A compound containing dibenzoquinoxaline and an organic electroluminescence device

Abstract

This application provides a compound containing dibenzoquinoxaline, the structure of which is shown in formula (I). It has a parent structure substituted with dibenzoquinoxaline, exhibiting efficient charge generation and charge transport properties. When used as a charge generation material, it can effectively improve the luminous efficiency of organic light-emitting devices (OLEDs), reduce the driving voltage of OLEDs, and minimize voltage fluctuations under constant current conditions. This can delay the aging of OLEDs, improve their operating efficiency, and extend their lifespan. This application also provides an organic light-emitting device and a display device comprising the above compound.

Description

Technical Field

[0001] This application relates to the field of organic light-emitting display technology, and in particular to a compound containing dibenzoquinoxaline and an organic electroluminescent device. Background Technology

[0002] Organic electroluminescent materials include those used in single organic electroluminescent devices (OLEDs) and those used in stacked OLEDs. Stacked OLEDs are formed by connecting multiple individual OLEDs in series through a charge generation layer. The stacked structure of stacked OLEDs can effectively improve the device's lifetime, thus becoming a research hotspot in recent years. For stacked OLEDs, the charge generation layer is a key material affecting its driving voltage and operating efficiency. Therefore, developing high-efficiency charge generation materials that can reduce the driving voltage of stacked OLEDs has become a key research focus in this field. Summary of the Invention

[0003] The purpose of this application is to provide a compound containing dibenzoquinoxaline and an organic electroluminescent device and display device containing the same. When the compound is used as a charge-generating material, it can reduce the driving voltage of the organic electroluminescent device, improve its operating efficiency, and extend its service life.

[0004] The first aspect of this application provides a compound containing dibenzoquinoxaline, as shown in formula (I):

[0005]

[0006] in,

[0007] L is selected from the chemically bonded, unsubstituted, or Ra-substituted groups shown in L1 to L4:

[0008]

[0009] When L is selected from a chemical bond, R is selected from the unsubstituted or Ra-substituted groups shown in R1 to R9:

[0010]

[0011] When L is selected from the unsubstituted or Ra-substituted groups shown in L1 to L4

[0012] R is selected from hydrogen, deuterium, C1-C4 alkyl, unsubstituted or Ra-substituted groups shown in R1 to R9:

[0013]

[0014] Each of the Ra is independently selected from hydrogen, deuterium, C1-C6 alkyl, phenyl, biphenyl, terphenyl, pyrimidinyl, naphthyl, pyridinyl, or 2-phenylpyridinyl.

[0015] A second aspect of this application provides a charge-generating material comprising at least one of the compounds provided in the first aspect of this application.

[0016] A third aspect of this application provides an organic electroluminescent device comprising a charge generation layer comprising at least one of the charge generation materials provided in the second aspect of this application.

[0017] A fourth aspect of this application provides a display device that includes the organic electroluminescent device provided in the third aspect of this application.

[0018] The compound provided in this application has a substituted dibenzoquinoxaline parent structure, exhibiting highly efficient charge generation and electron transport properties. When used as a charge-generating material, it can effectively improve the luminous efficiency of organic light-emitting diodes (OLEDs), while simultaneously reducing the driving voltage, thus increasing the operating efficiency and extending the lifespan of OLEDs. Furthermore, the charge-generating material used in this application also possesses high interatomic bond energy, a large conjugated plane, good thermal stability, and is conducive to solid-state molecular stacking, enabling it to achieve good luminous efficiency, reduce the driving voltage, and extend the lifespan of OLEDs. The display device provided in this application exhibits excellent display performance.

[0019] Of course, implementing any product or method of this application does not necessarily require achieving all of the advantages described above at the same time. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other embodiments can be obtained based on these accompanying drawings.

[0021] Figure 1 This is a schematic diagram of a typical organic electroluminescent device. Detailed Implementation

[0022] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. All other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0023] The first aspect of this application provides a compound containing dibenzoquinoxaline, as shown in formula (I):

[0024]

[0025] in,

[0026] L is selected from the chemically bonded, unsubstituted, or Ra-substituted groups shown in L1 to L4:

[0027]

[0028] When L is selected from a chemical bond, R is selected from the unsubstituted or Ra-substituted groups shown in R1 to R9:

[0029]

[0030] When L is selected from the unsubstituted or Ra-substituted groups shown in L1 to L4

[0031] R is selected from hydrogen, deuterium, C1-C4 alkyl, unsubstituted or Ra-substituted groups shown in R1 to R9:

[0032]

[0033] Each of the Ra is independently selected from hydrogen, deuterium, C1-C6 alkyl, phenyl, biphenyl, terphenyl, pyrimidinyl, naphthyl, pyridinyl, or 2-phenylpyridinyl.

[0034] Preferably, each Ra is independently selected from hydrogen or groups shown in Ra1 to Ra5:

[0035]

[0036] In one embodiment of this application, the compound is selected from the compounds shown in A1 to A20 below:

[0037]

[0038] The compound provided in this application has a substituted dibenzoquinoxaline parent structure, exhibiting efficient charge generation capability and efficient electron transport performance. When used as a charge generation material, it can effectively improve the luminous efficiency of organic electroluminescent devices, while reducing the driving voltage of organic electroluminescent devices and extending the service life of organic electroluminescent devices.

[0039] A second aspect of this application provides a charge-generating material comprising at least one of the compounds provided in the first aspect of this application.

[0040] The charge-generating material provided in this application can be used in organic electroluminescent devices to effectively improve the luminous efficiency of organic electroluminescent devices, reduce the driving voltage of organic electroluminescent devices, and extend the service life of organic electroluminescent devices.

[0041] A third aspect of this application provides an organic electroluminescent device comprising a charge generation layer comprising at least one of the charge generation materials provided in the second aspect of this application.

[0042] In one embodiment of this application, the charge generation layer comprises the charge generation material and a metal-containing material, wherein the content of the metal-containing material accounts for 0.5%-2.5% of the charge generation layer content; the metal-containing material is selected from at least one of a metal or a metal complex; the metal is selected from at least one of lithium (Li) or ytterbium (Yb), and the metal complex is selected from at least one of lithium 8-hydroxyquinoline (LiQ) or aluminum 8-hydroxyquinoline (AlQ3).

[0043] In one embodiment of this application, the thickness of the charge generation layer is 10nm-30nm.

[0044] In one embodiment of this application, the organic electroluminescent device is a multilayer organic electroluminescent device. The charge-generating material used in this application possesses high interatomic bond energy, a large conjugated plane, good thermal stability, and is conducive to solid-state molecular stacking. This allows for good luminous efficiency, reduced driving voltage, and extended lifespan in the multilayer organic electroluminescent device. Therefore, the multilayer organic electroluminescent device provided by this application has low driving voltage, high luminous efficiency, and a long lifespan.

[0045] In this application, there are no particular restrictions on the type and structure of organic electroluminescent devices. They can be organic electroluminescent devices of different types and structures known in the art, as long as at least one of the charge-generating materials provided in this application can be used.

[0046] In one embodiment of this application, the organic electroluminescent device includes an anode and a cathode, with m light-emitting units stacked between the anode and the cathode, and m-1 charge-generating layers between two adjacent light-emitting units. Each charge-generating layer includes an n-type charge-generating layer and a p-type charge-generating layer, where m is an integer ≥2. Each light-emitting unit includes at least one light-emitting layer, and the maximum emission wavelength of the light emitted in different light-emitting units is different. At least one of the n-type charge-generating layers includes at least one compound of formula (I) and a metal-containing material, wherein the metal-containing material includes metals, metal complexes, or combinations thereof.

[0047] In one embodiment of this application, the light-emitting unit in the organic electroluminescent device may include a first light-emitting unit and a second light-emitting unit, which may be the same or different; a charge generation layer may be disposed between the first light-emitting unit and the second light-emitting unit, the first light-emitting unit may be disposed between the anode and the charge generation layer, and the second light-emitting unit may be disposed between the charge generation layer and the cathode. The n-type charge generation layer of the charge generation layer may include at least one compound of formula (I) and a metal-containing material.

[0048] In one embodiment of this application, in an organic electroluminescent device with two light-emitting units, the first light-emitting unit may further include a hole transport (HT)-light-emitting auxiliary layer between the light-emitting layer and the anode of the first light-emitting unit, and the electron transport layer included in the first light-emitting unit may be the same as or different from the electron transport layer included in the second light-emitting unit.

[0049] In one embodiment of this application, the charge-generating material of this application is applied in an organic electroluminescent device. The organic electroluminescent device can be a top-emitting structure, which may include, in order on a substrate, an anode, a first light-emitting unit, a charge-generating layer, a second light-emitting unit, an electron injection layer, and a transparent or semi-transparent cathode.

[0050] The organic electroluminescent device of this application uses the charge generating material of this application in the organic electroluminescent device. The organic electroluminescent device can also be a bottom-emitting structure, which can be exemplified by having a transparent or semi-transparent anode, a first light-emitting unit, a charge generating layer, a second light-emitting unit, an electron injection layer, and a cathode sequentially on a substrate.

[0051] The organic electroluminescent device of this application uses the charge generating material of this application in the organic electroluminescent device. The organic electroluminescent device can also be a light-emitting device with a dual-sided light-emitting structure. For example, it can be a substrate that sequentially includes a transparent or semi-transparent anode, a first light-emitting unit, a charge generating layer, a second light-emitting unit, an electron injection layer, and a transparent or semi-transparent cathode.

[0052] The first light-emitting unit includes a first hole injection layer, 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 injection layer, a second hole transport layer, a second light-emitting layer and a second electron transport layer arranged in sequence.

[0053] Furthermore, the organic electroluminescent device of this application may have an electron blocking layer between the hole transport layer and the light-emitting layer, and a hole blocking layer between the light-emitting layer and the electron transport layer. A light extraction layer may be disposed on the transparent electrode on the light-emitting side. However, the structure of the organic electroluminescent device of this application is not limited to the specific structure described above. If necessary, the aforementioned layers may be omitted or added. This application does not impose any particular limitation on the thickness of the aforementioned anode, hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, electron injection layer, cathode, and light extraction layer, as long as the purpose of this application can be achieved. For example, an organic electroluminescent device may sequentially comprise, on a substrate, an anode (100nm to 150nm) made of metal, a first hole injection layer (5nm to 20nm), a first hole transport layer (80nm to 140nm), an electron blocking layer (5nm to 20nm), a first light-emitting layer (15nm to 40nm), a hole blocking layer (5nm to 20nm), a first electron transport layer (10nm to 40nm), a charge generation layer (10nm to 30nm), a second hole injection layer (5nm to 20nm), a second hole transport layer (80nm to 140nm), a second light-emitting layer (15nm to 40nm), a second electron transport layer (10nm to 40nm), an electron injection layer (5nm to 20nm), a transparent or semi-transparent cathode (100nm to 160nm), and a light extraction layer (50nm to 90nm). Exemplarily, Figure 1 A schematic diagram of a typical organic electroluminescent device 20 is shown, wherein, 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 electrode 28 are arranged sequentially.

[0054] Understandable. Figure 1 The structure of a typical organic electroluminescent device is shown only schematically. This application is not limited to this structure, and the charge-generating material of this application can be used in any type of organic electroluminescent device.

[0055] For convenience, the organic electroluminescent device of this application is described below, but this does not imply any limitation on the scope of protection of this application. It is understood that all organic electroluminescent devices capable of using the charge-generating materials of this application are within the scope of protection of this application.

[0056] In this application, there are no particular limitations on the substrate 21. Conventional substrates used in organic electroluminescent devices in the prior art can be used, such as glass, polymer materials, and glass and polymer materials with thin-film transistor (TFT) components.

[0057] In this application, there are no particular restrictions on the material of the reflective anode 22. It can be selected from transparent conductive materials known in the prior art such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO), or metallic materials such as silver and its alloys, aluminum and its alloys, or organic conductive materials such as poly(3,4-ethylenedioxythiophene) (PEDOT). Alternatively, the reflective anode 22 can be a multilayer structure formed from the above materials. This application does not have any particular restrictions on the number of layers in the multilayer structure. The number of layers can be selected according to actual needs, as long as it meets the purpose of this application. For example, one layer, two layers, three layers, or more layers.

[0058] In this application, there are no particular limitations on the materials of the first hole injection layer 23a and the second hole injection layer 23b. They can be made of hole injection materials or hole transport materials (HTMs) known in the art. For example, at least one known HTM can be selected as the hole injection material.

[0059] In this application, the first hole injection layer 23a and the second hole injection layer 23b may each include a p-type dopant. There is no particular limitation on the type of p-type dopant, and various p-type dopants known in the art can be used. For example, the p-type dopant may be selected from, but is not limited to, at least one of the following p-1 to p-3 compounds:

[0060]

[0061] In this application, there are no particular restrictions on the amount of p-type dopant used, and the amount can be any amount known to those skilled in the art.

[0062] In this application, there are no particular restrictions on the materials of the first hole transport layer 24a and the second hole transport layer 24b, and they can be made using HTM materials known in the art. There are no particular restrictions on the number of layers of the first hole transport layer 24a and the second hole transport layer 24b, and they can be adjusted according to actual needs, as long as the purpose of this application is met; for example, one, two, three, four, or more layers.

[0063] For example, HTM for hole injection materials and HTM for hole transport materials may be selected from, but not limited to, at least one of the following HT-1 to HT-31 compounds:

[0064]

[0065]

[0066] In this application, there are no particular restrictions on the materials of the first light-emitting layer 25a and the second light-emitting layer 25b. Each of them may contain a main material for the light-emitting layer and a guest material for the light-emitting layer. There are no particular restrictions on the amount of the main material for the light-emitting layer and the guest material for the light-emitting layer. They may be amounts known to those skilled in the art.

[0067] In this application, there are no particular limitations on the host materials of the first luminescent layer 25a and the second luminescent layer 25b; at least one of the red luminescent layer host materials known in the art can be used. For example, at least one of the following RH-1 to RH-13 compounds can be selected:

[0068]

[0069] The host material for the luminescent layer can also be at least one of the green luminescent layer host materials known in the art. For example, it can be at least one of the following GPH-1 to GPH-80 compounds:

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076] The host material for the luminescent layer can also be at least one of the blue luminescent layer host materials known in the art. For example, it can be at least one of the following compounds, but not limited to: BH-1 to BH-10.

[0077]

[0078] In this application, there are no particular limitations on the guest materials of the first luminescent layer 25a and the second luminescent layer 25b, and at least one of the red luminescent layer guest materials known in the art can be used. For example, at least one of the following compounds, but not limited to RPD-1 to RPD-28, can be used:

[0079]

[0080]

[0081] The luminescent layer guest material can be a green luminescent layer guest material, for example, it can be selected from at least one of the following GD01 to GD04 compounds:

[0082]

[0083] The luminescent layer guest material can be a blue luminescent layer guest material. For example, the luminescent layer guest material can be selected from, but is not limited to, at least one of the following BD-1 to BD-9 compounds:

[0084]

[0085] In this application, there are no particular restrictions on the amount of the luminescent layer guest material, and it can be any amount known to those skilled in the art.

[0086] In this application, there are no particular limitations on the materials of the first electron transport layer 26a and the second electron transport layer 26b, and they can be made of electron transport materials known in the art. There are no particular limitations on the number of layers of the first electron transport layer 26a and the second electron transport layer 26b, and they can be adjusted according to actual needs, as long as they can meet the purpose of this application, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.

[0087] For example, the electron transport material may be selected from, but is not limited to, at least one of the following ET-1 to ET-57 compounds:

[0088]

[0089]

[0090]

[0091]

[0092] In this application, the first electron transport layer 26a and the second electron transport layer 26b may each include an n-type dopant. There is no particular limitation on the type of n-type dopant, and various n-type dopants known in the art can be used, such as the following n-type dopant (LiQ):

[0093]

[0094] In this application, there are no particular restrictions on the amount of n-type dopant used, and the amount can be any amount known to those skilled in the art.

[0095] In this application, the charge generation layer 29 comprises at least one of the charge generation materials of this application, or may comprise a combination of at least one of the charge generation materials of this application and at least one of the following known charge generation materials.

[0096] For example, known charge-generating materials may be selected from, but are not limited to, at least one of the following CGL00R1 to CGL00R5 compounds:

[0097]

[0098] In this application, the charge generation layer may further include at least one of the following metals: Li, Yb.

[0099] In this application, there are no particular restrictions on the material of the electron injection layer 27. Known electron injection materials in the art can be used, such as at least one of the following materials in the prior art: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, etc.

[0100] In this application, there are no particular restrictions on the material of the cathode electrode 28, which can be selected from, but is not limited to, magnesium-silver mixtures (Mg / Ag), mixtures of lithium fluoride and aluminum (LiF / Al), ITO, Al and other metals, metal mixtures, oxides and the like.

[0101] There are no particular limitations on the method for preparing the organic electroluminescent device of this application; any method known in the art can be used. For example, the method for preparing the organic electroluminescent device of this application may include, but is not limited to, the following steps:

[0102] (1) Clean the reflective anode 22 on the substrate 21 of the top-emitting organic electroluminescent device 20. In the cleaning machine, the device undergoes chemical washing, water washing, brushing, high-pressure water washing, air knife and other steps, and then heat treatment.

[0103] (2) Hole injection material is vacuum-deposited on the reflective anode 22 as the first hole injection layer 23a;

[0104] (3) Hole transport material is vacuum-deposited on the first hole injection layer 23a to serve as the first hole transport layer 24a;

[0105] (4) A first light-emitting layer 25a is vacuum-deposited on the first hole transport layer 24a. The first light-emitting layer contains a light-emitting layer host material and a light-emitting layer guest material.

[0106] (5) Vacuum evaporation of electron transport material on the first light-emitting layer 25a serves as the first electron transport layer 26a;

[0107] (6) A charge generation material is vacuum-deposited on the first electron transport layer 26a as a charge generation layer 29;

[0108] (7) Hole injection material is vacuum-deposited on charge generation layer 29 as second hole injection layer 23b;

[0109] (8) Vacuum evaporation of hole transport material on the second hole injection layer 23b serves as the second hole transport layer 24b;

[0110] (9) Vacuum evaporation is performed on the second hole transport layer 24b to deposit a second light-emitting layer 25b, the second light-emitting layer containing a light-emitting layer host material and a light-emitting layer guest material;

[0111] (10) Vacuum evaporation of electron transport material on the second light-emitting layer 25b serves as the second electron transport layer 26b;

[0112] (11) Vacuum evaporation of electron injection material on the second electron transport layer 26b serves as electron injection layer 27;

[0113] (12) A cathode material is vacuum-deposited on the electron injection layer 27 as a cathode electrode 28.

[0114] The above describes only a typical structure and fabrication method of an organic electroluminescent device. It should be understood that this application is not limited to this structure. The charge-generating material of this application can be used in organic electroluminescent devices of any structure, and the organic electroluminescent device can be fabricated using any fabrication method known in the art.

[0115] A fourth aspect of this application provides a display device comprising the organic electroluminescent devices provided in the third aspect of this application. The display device includes, but is not limited to, a monitor, a television, a tablet computer, a mobile communication terminal, etc.

[0116] There are no particular limitations on the synthesis method of the compounds in this application; any method known to those skilled in the art can be used for synthesis. The following examples illustrate the synthesis process of the compounds in this application. As used herein, room temperature / normal temperature refers to 25±5℃.

[0117] Synthesis example

[0118] Synthesis of compound A1

[0119]

[0120] Under nitrogen protection, 400 mL of dioxane, 80 mL of water, 100 mmol of 2,9-dichloro-1,10-phenanthroline (CAS No.: 29176-55-4), 100 mmol of phenylboronic acid, 1.0 mol% tris(dibenzylacetone)dipalladium (bispalladium) in molar amount of 2,9-dichloro-1,10-phenanthroline, 100 mmol of tricyclohexylphosphine, and 41.4 g (300 mmol) of potassium carbonate were added to the reaction flask, and the reaction was carried out at 110 °C for 4.5 h. After the reaction was complete, the mixture was cooled to room temperature, 400 mL of water was added, and the mixture was stirred for 30 minutes. Then, 400 mL of dichloromethane (DCM) was added and stirred for 30 minutes. The mixture was separated, and the aqueous phase was extracted with DCM. The separated and extracted organic phases were combined, washed with 800 mL of water, and the washed organic phase was evaporated to dryness. 300 mL of DCM was added to the resulting solid, and the mixture was passed through a silica gel column (using a solvent with a volume ratio of petroleum ether to ethyl acetate of 50:1, 200 mesh). The resulting solution was evaporated to dryness and dried to obtain a white solid M1.

[0121] Under nitrogen protection, 1300 mL of xylene, 100 mmol of M1, 29.4 g (300 mmol) of potassium acetate, 1.0 mol% of bis-palladium (M1), 1.5 mol% of 2-biscyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos) (M1), and 100 mmol of pinacol diborate were added to a reaction flask, and the reaction was carried out at 140 °C for 8 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, and the mixture was separated. The organic phase obtained from the separation was washed with water, and the aqueous phases obtained from the separation and washing were combined. The combined aqueous phases were extracted with ethyl acetate (EA). The combined organic phases obtained from the washing and extraction were combined and rotary evaporated to dryness. DCM was added to dissolve the product, and the solution was passed through a silica gel column (solvent with a volume ratio of petroleum ether to ethyl acetate of 50:1, 200 mesh). The organic phase was rotary evaporated and dried for 8 h to obtain a white solid M2.

[0122] 100 mmol of 3-bromo-9,10-phenanthrenequinone (CAS No.: 13292-05-2), 1000 mmol of hydroxylamine hydrochloride, 50 mL of pyridine, and 1000 mL of ethanol were added to a reaction flask. The mixture was heated to reflux at 100 °C for 8 h. Then, 500 mL of 10% hydrochloric acid was added to the reaction solution, and the mixture was stirred until homogeneous. A solid precipitated out and was filtered to obtain a solid. This solid was added to a reaction flask, and 1000 mmol of zinc powder and 1000 mmol of ammonium chloride were added. The mixture was then dissolved in 1000 mL of ethanol and heated to reflux at 100 °C for 3 h. After the reaction was complete, the mixture was filtered, and the filtrate was concentrated to obtain a solid. 100 mL of ethylene oxalate was added, and the mixture was heated to 130 °C for 3 h. After the reaction was complete, the reaction solution was added to ethanol, and a solid precipitated out. The obtained solid was recrystallized from ethanol to obtain M3.

[0123] 100 mmol of M2, 100 mmol of M3, 41.4 g (300 mmol) of potassium carbonate, 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1.0 mol% tetra(triphenylphosphine)palladium (Pd(PPh3)4) of M2. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4.

[0124] Add 10 mmol of M4 to the reaction flask and dissolve it in 200 mL of DMF. At room temperature, add 100 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 1000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M5.

[0125] 100 mmol of M5, 200 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M5. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, Al.

[0126] 1 H NMR (400MHz, Chloroform-d) δ9.61(s,1H),8.93(s,1H),8.51-8.41(m,3H),8.33-8.16(m,2H),8.08-7.90(m,10H),7.66-7.38(m,7H),7.24(m,4H).

[0127] M / Z: Experimental value, 638.24; Theoretical value, 637.23.

[0128] Synthesis of compound A2

[0129]

[0130] Under nitrogen protection, 400 mL of dioxane, 80 mL of water, 100 mmol of 2,9-dichloro-1,10-phenanthroline, 100 mmol of phenylboronic acid, 1.0 mol% tris(dibenzylacetone)dipalladium (molar amount of 2,9-dichloro-1,10-phenanthroline), 100 mmol of tricyclohexylphosphine, and 41.4 g (300 mmol) of potassium carbonate were added to the reaction flask, and the reaction was carried out at 110 °C for 4.5 h. After the reaction was complete, the mixture was cooled to room temperature, 400 mL of water was added, and the mixture was stirred for 30 minutes. Then, 400 mL of DCM was added and stirred for another 30 minutes. The mixture was separated, and the aqueous phase was extracted with DCM. The separated and extracted organic phases were combined, washed with 800 mL of water, and the washed organic phase was evaporated to dryness. 300 mL of DCM was added to the resulting solid, and the mixture was passed through a silica gel column (using a solvent with a volume ratio of petroleum ether to ethyl acetate of 50:1, 200 mesh). The resulting solution was evaporated to dryness and dried to obtain a white solid M1.

[0131] 100 mmol of M1, 100 mmol of 4-bromophenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M1. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2.

[0132] 100 mmol of M2, 100 mmol of pinacol diborate, 29.4 g (300 mmol) of potassium acetate, and 800 mL of dioxane were added to a reaction flask, along with 1.0 mol% of dichloro(1,1'-bis(diphenylphosphine)ferrocene)palladium (Pd(dppf)Cl2) in the molar amount of M2. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4.

[0133] 100 mmol of 3-bromo-9,10-phenanthrenequinone, 1000 mmol of hydroxylamine hydrochloride, 50 mL of pyridine, and 1000 mL of ethanol were added to a reaction flask. The mixture was heated to reflux at 100 °C for 8 h. Then, 500 mL of 10% hydrochloric acid was added to the reaction solution, and the mixture was stirred until homogeneous. A solid precipitated out and was filtered to obtain a solid. This solid was added to a reaction flask, and 1000 mmol of zinc powder and 1000 mmol of ammonium chloride were added. The mixture was then dissolved in 1000 mL of ethanol and heated to reflux at 100 °C for 3 h. After the reaction was complete, the mixture was filtered, and the filtrate was concentrated to obtain a solid. 100 mL of ethylene oxalate was added, and the mixture was heated to 130 °C for 3 h. After the reaction was complete, the reaction solution was added to ethanol, and a solid precipitated out. The obtained solid was recrystallized from ethanol to obtain M3.

[0134] 100 mmol of M3, 100 mmol of M4, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% (Pd(PPh3)4) of M4. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M5.

[0135] Add 10 mmol of M5 to the reaction flask and dissolve it in 200 mL of DMF. At room temperature, add 100 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 1000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M6.

[0136] 100 mmol of M6, 200 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M6. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder A2.

[0137] 1 H NMR(400MHz,Chloroform-d)δ9.00(s,1H),8.69-8.47(m,5H),8.32(s,1H),8.17-8 .08(m,3H),8.05-7.89(m,11H),7.68-7.61(m,2H),7.56-7.38(m,5H),7.24(m,4H).

[0138] M / Z: Experimental value, 713.25; Theoretical value, 712.26.

[0139] Synthesis of compound A5

[0140]

[0141] 100 mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine (CAS No.: 3842-55-5), 100 mmol of 4-bromophenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask. 1.0 mol% Pd(PPh3)4 of 2-chloro-4,6-diphenyl-1,3,5-triazine was also added, and the mixture was reacted at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1.

[0142] 100 mmol of M1, 100 mmol of pinacol diborate, 29.4 g (300 mmol) of potassium acetate, and 800 mL of dioxane were added to a reaction flask, along with 1.0 mol% Pd(dppf)Cl2 (M1 molar amount). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2.

[0143] 100 mmol of M2, 100 mmol of M3 (the synthesis method of M3 is the same as that used in the synthesis of compound A1), 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M2. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4.

[0144] Add 10 mmol of M4 to the reaction flask and dissolve it in 200 mL of DMF. At room temperature, add 100 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 1000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M5.

[0145] 100 mmol of M5, 200 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M5. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A5.

[0146] 1 H NMR (400MHz, Chloroform-d) δ9.00(s,1H),8.68(s,1H),8.38-8.29(m,5H),8.17-7.99(m,8H),7.86-7.61(m,4H),7.56-7.47(m,8H),7.24(m,4H).

[0147] M / Z: Experimental value, 690.27; Theoretical value, 689.26.

[0148] Synthesis of compound A6

[0149]

[0150] 100 mmol of 2,3-dichloro-5,6-diphenylpyrazine (CAS No.: 57038-62-7), 100 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask. 1.0 mol% Pd(PPh3)4 of 2,3-dichloro-5,6-diphenylpyrazine was also added, and the mixture was reacted at 120 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1.

[0151] 100 mmol of M1, 100 mmol of 4-chlorophenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask. 1.0 mol% Pd(PPh3)4 (4-chlorophenylboronic acid) was also added, and the mixture was reacted at 120 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2.

[0152] 100 mmol of M2, 100 mmol of pinacol diborate, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M2. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4.

[0153] 100 mmol of M4, 100 mmol of M3 (the synthesis method of M3 is the same as that used in the synthesis of compound A1), 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M3. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M5.

[0154] Add 10 mmol of M5 to the reaction flask and dissolve it in 200 mL of DMF. At room temperature, add 100 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 1000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M6.

[0155] 100 mmol of M6, 200 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M6. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A6.

[0156] 1 H NMR (400MHz, Chloroform-d) δ8.96(s,1H),8.66(s,1H),8.30(s,1H),8.19-7.99(m,14H),7.92-7.85(m,2H),7.68-7.52(m,7H),7.24(m,10H).

[0157] M / Z: Experimental value, 765.28; Theoretical value, 764.29.

[0158] Synthesis of compound A7

[0159]

[0160] 100 mmol of 3-bromo-9,10-phenanthrenequinone, 100 mmol of pinacol diborate, 29.4 g (300 mmol) of potassium acetate, and 800 mL of dioxane were added to a reaction flask, along with 1.0 mol% Pd(dppf)Cl2 of 3-bromo-9,10-phenanthrenequinone. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1.

[0161] 100 mmol of M1, 100 mmol of 3-bromo-9,10-phenanthrenequinone, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask. 1.0 mol% of Pd(PPh3)4 (M1 molar amount) was also added. The reaction was carried out at 120 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2.

[0162] Add 100 mmol of M2, 2000 mmol of hydroxylamine hydrochloride, 100 mL of pyridine, and 2000 mL of ethanol to a reaction flask. Heat under reflux at 100°C for 8 hours. Then add 1000 mL of 10% hydrochloric acid to the reaction solution and stir until homogeneous. A solid precipitates out; filter to obtain the solid. Add this solid to a reaction flask, along with 2000 mmol of zinc powder and 2000 mmol of ammonium chloride. Mix and dissolve in 2000 mL of ethanol. Heat under reflux at 100°C for 3 hours. After the reaction is complete, filter and concentrate the filtrate to obtain the solid. Add 200 mL of ethylene oxalate and heat to 130°C for 3 hours. After the reaction is complete, add the reaction solution to ethanol; a solid precipitates out. Recrystallize the obtained solid from ethanol to obtain M3.

[0163] Add 10 mmol of M3 to the reaction flask and dissolve it in 400 mL of DMF. At room temperature, add 200 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 2000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M4.

[0164] 100 mmol of M4, 400 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M4. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A7.

[0165] 1 H NMR (400MHz, Chloroform-d) δ9.60 (s, 1H), 8.85 (m, 2H), 7.96-7.77 (m, 15H), 7.52 (m, 4H), 7.39-7.27 (m, 12H).

[0166] M / Z: Experimental value, 763.28; Theoretical value, 762.28.

[0167] Synthesis of compound A9

[0168]

[0169] 100 mmol of 9,9-dimethyl-2-bromofluorene (CAS No.: 28320-31-2), 100 mmol of pinacol diborate, 29.4 g (300 mmol) of potassium acetate, and 800 mL of dioxane were added to a reaction flask, along with 1.0 mol% Pd(dppf)Cl2 containing 9,9-dimethyl-2-bromofluorene. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1.

[0170] 100 mmol of M1, 100 mmol of M3 (the synthesis method of M3 is the same as that used in the synthesis of compound A1), 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M1. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2.

[0171] Add 10 mmol of M2 to the reaction flask and dissolve it in 200 mL of DMF. At room temperature, add 100 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 1000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M4.

[0172] 100 mmol of M4, 200 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M4. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A9.

[0173] 1 H NMR(400MHz,Chloroform-d)δ8.96(s,1H),8.67(s,1H),8.30-8.15(m,3H),8 .06-7.84(m,8H),7.68-7.48(m,6H),7.45(s,1H),7.24(m,4H),1.72(m,6H).

[0174] M / Z: Experimental value, 575.25; Theoretical value, 574.24.

[0175] Synthesis of compound A12

[0176]

[0177] 100 mmol of 2-bromonaphthalene (CAS No.: 580-13-2), 100 mmol of 4-bromophenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of 2-bromonaphthalene. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1.

[0178] 100 mmol of M1, 100 mmol of pinacol diborate, 29.4 g (300 mmol) of potassium acetate, and 800 mL of dioxane were added to a reaction flask, along with 1.0 mol% Pd(dppf)Cl2 (M1 molar amount). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2.

[0179] 100 mmol of M2, 100 mmol of M3 (the synthesis method of M3 is the same as that used in the synthesis of compound A1), 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M2. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4.

[0180] Add 10 mmol of M4 to the reaction flask and dissolve it in 200 mL of DMF. At room temperature, add 100 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 1000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M5.

[0181] 100 mmol of M5, 200 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M5. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, Al2.

[0182] 1 H NMR (400MHz, Chloroform-d) δ8.98(s,1H),8.68(s,1H),8.31(s,1H),8.16-7.96(m,9H),7.91(m 5H),7.75-7.52(m,7H),7.24(m,4H).

[0183] M / Z: Experimental value, 585.23; Theoretical value, 584.23.

[0184] Synthesis of compound A13

[0185]

[0186] 100 mmol of 9,9-dimethyl-2-bromofluorene, 100 mmol of 5-bromopyridine-2-boric acid (CAS No.: 652148-97-5), 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of 9,9-dimethyl-2-bromofluorene. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1.

[0187] 100 mmol of M1, 100 mmol of pinacol diborate, 29.4 g (300 mmol) of potassium acetate, and 800 mL of dioxane were added to a reaction flask, along with 1.0 mol% Pd(dppf)Cl2 (M1 molar amount). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2.

[0188] 100 mmol of M2, 100 mmol of M3 (the synthesis method of M3 is the same as that used in the synthesis of compound A1), 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M2. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4.

[0189] Add 10 mmol of M4 to the reaction flask and dissolve it in 200 mL of DMF. At room temperature, add 100 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 1000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M5.

[0190] 100 mmol of M5, 200 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M5. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, Al3.

[0191] 1H NMR (400MHz, Chloroform-d) δ9.19-8.98(m,2H),8.68(s,1H),8.31-8.15(m,4H),8.10-7.96(m,8H),7.83-7.41(m,8H),7.28-7.20(m,4H),1.73(m,6H).

[0192] M / Z: Experimental value, 652.28; Theoretical value, 651.27.

[0193] Synthesis of compound A15

[0194]

[0195] 100 mmol of 3-bromodibenzo[B,D]furan (CAS No.: 26608-06-0), 100 mmol of 5-bromopyridine-2-boric acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask. 1.0 mol% of Pd(PPh3)4 (3-bromodibenzo[B,D]furan) was also added, and the mixture was reacted at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1.

[0196] 100 mmol of M1, 100 mmol of pinacol diborate, 29.4 g (300 mmol) of potassium acetate, and 800 mL of dioxane were added to a reaction flask, along with 1.0 mol% Pd(dppf)Cl2 (M1 molar amount). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2.

[0197] 100 mmol of M2, 100 mmol of M3 (the synthesis method of M3 is the same as that used in the synthesis of compound A1), 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M2. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4.

[0198] Add 10 mmol of M4 to the reaction flask and dissolve it in 200 mL of DMF. At room temperature, add 100 mmol of phosphorus trichloride dropwise, then heat to 100 °C and reflux for 3 h. After the reaction is complete, add the reaction solution to 1000 mL of water. A solid is produced. Stir, filter, and obtain the solid. Recrystallize from toluene to obtain M5.

[0199] 100 mmol of M5, 200 mmol of phenylboronic acid, 41.4 g (300 mmol) of potassium carbonate, 800 mL of THF, and 200 mL of water were added to a reaction flask, along with 1.0 mol% Pd(PPh3)4 of M5. The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reaction solution was cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A15.

[0200] 1 H NMR(400MHz,Chloroform-d)δ9.28-9.25(m,2H),8.97(s,1H),8.62-8.46(m,2H),8.2 9-8.12(m,4H),8.02-7.90(m,7H),7.74-7.48(m,5H),7.44-7.35(m,2H),7.24(m,4H).

[0201] M / Z: Experimental value, 626.23; Theoretical value, 625.22.

[0202] Other compounds in this application can be synthesized by selecting suitable starting materials according to the above synthetic examples, or by selecting any other suitable method and starting materials.

[0203] Example 1

[0204] A glass substrate coated with a 150nm 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 until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to obtain a glass substrate with an anode.

[0205] Then, the glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of less than 10. -5A first hole injection layer is vacuum-deposited on the anolyte film of the aforementioned glass substrate with an anode. The material of the first hole injection layer includes hole injection material HT-11 and p-type dopant p-1. The deposition is performed using a multi-source co-evaporation method. The deposition rate of hole injection material HT-11 is adjusted to 0.1 nm / s, and the deposition rate of p-type dopant p-1 is 3% of the deposition rate of hole injection material HT-11. The total film thickness is 10 nm. The hole injection material HT-11 and p-type dopant p-1 are as follows:

[0206]

[0207] Then, hole transport material HT-5 is vacuum-deposited on the first hole injection layer as the first hole transport layer, wherein the deposition rate is 0.1 nm / s and the deposition film thickness is 80 nm. The hole transport material HT-5 is as follows:

[0208]

[0209] Then, a first light-emitting layer is vacuum-deposited on the first hole transport layer. The first light-emitting layer includes a blue light-emitting substrate material BH-5 and a blue light-emitting guest material BD-1. The deposition is performed using a multi-source co-evaporation method. The deposition rate of the blue light-emitting substrate material BH-5 is adjusted to 0.1 nm / s, and the deposition rate of the blue light-emitting guest material BD-1 is 3% of the deposition rate of the blue light-emitting substrate material BH-5. The total film thickness is 30 nm. The blue light-emitting substrate material BH-5 and the blue light-emitting guest material BD-1 are as follows:

[0210]

[0211] Then, a first electron transport layer is vacuum-deposited on top of the first light-emitting layer. The electron transport material ET-32 and the n-type dopant LiQ are deposited to form the first electron transport layer. The deposition rate of the electron transport material ET-32 is 0.1 nm / s, the deposition rate ratio of the electron transport material ET-32 to the n-type dopant LiQ is 50:50, and the total film thickness is 30 nm. The electron transport materials ET-32 and LiQ are as follows:

[0212]

[0213] The first hole injection layer, the first hole transport layer, the first light-emitting layer, and the first electron transport layer together constitute the first light-emitting unit;

[0214] On the uppermost first electron transport layer of the first light-emitting unit, compound A1 provided in this application is used as a charge-generating material and deposited with ytterbium (Yb) as a charge-generating layer. The deposition rate of compound A1 is 0.01 nm / s, the deposition rate ratio of compound A1 to Yb is 99:1, and the total deposition film thickness is 10 nm.

[0215] A second hole injection layer is deposited on top of the charge generation layer. The material of the second hole injection layer includes hole injection material HT-11 and p-type dopant p-1. The evaporation rate of hole injection material HT-11 is adjusted to 0.1 nm / s, the ratio of the evaporation rates of hole injection material HT-11 and p-type dopant p-1 is 99:1, and the total film thickness is 10 nm.

[0216] Then, hole transport material HT-5 is vacuum-deposited on the second hole injection layer as the second hole transport layer, wherein the deposition rate is 0.1 nm / s and the deposition film thickness is 80 nm.

[0217] Then, a second light-emitting layer is vacuum-deposited on the second hole transport layer. The second light-emitting layer includes a blue light-emitting layer host material BH-5 and a blue light-emitting layer guest material BD-1. The deposition is performed using a multi-source co-evaporation method. The deposition rate of the blue light-emitting layer host material BH-5 is adjusted to 0.1 nm / s, the deposition rate of the blue light-emitting layer guest material BD-1 is 3% of the deposition rate of the blue light-emitting layer host material BH-5, and the total deposition film thickness is 30 nm.

[0218] Then, a second electron transport layer is vacuum-deposited on the second light-emitting layer. The electron transport material ET-32 and the n-type dopant LiQ are deposited to form the second electron transport layer. The deposition rate of the electron transport material ET-32 is 0.1 nm / s, the deposition rate ratio of the electron transport material ET-32 to the n-type dopant LiQ is 50:50, and the total deposition film thickness is 30 nm.

[0219] The second hole injection layer, the second hole transport layer, the second light-emitting layer, and the second electron transport layer together constitute the second light-emitting unit;

[0220] Then, a 5 nm thick LiF layer is vacuum-deposited on the uppermost second electron transport layer of the second light-emitting unit as an electron injection layer, wherein the deposition rate is 0.1 nm / s;

[0221] Finally, an Al layer with a thickness of 150 nm was vacuum-deposited on the electron injection layer as the cathode electrode of the stacked organic electroluminescent device, wherein the deposition rate was 0.1 nm / s.

[0222] Examples 2 to 9

[0223] Except for replacing A1 with A2, A5, A6, A7, A9, A12, A13, and A15 respectively for the charge-generating materials, everything else is the same as in Example 1. See Table 1 for details.

[0224] Comparative Example 1

[0225] Except for replacing A1 with CGL00R1 as the charge-generating material, everything else is the same as in Example 1.

[0226]

[0227] Comparative Example 2

[0228] Except for replacing A1 with B1 as the charge-generating material, everything else is the same as in Example 1.

[0229]

[0230] Comparative Example 3

[0231] Except for replacing A1 with B2 as the charge-generating material, everything else is the same as in Example 1.

[0232]

[0233] The following performance measurements were performed on the multilayer organic electroluminescent devices prepared by the above process:

[0234] At the same brightness, the driving voltage, blue light index, voltage fluctuation value (ΔCCV) under constant current, and device lifetime of the organic electroluminescent devices prepared in the examples and comparative examples were measured using a digital source meter. Specifically, the voltage was increased at a rate of 0.1V per second, and the measurement was performed when the brightness of the organic electroluminescent device reached 1000 cd / m². 2 The voltage at that moment is the driving voltage, and the current density at that moment is also measured; the ratio of brightness to current density is the current efficiency; under normal temperature conditions, a brightness-current density-voltage (BJV) test system is used, with a test J = 50 mA / cm². 2 The current is measured, and then the voltage fluctuation value ΔCCV is measured while the current value is constant; the life test of LT95 is as follows: using a luminance meter at 1000 cd / m 2 At a constant current, the brightness of the organic electroluminescent device decreased to 950 cd / m² under the specified brightness. 2 The time is measured in hours. For blue light devices, the luminous efficiency is evaluated using the blue light index (BI), which is the ratio of the measured current efficiency of the device to the color coordinate CIEy. The color coordinate CIEy values ​​for Examples 1-9 and Comparative Examples 1-3 are all 0.045. The performance results are shown in Table 1.

[0235] Table 1. Performance results of organic electroluminescent devices

[0236]

[0237] As shown in Table 1, when compounds A1, A2, A5, A6, A7, A9, A12, A13, and A15 of this application are used as charge-generating materials in organic electroluminescent devices, compared to the known materials in the prior art used in Comparative Examples 1 to 3, the organic electroluminescent devices of this application exhibit lower driving voltage, smaller ΔCCV, higher blue light index, and longer lifespan. This demonstrates that the compounds provided in this application, when used as charge-generating materials in organic electroluminescent devices, can effectively reduce the driving voltage of the organic electroluminescent devices, making the voltage of the organic electroluminescent devices more stable, delaying the aging of the organic electroluminescent devices, improving the luminous efficiency of the organic electroluminescent devices, and further extending the lifespan of the organic electroluminescent devices, making them high-performance charge-generating materials.

[0238] It is understood that the organic electroluminescent device in the embodiments is a blue organic electroluminescent device, and the above embodiments are only examples. The compounds provided in this application are used as 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.

[0239] The above description is only a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of protection of this application.

Claims

1. A compound containing dibenzoquinoxaline, as shown in formula (I): in, L is selected from the chemically bonded, unsubstituted, or Ra-substituted groups shown in L1 to L4: When L is selected from a chemical bond, R is selected from the unsubstituted or Ra-substituted groups shown in R1 to R9: When L is selected from the unsubstituted or Ra-substituted groups shown in L1 to L4 R is selected from hydrogen, deuterium, C1-C4 alkyl, unsubstituted or Ra-substituted groups shown in R1 to R9: Each of the Ra is independently selected from hydrogen, deuterium, C1-C6 alkyl, phenyl, biphenyl, terphenyl, pyrimidinyl, naphthyl, pyridinyl, or 2-phenylpyridinyl.

2. The compound according to claim 1, wherein, Each Ra is independently selected from hydrogen or the groups shown in Ra1 to Ra5:

3. The compound according to claim 1, wherein, The compound is selected from the compounds shown in A1 to A20 below:

4. A charge-generating material comprising at least one of the compounds according to any one of claims 1-3.

5. An organic electroluminescent device, wherein, The organic electroluminescent device includes a charge generation layer, which comprises at least one of the charge generation materials of claim 4.

6. The organic electroluminescent device according to claim 5, wherein, The charge-generating layer comprises the charge-generating material and a metal-containing material, wherein the content of the metal-containing material accounts for 0.5%-2.5% of the charge-generating layer content; the metal-containing material is selected from at least one of a metal or a metal complex; the metal is selected from at least one of lithium or ytterbium, and the metal complex is selected from at least one of lithium 8-hydroxyquinoline or aluminum 8-hydroxyquinoline.

7. The organic electroluminescent device according to claim 5 or 6, wherein, The thickness of the charge generation layer is 10nm-30nm.

8. The organic electroluminescent device according to claim 5, wherein, The organic electroluminescent device is a stacked organic electroluminescent device.

9. A display device comprising the organic electroluminescent device according to any one of claims 5-8.

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