluminescent device 20, in which, from bottom to top, a substrate 21, a reflective anode 22, a first hole injection layer 23a, a first hole transport layer 24a, a first light-emitting layer 25a, a first electron transport layer 26a, a charge generation layer 29, a second hole injection layer 23b, a second hole transport layer 24b, a second light-emitting layer 25b, a second electron transport layer 26b, an electron injection layer 27, and a cathode 28 are sequentially arranged.

It can be understood that FIG. 1 and FIG. 2 only schematically show the structures of two typical organic electroluminescent devices, and the present application is not limited to such structures. The electron transport material or charge generation material of the present application can be used in any type of organic electroluminescent device.

In the organic electroluminescent device of the present application, except that the electron transport layer comprises the electron transport material provided in the present application or the charge generation layer comprises the charge generation material of the present application, other layers may use various materials used for the layers in the prior art.

For convenience, the organic electroluminescent device of the present application is exemplified below, but this does not mean any limitation on the protection scope of the present application. It is understood that all organic electroluminescent devices that can use the electron transport material or charge generation material of the present application are within the protection scope of the present application.

In the present application, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the prior art may be used, such as glass, polymer materials, and glass and polymer materials with thin film transistor (TFT) components.

In the present application, the material 2 of the above-mentioned reflective anode is not particularly limited, and can be selected from transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide ( _SnO2 ), zinc oxide (ZnO) known in the prior art, or metal materials such as silver and its alloys, aluminum and its alloys, or organic conductive materials such as poly (3,4-ethylenedioxythiophene) (PEDOT), or the reflective anode is a multilayer structure formed by the above materials. The present application has no particular limitation on the number of layers of the multilayer structure, which can be selected according to actual needs as long as it can meet the purpose of the present application, for example, 1 layer, 2 layers, 3 layers or more layers.

In the present application, the material of the hole injection layer 3 is not particularly limited, and can be made of hole injection layer materials known in the art. For example, at least one of the known hole transport materials (HTM) is selected as the hole injection material.

In the present application, the hole injection layer 3 may further include a p-type dopant, and the type of the p-type dopant is not particularly limited, and various p-type dopants known in the art may be used. For example, the p-type dopant may be selected from but not limited to at least one of the following p-1 to p-3 compounds:

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

In the present application, the material of the hole transport layer 4 is not particularly limited, and can be made of hole transport materials (HTM) known in the art. The number of layers of the hole transport layer 4 is not particularly limited, and can be adjusted according to actual needs, as long as it can meet the purpose of the present application, for example, 1 layer, 2 layers, 3 layers, 4 layers or more layers.

For example, the HTM for the hole injection layer material and the HTM for the hole transport layer material may be selected from, but not limited to, at least one of the following HT-1 to HT-31 compounds:

In the present application, the material of the above-mentioned light-emitting layer 5 includes a light-emitting layer host material and a light-emitting layer guest material, wherein the amounts of the light-emitting layer host material and the light-emitting layer guest material are not particularly limited and can be amounts known to those skilled in the art.

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

The main material of the light-emitting layer may also use at least one of the green light-emitting layer main materials known in the art. For example, it may be selected from but not limited to at least one of the following GPH-1 to GPH-80 compounds:

The main material of the light-emitting layer may also use at least one of the main materials of the blue light-emitting layer known in the art. For example, it may be selected from but not limited to at least one of the following BH-1 to BH-10 compounds:

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

The light-emitting layer guest material may be a green light-emitting layer guest material, for example, may be selected from but not limited to at least one of the following GD01 to GD04 compounds:

The light-emitting layer guest material may be a blue light-emitting layer guest material. For example, the light-emitting layer guest material may be selected from but not limited to at least one of the following BD-1 to BD-9 compounds:

In the present application, the amount of the guest material in the light-emitting layer is not particularly limited and can be an amount known to those skilled in the art.

In the present application, the electron transport layer 6 includes at least one of the electron transport materials of the present application, and may also include a combination of at least one of the electron transport materials of the present application and at least one of the known electron transport materials. The number of layers of the electron transport layer 6 is not particularly limited and can be adjusted according to actual needs as long as the purpose of the present application can be met, for example, 1 layer, 2 layers, 3 layers, 4 layers or more layers.

For example, the known electron transport material may be selected from, but not limited to, at least one of the following ET-1 to ET-57 compounds:

In the present application, the electron transport layer 6 may further include an n-type dopant. The type of the n-type dopant is not particularly limited, and various n-type dopants known in the art may be used. For example, the following n-type dopants may be used:

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

In the present application, the charge generating layer may include at least one of the charge generating materials of the present application, or may include a combination of at least one of the charge generating materials of the present application and at least one of the following known charge generating materials.

For example, the known charge generating material may be selected from, but not limited to, at least one of the following CGL00R1 to CGL00R4 compounds:

In the present application, the charge generation layer may further include at least one of the following metals: Li, Yb.

In the present application, the amount of the above metals is not particularly limited and can be any amount 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 can be used, for example, including but not limited to at least one of 8-hydroxyquinoline lithium (LiQ), LiF, NaCl, CsF, Li ₂ O, Cs ₂ CO ₃ , BaO, Na, Li, Ca and other materials in the prior art.

In the present application, the material of the cathode electrode 8 is not particularly limited, and can be selected from but not limited to magnesium-silver mixture, LiF/Al, ITO, Al and other metals, oxides and the like.

The method for preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be used. For example, the present application may be prepared by the following preparation method:

(1) cleaning the reflective anode electrode 2 on the substrate 1 of the top-emitting OLED device by using a cleaning machine through steps such as chemical cleaning, water cleaning, brushing, high-pressure water cleaning, and air knife cleaning, and then performing a heat treatment;

(2) vacuum evaporating a hole injection material on the reflective anode electrode 2 to form a hole injection layer 3;

(3) vacuum evaporating a hole transport material on the hole injection layer 3 to form 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 contains a host material and a guest material;

(5) vacuum evaporating an electron transport material on the light emitting layer 5 to form an electron transport layer 6;

(6) vacuum evaporating an electron injection material on the electron transport layer 6 to form an electron injection layer 7;

(7) A cathode material is vacuum-deposited on the electron injection layer 7 to form a cathode electrode 8 .

The method for preparing the organic electroluminescent device of the present application may also include but is not limited to the following steps:

(1) cleaning the reflective anode 22 on the top-emitting organic electroluminescent device substrate 21 by using a cleaning machine through steps such as chemical cleaning, water cleaning, brushing, high-pressure water cleaning, and air knife cleaning, and then heating treatment;

(2) vacuum evaporating a hole injection material on the reflective anode 22 to form a first hole injection layer 23a;

(3) vacuum evaporating a hole transport material on the first hole injection layer 23a to form a first hole transport layer 24a;

(4) vacuum evaporating a first light-emitting layer 25a on the first hole transport layer 24a, wherein the light-emitting layer includes a host material and a guest material;

(5) vacuum evaporating an electron transport material on the first light-emitting layer 25a to form a first electron transport layer 26a;

(6) vacuum evaporating a charge generating material on the first electron transport layer 26a to form a charge generating layer 29;

(7) vacuum evaporating a hole injection material on the charge generation layer 29 to form a second hole injection layer 23b;

(8) vacuum evaporating a hole transport material on the second hole injection layer 23b to form a second hole transport layer 24b;

(9) vacuum evaporating a second light-emitting layer 25b on the second hole transport layer 24b, wherein the light-emitting layer includes a host material and a guest material;

(10) vacuum evaporating an electron transport material on the second light-emitting layer 25b to form a second electron transport layer 26b;

(11) vacuum evaporating an electron injection material on the second electron transport layer 26 b to form an electron injection layer 27;

(12) A cathode material is vacuum-deposited on the electron injection layer 27 to form the cathode 28 .

The above only describes a typical structure of an organic electroluminescent device and its preparation method. It should be understood that the present application is not limited to this structure. The electron transport material or charge generation material of the present application can be used in an organic electroluminescent device of any structure, and the organic electroluminescent device can be prepared by any preparation method known in the art.

The fifth aspect of the present application provides a display device, which includes the organic electroluminescent device provided in the fourth aspect of the present application. The display device includes but is not limited to a display, a television, a tablet computer, a mobile communication terminal, etc.

The synthesis method of the compound of the present application is not particularly limited, and any method known to those skilled in the art can be used for synthesis. The following examples illustrate the synthesis process of the compound of the present application.

Synthesis Example

Synthesis of compound A1:

100 mmol of 5-chloro-o-phenanthroline, 100 mmol of m-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF) and 200 mL of water were added to a reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 5-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of M1, 100 mmol of M2, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

¹ H NMR (400MHz, Chloroform)8.74(d,J＝8.0Hz,4H),8.14-8.08(m,6H),7.88(s,2H),7.61(d,J＝8.0Hz,6H),7.39( s,2H),7.32(s,2H).

Synthesis of compound A4:

100 mmol of 5-chloro-o-phenanthroline, 100 mmol of m-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 5-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of M2, 100 mmol of m-chlorobromobenzene, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M3. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M2.

100 mmol of 5-chloro-o-phenanthroline, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 5-chloro-o-phenanthroline.

100 mmol of M4, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to the reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M5. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M4.

100 mmol of M3, 100 mmol of M5, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A4. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M3.

¹ H NMR (400MHz, Chloroform)8.81(d,J＝8.0Hz,3H),8.67(s,1H),8.22-8.00(m,7H),7.88(s,1H),7.70-7.61(m,5H ),7.40(d,J＝10.0Hz,3H),7.32(d,J＝10.0Hz,6H).

Synthesis of compound A6:

100 mmol of 2-chloro-o-phenanthroline, 100 mmol of m-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 2-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of 3-bromophenanthroline, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M3. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 3-bromophenanthroline.

100 mmol of M2, 100 mmol of M3, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A6. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M2.

¹ H NMR (400MHz, Chloroform)8.80(s,1H),8.49(s,1H),8.26-7.98(m,3H),7.80-7.67(m,5H),7.58(d,J＝10.0Hz,6H ),7.34-7.22(m,6H).

Synthesis of compound A8:

100 mmol of 2-chloro-o-phenanthroline, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 2-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of M2, 100 mmol of m-chlorobromobenzene, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M3. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M2.

100 mmol of 4,7-dichlorophenanthroline, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M4. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 3-bromophenanthroline.

100 mmol of M4, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M5. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M4.

100 mmol of M5, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to the reaction flask, and the reaction was carried out at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M6. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M5.

100 mmol of M3, 100 mmol of M6, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A8. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M3.

¹ H NMR (400MHz, Chloroform)8.87(s,1H),8.74(d,J＝8.0Hz,2H),8.42(d,J＝10.0Hz,2H),8.11(s,1H),7.87(d, J＝10.0Hz,3H),7.80(d,J＝8.0Hz,4H),7.77-7.64(m,6H),7.59-7.48(m,5H),7.37-7.12(m,4H).

Synthesis of compound A11:

100 mmol of 2-chloro-o-phenanthroline, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 2-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of 2,6-dibromopyridine, 200 mmol of M2, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A11. The amount of Pd(PPh ₃ ) ₄ added was 2 mol% of 2,6-dibromopyridine.

¹ H NMR (400MHz, Chloroform)8.80(s,2H),8.42(d,J＝10.0Hz,6H),7.88(s,1H),7.57(d,J＝10.0Hz,6H),7.26(d, J＝8.0Hz, 6H), 6.94 (d, J＝8.0Hz, 4H).

Synthesis of compound A15:

100 mmol of 4-chloro-2,9-dimethyl-o-phenanthroline, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 4-chloro-2,9-dimethyl-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of 2,6-dibromopyridine, 100 mmol of M2, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 2,6-dibromopyridine.

100 mmol of 4-chloro-2,9-dimethyl-o-phenanthroline, 100 mmol of m-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M4. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 4-chloro-2,9-dimethyl-o-phenanthroline.

100 mmol of M4, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to the reaction flask, and the reaction was carried out at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M5. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M4.

100 mmol of M3, 100 mmol of M5, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A15. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M3.

¹ H NMR (400MHz, Chloroform) 8.69 (s, 2H), 8.33-8.16 (m, 5H), 7.69 (d, J = 8.0Hz, 6H), 7.55 (d, J = 9.2Hz, 4H), 7.37 ( d,J＝10.0Hz,4H),2.76(s,6H),2.69(s,6H).

Synthesis of compound A21:

100 mmol of 2-chloro-o-phenanthroline, 100 mmol of m-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 2-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of 1,4-dibromonaphthalene, 200 mmol of M2, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain a white powder A21. The amount of Pd(PPh ₃ ) ₄ added was 2 mol% of 1,4-dibromonaphthalene.

¹ H NMR(400MHz,Chloroform)9.00(s,2H),8.80(s,2H),8.66-8.39(m,8H),7.88(s,2H),7.70(s,2H),7.67-7.54(m ,6H),7.33(d,J＝8.0Hz,6H).

Synthesis of compound A26:

100 mmol of 2-chloro-o-phenanthroline, 100 mmol of m-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 2-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of 3,8-dibromophenanthroline, 100 mmol of 3-pyridineboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M3. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 3,8-dibromophenanthroline.

100 mmol of M3, 100 mmol of m-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to the reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M4. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M3.

100 mmol of M2, 100 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A26. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M2.

¹ H NMR (400MHz, Chloroform)9.24(s,1H),8.70-8.60(m,3H),8.49(d,J＝8.8Hz,2H),8.41–8.18(m,4H),8.04-7.84(m ,6H),7.63-7.53(m,5H),7.40(d,J＝10.0Hz,4H).

Synthesis of compound A31:

100 mmol of 2-chloro-o-phenanthroline, 100 mmol of m-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 2-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of 1,5-dibromonaphthalene, 200 mmol of M2, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A31. The amount of Pd(PPh ₃ ) ₄ added was 2 mol% of 1,5-dibromonaphthalene.

¹ H NMR (400MHz, Chloroform)8.89(s,1H),8.80(s,1H),8.45(d,J＝8.4Hz,2H),8.38(d,J＝10.0Hz,4H),8.13-7.88( m,6H),7.70(s,1H),7.63-7.50(m,9H),7.34(d,J＝10.0Hz,4H).

Synthesis of compound A32:

100 mmol of 5-chloro-o-phenanthroline, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 5-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of M2, 100 mmol of m-chlorobromobenzene, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M3. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M2.

100 mmol of M3, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to the reaction flask, and the reaction was carried out at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M3.

100 mmol of M4, 100 mmol of 3,8-dibromodibenzofuran, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M5. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M4.

100 mmol of M5, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to the reaction flask, and the reaction was carried out at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M6. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M5.

100 mmol of M6, 100 mmol of 5-chlorophenanthroline, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A32. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M6.

¹ H NMR(400MHz,Chloroform)8.74(d,J＝11.2Hz,2H),8.17–8.08(m,4H),7.99(s,1H),7.96(d,J＝8.4Hz,4H),7.90( d,J＝7.2Hz,3H),7.70(s,1H),7.59(d,J＝10.0Hz,6H),7.42-7.32(m,7H).

Synthesis of compound A33:

100 mmol of 5-chloro-o-phenanthroline, 100 mmol of m-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of 5-chloro-o-phenanthroline.

100 mmol of M1, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane, and 1 mol% of Pd(PPh ₃ ) ₄ were added to a reaction flask, and the mixture was reacted at 100° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was recrystallized and purified with toluene to obtain white powder M2. The amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M1.

100 mmol of M2, 100 mmol of 3,5-dibromobenzonitrile, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water were added to a reaction flask, and 1 mol% of Pd(PPh ₃ ) ₄ was added, and the reaction was carried out at 60° C. for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A33. Among them, the amount of Pd(PPh ₃ ) ₄ added was 1 mol% of M2.

¹ H NMR (400MHz, Chloroform)8.74(d,J＝10.0Hz,4H),8.38(s,1H),8.17(s,1H),8.13–8.07(m,6H),7.88-7.70(m,5H) ),7.61(d,J＝10.0Hz,4H),7.39(d,J＝10.0Hz,4H).

Other compounds of the present application can be synthesized by selecting appropriate raw materials according to the ideas of synthesizing compounds A1, A4, A6, A8, A11, A15, A21, A26, A31, A32 or A33 mentioned above, or by selecting any other suitable methods and raw materials for synthesis.

Example 1

A glass plate coated with a 150 nm thick ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone-ethanol mixed solvent, baked in a clean environment to completely remove water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

Then, the glass substrate with the anode is placed in a vacuum chamber, and the vacuum is evacuated to less than 10 ^-5 Torr. A hole injection layer is vacuum-deposited on the anode layer. The hole injection layer includes hole injection layer material HT-11 and p-type dopant p-1. The evaporation is performed by a multi-source co-evaporation method. The evaporation rate of the hole injection layer material HT-11 is adjusted to 0.1 nm/s, the evaporation rate of the p-type dopant p-1 is 3% of the evaporation rate of the hole injection layer material HT-11, and the evaporation film thickness is 10 nm. The hole injection layer material HT-11 and the p-type dopant p-1 are as follows:

Then, a hole transport material HT-5 was vacuum-deposited on the hole injection layer as a hole transport layer, wherein the evaporation rate was 0.1 nm/s, the evaporation film thickness was 80 nm, and the hole transport material HT-5 was as follows:

Then, a light-emitting layer is vacuum-deposited on the hole transport layer. The light-emitting layer includes a main material BH-2 and a guest material BD-1. The evaporation is performed by a multi-source co-evaporation method. The evaporation rate of the main material BH-2 is adjusted to 0.1 nm/s, the evaporation rate of the guest material BD-1 is adjusted to 3% of the evaporation rate of the main material BH-2, and the evaporation film thickness is 30 nm. The main material BH-2 and the guest material BD-1 are as follows:

Then, an electron transport layer is vacuum evaporated on the light-emitting layer, and the electron transport material is the compound A1 provided in the present application, wherein the evaporation rate is 0.1 nm/s and the evaporation film thickness is 30 nm; the electron transport material A1 is as follows:

Then, LiF with a thickness of 5 nm was vacuum-deposited on the electron transport layer as an electron injection layer, wherein the evaporation rate was 0.1 nm/s;

Finally, an Al layer with a thickness of 150 nm was vacuum evaporated on the electron injection layer as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate was 0.1 nm/s.

Example 2-11

Except that the electron transport material is replaced by compound A4, A6, A8, A11, A15, A21, A26, A31, A32 or A33 instead of compound A1, the rest is the same as Example 1. See Table 1 for details.

Comparative Example 1

Except that ET-11 is selected as the electron transport material, the rest is the same as Example 1; ET-11 is as follows:

The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

At the same brightness, the driving voltage, current efficiency and device life of the organic electroluminescent devices prepared in Examples 1-11 and Comparative Example 1 were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the voltage when the brightness of the organic electroluminescent device reached 1000 cd/ ^m2 , i.e., the driving voltage, was measured, and the current density at this time was measured; the ratio of the brightness to the current density was the current efficiency; the life test of LT95 was as follows: the brightness meter was used to maintain a constant current at a brightness of 1000 cd/ ^m2 , and the time in hours for the brightness of the organic electroluminescent device to drop to 950 cd/ ^m2 was measured. The results are shown in Table 1.

Table 1 Performance results of organic electroluminescent devices

As can be seen from Table 1, the organic electroluminescent devices prepared in Examples 1 to 11 use the compounds A1, A4, A6, A8, A11, A15, A21, A26, A31, A32 or A33 provided in the present application as electron transport materials. Compared with the known materials in the prior art used in Comparative Example 1 as electron transport materials for organic electroluminescent devices, the organic electroluminescent devices of the present application have lower driving voltages, higher current efficiency and longer LT95 lifespans. Thus, it is shown that the compounds A1, A4, A6, A8, A11, A15, A21, A26, A31, A32 or A33 prepared in the present application are used as electron transport materials for organic electroluminescent devices, which can effectively reduce driving voltages, improve current efficiency and extend device lifespans.

Example 12

A glass plate coated with a 150 nm thick ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone-ethanol mixed solvent, baked in a clean environment to completely remove water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

Then, the glass substrate with the anode is placed in a vacuum chamber, and the vacuum is evacuated to less than 10 ^-5 Torr. A first hole injection layer is vacuum-deposited on the anode layer. The material of the first hole injection layer includes hole injection layer material HT-11 and p-type dopant p-1. The evaporation is performed by a multi-source co-evaporation method. The evaporation rate of the hole injection layer material HT-11 is adjusted to 0.1 nm/s, and the evaporation rate of the p-type dopant p-1 is 3% of the evaporation rate of the hole injection layer material HT-11. The evaporation film thickness is 10 nm. The hole injection layer material HT-11 and the p-type dopant p-1 are as follows:

Then, a hole transport material HT-5 was vacuum-deposited on the first hole injection layer as the first hole transport layer, wherein the evaporation rate was 0.1 nm/s, the evaporation film thickness was 80 nm, and the hole transport material HT-5 was as follows:

Then, a first light-emitting layer is vacuum-deposited on the first hole transport layer. The first light-emitting layer includes a main material BH-2 and a guest material BD-1. The deposition is performed by a multi-source co-evaporation method. The deposition rate of the main material BH-2 is adjusted to 0.1 nm/s, the deposition rate of the guest material BD-1 is adjusted to 3% of the deposition rate of the main material BH-2, and the deposition film thickness is 30 nm. The main material BH-2 and the guest material BD-1 are as follows:

Then, a first electron transport layer is vacuum-deposited on the first light-emitting layer, wherein the electron transport material is compound ET-11, wherein the evaporation rate is 0.1 nm/s, and the evaporation film thickness is 30 nm; the electron transport material ET-11 is as follows:

The first hole injection layer, the first hole transport layer, the first light-emitting layer and the first electron transport layer together constitute a first light-emitting unit;

On the topmost first electron transport layer of the first light-emitting unit, the compound A1 provided by the present application and metal ytterbium (Yb) are evaporated to form a charge generation layer, wherein the evaporation rate of the compound A1 is 0.1 nm/s, the evaporation rate ratio of the compound A1 to Yb is 99:1, and the evaporation film thickness is 10 nm;

A second hole injection layer is evaporated on the charge generation layer, wherein the material of the second hole injection layer includes hole injection layer material HT-11 and p-type dopant p-1, wherein the evaporation rate of the hole injection layer material HT-11 is adjusted to 0.1 nm/s, the evaporation rate ratio of the hole injection layer material HT-11 to the p-type dopant p-1 is 99:1, and the evaporated film thickness is 10 nm;

Then, a hole transport material HT-5 was vacuum-deposited on the second hole injection layer as a second hole transport layer, wherein the evaporation rate was 0.1 nm/s and the evaporation film thickness was 80 nm;

Then, a second light-emitting layer is vacuum-evaporated on the second hole transport layer, wherein the second light-emitting layer includes a main material BH-2 and a guest material BD-1, and the evaporation is performed by a multi-source co-evaporation method, wherein the evaporation rate of the main material BH-2 is adjusted to 0.1 nm/s, the evaporation rate of the guest material BD-1 is adjusted to 3% of the evaporation rate of the main material BH-2, and the evaporation film thickness is 30 nm;

Then, a second electron transport layer is vacuum-deposited on the second light-emitting layer, wherein the electron transport material is compound ET-11, wherein the evaporation rate is 0.1 nm/s and the evaporation film thickness is 30 nm;

The second hole injection layer, the second hole transport layer, the second light-emitting layer and the second electron transport layer together constitute a second light-emitting unit;

Then, LiF with a thickness of 5 nm was vacuum-deposited on the second electron transport layer at the top of the second light-emitting unit as an electron injection layer, wherein the evaporation rate was 0.1 nm/s;

Finally, an Al layer with a thickness of 150 nm was vacuum evaporated on the electron injection layer as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate was 0.1 nm/s.

Examples 13-22

Except that the charge generation layer uses compound A4, A6, A8, A11, A15, A21, A26, A31, A32 or A33 instead of compound A1, the rest is the same as Example 12. See Table 2 for details.

Comparative Example 2

Except that the charge generating material is CGL00R1 instead of compound A1, the rest is the same as Example 12; CGL00R1 is as follows:

The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

At the same brightness, the driving voltage, current efficiency and device life of the organic electroluminescent devices prepared in Examples 12-22 and Comparative Example 2 were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the voltage when the brightness of the organic electroluminescent device reached 1000 cd/ ^m2 , i.e., the driving voltage, was measured, and the current density at this time was measured; the ratio of the brightness to the current density was the current efficiency; the life test of LT95 was as follows: the brightness meter was used to maintain a constant current at a brightness of 1000 cd/ ^m2 , and the time in hours for the brightness of the organic electroluminescent device to drop to 950 cd/ ^m2 was measured. The results are shown in Table 2.

Table 2 Performance results of organic electroluminescent devices

As can be seen from Table 2, the organic electroluminescent devices prepared in Examples 12 to 22 use the compounds A1, A4, A6, A8, A11, A15, A21, A26, A31, A32 or A33 provided in the present application as charge generating materials. Compared with the known materials in the prior art used in Comparative Example 2 as charge generating materials for organic electroluminescent devices, the organic electroluminescent devices of the present application have lower driving voltages, higher current efficiency and longer LT95 lifespans. This shows that the compounds A1, A4, A6, A8, A11, A15, A21, A26, A31, A32 or A33 prepared in the present application are used as charge generating materials for organic electroluminescent devices, which can effectively reduce driving voltages, improve current efficiency and extend device lifespans.

It can be understood that the organic electroluminescent devices in Examples 1 to 22 are blue organic electroluminescent devices, and the above examples are only examples. The compounds provided in the present application are used as electron transport materials or charge generating materials, and can also be applied to red organic electroluminescent devices and green organic electroluminescent devices to reduce the driving voltage of red organic electroluminescent devices and green organic electroluminescent devices, improve their luminous efficiency, and extend their service life.

The above description is only a preferred embodiment of the present application and is not intended to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (10)

1. A compound of formula (I):

wherein,

Q ¹ and Q ² Each independently selected from:

Q ¹ the hydrogen atoms of the radicals may each independently be replaced by R ₁ Substitution, said R ₁ Selected from C ₁ -C ₄ Alkyl, C unsubstituted or substituted by Rc ₆ -C ₃₀ Aryl, C unsubstituted or substituted by Rc ₃ -C ₃₀ Heteroaryl;

Q ² the hydrogen atoms of the radicals may each independently be replaced by R ₂ Substitution, said R ₂ Selected from C ₁ -C ₄ Alkyl, C unsubstituted or substituted by Rc ₆ -C ₃₀ Aryl, C unsubstituted or substituted by Rc ₃ -C ₃₀ Heteroaryl;

L ¹ and L ² Each independently selected from the group consisting of a bond, C which is unsubstituted or substituted with Rc ₆ -C ₃₀ Arylene, C unsubstituted or substituted with Rc ₃ -C ₃₀ Heteroarylene;

m is selected from

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

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

2. The compound of claim 1, wherein said R ₁ And R is ₂ Each independently selected from C ₁ -C ₄ Alkyl, C unsubstituted or substituted by Rc ₆ -C ₁₈ Aryl, C unsubstituted or substituted by Rc ₃ -C ₁₈ Heteroaryl groups.

3. The compound of claim 1, wherein L ¹ And L ² Each independently selected from the group consisting of a bond, C which is unsubstituted or substituted with Rc ₆ -C ₁₈ Arylene, C unsubstituted or substituted with Rc ₃ -C ₁₈ Heteroarylene group.

4. The compound of claim 1, wherein said R ₁ And R is ₂ Each independently selected from methyl, ethyl, isopropyl, tert-butyl, unsubstituted or substituted with RcThe following 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, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl.

5. The compound of claim 1, wherein L ¹ And L ² Each independently selected from the group consisting of a bond, a subunit of the following compounds unsubstituted or substituted with Rc: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thiophene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene.

6. The compound of claim 1, wherein the compound is selected from the group consisting of the compounds shown in A1 to a33 below:

7. an electron transport material comprising at least one of the compounds of any one of claims 1-6.

8. A charge generating material comprising at least one of the compounds of any one of claims 1-6.

9. An organic electroluminescent device comprising at least one of the electron transporting material of claim 7 or the charge generating material of claim 8.

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