Phosphine-substituted phenanthroline compound, organic electroluminescent device and display device

Abstract

The invention belongs to the technical field of organic light-emitting display, and particularly relates to a phosphine-substituted phenanthroline compound, an organic light-emitting device and a display device. The structure of the compound is shown as a formula (I). The organic light-emitting device provided by the invention comprises the charge generation layer and the electron transport layer, the charge generation layer is made of the phosphine substituted phenanthroline compound, has efficient charge generation capability, can effectively improve the light-emitting efficiency of the organic light-emitting device, and has a relatively shallow energy level, so that the light-emitting efficiency of the organic light-emitting device is improved. The organic electroluminescent device can be better matched with an adjacent layer material for use, the charge transmission performance of the organic electroluminescent device can be effectively improved, the luminous efficiency of the organic electroluminescent device is improved, the driving voltage of the organic electroluminescent device is reduced, and the service life of the organic electroluminescent device is prolonged. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic light-emitting display, and in particular relates to a phosphine-substituted phenanthroline compound, an organic electroluminescent device and a display apparatus. Background Art

[0002] 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, organic electroluminescent displays do not require backlight sources, have large viewing angles, low power consumption, and their response speed can reach 1000 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.

[0003] 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 the optimized combination of device structure and various organic materials. This has brought great opportunities and challenges to chemists in designing and developing functional materials of various structures. Laminated devices can effectively improve the working life of devices, so they have been a research hotspot in recent years. How to develop high-efficiency charge generation layer materials and select matching light-emitting units to improve the luminous efficiency of organic electroluminescent devices and extend their service life has become a technical problem that technicians in this field need to solve urgently. Summary of the invention

[0004] The object of the present invention is to provide a phosphine-substituted phenanthroline compound, an organic electroluminescent device and a display device, so as to improve the luminous efficiency of the organic electroluminescent device and prolong its service life.

[0005] The first aspect of the present invention is to provide a phosphine-substituted phenanthroline compound, the structure of which is shown in formula (I):

[0006]

[0007] in,

[0008] R 1 , R 2 , R 3 , R 4 Each independently selected from C1-C5 alkanes, C3-C6 cycloalkanes, C6-C 30Aryl, C3-C unsubstituted or substituted by Rc 30 Heteroaryl;

[0009] L 1 、L 2 、L 3 Each independently selected from a chemical bond, C6-C unsubstituted or substituted by Rc 30 Arylene, C3-C unsubstituted or substituted by Rc 30 Heteroarylene;

[0010] X 1 -X 5 Each independently selected from N or C, and at least one is N;

[0011] m and n each independently selected from 0, 1, and m + n ≥ 1;

[0012] The heteroatoms on the heteroaryl or heteroarylene each independently selected from O, S or N;

[0013] The substituents Rc of each group each independently selected from hydrogen, deuterium, halogen, nitro, cyano, C1-C4 alkyl, phenyl, biphenyl, terphenyl, pyridyl, pyrimidinyl or naphthyl.

[0014] Preferably, the R 1 、R 2 、R 3 、R 4 Each independently selected from C6-C unsubstituted or substituted by Rc 18 Aryl, C3-C unsubstituted or substituted by Rc 18 Heteroaryl; and / or,

[0015] The L 1 、L 2 、L 3 Each independently selected from a chemical bond, C6-C unsubstituted or substituted by Rc 18 Arylene, C3-C unsubstituted or substituted by Rc 30 Heteroarylene.

[0016] More preferably, the R 1 、R 2 、R 3 、R 4 Each independently selected from methyl, ethyl, isopropyl, and the groups of the following compounds unsubstituted or substituted by Rc: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, dibenzofuran, dibenzothiophene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirofluorene.

[0017] More preferably, the L 1 、L 2 、L3 Each independently selected from a chemical bond and a group of the following compounds which are unsubstituted or substituted by Rc: phenyl, pyridyl, pyrimidinyl, quinoxalinyl, quinazolinyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, anthryl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorene.

[0018] Preferably, the compound of formula (I) is selected from the compounds shown in the following A1 to A30:

[0019]

[0020]

[0021] Another object of the present invention is to provide an organic electroluminescent device, which comprises a charge generation layer and an electron transport layer, and the charge generation layer material comprises the compound of formula (I).

[0022] Preferably, the charge generation layer material comprises metal Li or Yb, and based on the mass of the charge generation layer material, the mass percentage content of the metal Li or Yb is 0.5%-2.5%.

[0023] Preferably, the thickness of the charge generation layer is 10nm - 30nm, and the thickness of the electron transport layer is 10nm - 40nm.

[0024] Another object of the present invention is to provide a display device, which comprises the above-mentioned organic electroluminescent device.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] For the organic electroluminescent device provided by the present invention, the charge generation layer material is a phosphine-substituted phenanthroline compound, which has high charge generation ability, can effectively improve the luminous efficiency of the organic electroluminescent device, and at the same time has a relatively shallow energy level, can be used in combination with adjacent layer materials, can effectively improve the charge transport performance of the organic electroluminescent device, improve the luminous efficiency of the organic electroluminescent device, reduce its driving voltage and extend its service life. The display device provided by the present invention has excellent display effects.

[0027] Of course, it is not necessary for any product or method implementing the present invention to achieve all the above-mentioned advantages simultaneously. Description of the Drawings

[0028] To more clearly illustrate the technical solutions in the present invention, the following will briefly introduce the accompanying drawings required for the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other embodiments can also be obtained based on these drawings.

[0029] Figure 1 It is a schematic structural diagram of a typical organic electroluminescent device 20. Each part is respectively: 21, a substrate; 22, a reflective anode; 231, a first hole injection layer; 241, a first hole transport layer; 251, a first light-emitting layer; 261, a first electron transport layer; 27, a charge generation layer; 232, a second hole injection layer; 242, a second hole transport layer; 252, a second light-emitting layer; 262, a second electron transport layer; 28, an electron injection layer; 29, a cathode electrode. Specific embodiments

[0030] The following will clearly and completely describe the technical solutions in the present invention with reference to the accompanying drawings in the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the present invention fall within the scope of protection of the present invention.

[0031] In the present invention, there is no particular limitation on the type and structure of the organic electroluminescent device, and it can be organic electroluminescent devices of different types and structures well-known in the art, as long as at least one of the charge generation materials and at least one of the electron transport materials provided by the present invention can be used.

[0032] In one embodiment of the present invention, the organic electroluminescent device includes an anode and a cathode, and m light-emitting units and m - 1 charge generation layers are stacked between the anode and the cathode. The charge generation layers are between two adjacent light-emitting units. Each charge generation layer includes an n-type charge generation layer and a p-type charge generation layer, where m is an integer greater than or equal to 2; each light-emitting unit includes at least one light-emitting layer, and the maximum emission wavelengths of the light emitted in different light-emitting units are different; at least one of the n-type charge generation layers includes at least one compound represented by formula (I) and a metal-containing material, and the metal-containing material includes a metal, a metal complex, or a combination thereof.

[0033] In an embodiment of the present invention, the light-emitting unit in the organic electroluminescent device may include a first light-emitting unit and a second light-emitting unit, and the two light-emitting units may be the same or different; the charge generation layer 27 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, the second light-emitting unit may be disposed between the charge generation layer and the cathode, and the n-type charge generation layer of the charge generation layer may include at least one compound represented by formula (I) and a metal-containing material.

[0034] In some other embodiments of the present invention, the organic electroluminescent device of the present invention may be a top-emitting structure light-emitting device, and may sequentially include an anode, a first light-emitting unit, a charge generation layer, a second light-emitting unit, an electron injection layer, and a transparent or semi-transparent cathode on a substrate.

[0035] The organic electroluminescent device of the present invention may also be a bottom-emitting structure light-emitting device, and may sequentially include a transparent or semi-transparent anode, a first light-emitting unit, a charge generation layer, a second light-emitting unit, an electron injection layer, and a cathode on a substrate.

[0036] The organic electroluminescent device of the present invention may also be a double-sided emitting structure light-emitting device, and may sequentially include a transparent or semi-transparent anode, a first light-emitting unit, a charge generation layer, a second light-emitting unit, an electron injection layer, and a transparent or semi-transparent cathode on a substrate.

[0037] 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 disposed 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 disposed in sequence.

[0038] In addition, in the organic electroluminescent device of the present invention, an electron blocking layer may be provided between the hole transport layer and the light-emitting layer, a hole blocking layer may be provided between the light-emitting layer and the electron transport layer, and a light extraction layer may be provided on the transparent electrode on the light-emitting side. However, the structure of the organic electroluminescent device of the present invention is not limited to the above specific structure, and if necessary, the above layers may be omitted or added. The present invention places no particular limitation on the thicknesses of the above anode, hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron injection layer, cathode, and light extraction layer, as long as the object of the present invention can be achieved. For example, the organic electroluminescent device may sequentially include, on a substrate, an anode made of metal (100 nm to 150 nm), a first hole injection layer (5 nm to 20 nm), a first hole transport layer (80 nm to 140 nm), an electron blocking layer (5 nm to 20 nm), a first light-emitting layer (15 nm to 40 nm), a hole blocking layer (5 nm to 20 nm), a first electron transport layer (10 nm to 40 nm), a charge generation layer (10 nm to 30 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 (15 nm to 40 nm), a second electron transport layer (10 nm to 40 nm), an electron injection layer (5 nm to 20 nm), a transparent or semi-transparent cathode, and a light extraction layer (50 nm to 90 nm). Exemplarily, Figure 1 FIG. shows a schematic diagram of a typical organic electroluminescent device 20, in which, from bottom to top, a substrate 21, a reflective anode 22, a first hole injection layer 231, a first hole transport layer 241, a first light-emitting layer 251, a first electron transport layer 261, a charge generation layer 27, a second hole injection layer 232, a second hole transport layer 242, a second light-emitting layer 252, a second electron transport layer 262, an electron injection layer 28, and a cathode electrode 29 are sequentially provided. It can be understood that Figure 1 only schematically shows the structure of a typical organic electroluminescent device, and the present invention is not limited to this structure. The charge generation layer material or electron transport layer material of the present invention can be used in any type of organic electroluminescent device.

[0039] For convenience, the organic electroluminescent device of the present invention will be described below, but this does not mean any limitation on the protection scope of the present invention. It can be understood that all organic electroluminescent devices using the charge generation layer material or electron transport layer material of the present invention are within the protection scope of the present invention.

[0040] In the present invention, there is no particular limitation on the substrate 21, and 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, etc.

[0041] In the present invention, there is no particular limitation on the material of the reflective anode 22, and it may be selected from transparent conductive materials known in the prior art such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), etc., or may be selected from metal materials such as silver and its alloys, aluminum and its alloys, etc., or may also be selected from organic conductive materials such as poly(3,4-ethylenedioxythiophene) (PEDOT), or the reflective anode 22 is a multilayer structure formed of the above materials. There is no particular limitation on the number of layers of the multilayer structure in the present invention, and it can be selected according to actual needs as long as it can meet the purpose of the present invention. For example, it can be 1 layer, 2 layers, 3 layers or more layers.

[0042] In the present invention, there is no particular limitation on the materials of the first hole injection layer 231 and the second hole injection layer 232, and they can be made of hole injection layer materials well-known in the art or made of hole transport layer materials (HTM) well-known in the art. For example, at least one of the known hole transport layer materials (HTM) is selected as the hole injection layer material.

[0043] In the present invention, the first hole injection layer 231 and the second hole injection layer 232 may further include a p-type dopant. There is no particular limitation on the type of the p-type dopant in the present invention, and various p-type dopants known in the art can be adopted. For example, the p-type dopant can be selected from but not limited to at least one of the following compounds p-1 to p-3:

[0044]

[0045] In the present invention, there is no particular limitation on the dosage of the p-type dopant, and it can be the dosage well-known to those skilled in the art.

[0046] In the present invention, there is no particular limitation on the materials of the first hole transport layer 241 and the second hole transport layer 242, and they can be made of hole transport layer materials (HTM) well-known in the art. There is no particular limitation on the number of layers of the hole transport layer in the present invention, and it can be adjusted according to actual needs as long as it can meet the purpose of the present invention. For example, it can be 1 layer, 2 layers, 3 layers, 4 layers or more layers.

[0047] For example, the HTM for the hole injection layer material and the HTM for the hole transport layer material can be selected from but not limited to at least one of the following compounds HT-1 to HT-31:

[0048]

[0049]

[0050]

[0051] In the present invention, there are no particular limitations on the materials of the first light-emitting layer 251 and the second light-emitting layer 252. They may each contain a light-emitting layer host material and a light-emitting layer guest material. Among them, there are no particular limitations on the amounts of the light-emitting layer host material and the light-emitting layer guest material, and they may be amounts known to those skilled in the art.

[0052] In the present invention, the light-emitting layer may include a blue light-emitting layer, a green light-emitting layer or a red light-emitting layer. There are no particular limitations on the light-emitting materials in the light-emitting layer, and various light-emitting materials known to those skilled in the art may be used.

[0053] In the present invention, there are no particular limitations on the light-emitting layer host material, and at least one of the light-emitting layer host materials known in the art may be used. For example, it may be selected from at least one of the following compounds BH-1 to BH-10:

[0054]

[0055] In the present invention, there are no particular limitations on the light-emitting layer guest material, and at least one of the light-emitting layer guest materials known in the art may be used. For example, the light-emitting layer guest material may be selected from at least one of the following compounds BD-1 to BD-9:

[0056]

[0057] In the present invention, the above-mentioned first electron transport layer 261 and second electron transport layer 262 contain at least one of the electron transport layer materials of the present invention, and may also contain a combination of at least one of the electron transport layer materials of the present invention and at least one of the known electron transport materials. There are no particular limitations on the number of layers of the electron transport layer, and it may be adjusted according to actual needs as long as the purpose of the present invention can be satisfied. For example, 1 layer, 2 layers, 3 layers, 4 layers or more layers.

[0058] For example, the known electron transport materials may be selected from at least one of the following compounds ET-1 to ET-57:

[0059]

[0060]

[0061]

[0062] In the present invention, the first electron transport layer 261 and the second electron transport layer 262 may also each include an n-type dopant. There are no particular limitations on the type of the n-type dopant, and various n-type dopants known in the art may be used. For example, the following n-type dopant lithium 8-hydroxyquinoline (LiQ) may be used:

[0063]

[0064] In the present invention, there is no particular limitation on the amount of the n-type dopant, and it may be an amount known to those skilled in the art.

[0065] In the present invention, the charge generation layer 27 may include at least one of the charge generation layer materials of the present invention, or may include a combination of at least one of the charge generation layer materials of the present invention and at least one of known charge generation materials.

[0066] For example, the known charge generation materials may be selected from, but not limited to, at least one of the following compounds CGL00R1 to CGL00R5:

[0067]

[0068] In the present invention, there is no particular limitation on the material of the above-mentioned electron injection layer 28, and known electron injection layer materials in the art can be used. For example, it may include, but not limited to, at least one of the materials such as lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, etc. in the prior art.

[0069] In the present invention, there is no particular limitation on the material of the cathode electrode 29, and it may be selected from, but not limited to, metals, metal mixtures, oxides such as magnesium-silver mixture, LiF / Al, ITO, Al, etc.

[0070] There is no particular limitation on the method for preparing the organic electroluminescent device of the present invention, and any method known in the art can be adopted. For example, the present invention can be prepared by the following preparation method:

[0071] The method for preparing the organic electroluminescent device of the present invention may further include, but not limited to, the following steps:

[0072] (1) Cleaning the reflective anode 22 on the top-emitting organic electroluminescent device substrate 21, and respectively passing through steps such as chemical washing, water washing, brushing, high-pressure water washing, air knife, etc. in a cleaning machine, and then performing heat treatment;

[0073] (2) Vacuum-evaporating a hole injection material on the reflective anode 22 as the first hole injection layer 231;

[0074] (3) Vacuum-evaporating a hole transport layer material on the first hole injection layer 231 as the first hole transport layer 241;

[0075] (4) Vacuum-evaporating a first light-emitting layer 251 on the first hole transport layer 241, and the light-emitting layer contains a light-emitting layer host material and a light-emitting layer guest material;

[0076] (5) Vacuum deposit an electron transport material on the first light-emitting layer 251 as the first electron transport layer 261;

[0077] (6) Vacuum deposit a charge generation material on the first electron transport layer 261 as the charge generation layer 27;

[0078] (7) Vacuum deposit a hole injection material on the charge generation layer 27 as the second hole injection layer 232;

[0079] (8) Vacuum deposit a hole transport layer material on the second hole injection layer 232 as the second hole transport layer 242;

[0080] (9) Vacuum deposit a second light-emitting layer 252 on the second hole transport layer 242, and the light-emitting layer contains a light-emitting layer host material and a light-emitting layer guest material;

[0081] (10) Vacuum deposit an electron transport material on the second light-emitting layer 252 as the second electron transport layer 262;

[0082] (11) Vacuum deposit an electron injection material on the second electron transport layer 262 as the electron injection layer 28;

[0083] (12) Vacuum deposit a cathode material on the electron injection layer 28 as the cathode 29.

[0084] The above only describes the structure and preparation method of a typical organic electroluminescent device. It should be understood that the present invention is not limited to this structure. The charge generation layer material or electron transport layer material of the present invention can be used in organic electroluminescent devices of any structure, and any preparation method known in the art can be used to prepare the organic electroluminescent device.

[0085] The present invention also provides a display device, which includes the above-mentioned organic electroluminescent device of the present invention. The display device includes, but is not limited to, a display, a television, a tablet computer, a mobile communication terminal, etc.

[0086] There is no particular limitation on the synthesis method of the compounds of the present invention, and any method known to those skilled in the art can be used for synthesis. The following examples illustrate the synthesis process of the compounds of the present invention.

[0087] Synthesis Example 1

[0088] Synthesis of Compound A1:

[0089]

[0090] Add 100 mmol of 2-bromo-5-chloropyridine, 100 mmol of diphenylphosphine oxide, 41.4 g of potassium carbonate (300 mmol), 800 mL of toluene into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 80 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M1. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2-bromo-5-chloropyridine.

[0091] Add 100 mmol of M1, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M2. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M1.

[0092] Add 100 mmol of 2,9-dichloro-1,10-phenanthroline, 100 mmol of 4-biphenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M3. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2,9-dichloro-1,10-phenanthroline.

[0093] Add 100 mmol of M2, 100 mmol of M3, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF) and 200 mL of water into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder A1. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M2.

[0094] 11H NMR (400 MHz, Chloroform) δ 9.52 (s, 1H), 8.69 (d, J = 7.6 Hz, 2H), 8.52 (s, 2H), 8.38 (d, J = 7.6 Hz, 2H), 7.85 - 7.66 (m, 10H), 7.59 - 7.38 (m, 10H), 7.34 (d, J = 10.0 Hz, 1H).

[0095] Synthesis Example 2

[0096] Synthesis of Compound A4:

[0097]

[0098] 100 mmol of p-chlorobromobenzene, 100 mmol of diphenylphosphine oxide, 41.4 g of potassium carbonate (300 mmol), 800 mL of toluene were added to a reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was carried out at 80 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature. Water was added, and the mixture was filtered and washed with water. The obtained solid was purified by recrystallization from toluene to obtain white powder M1. Among them, the addition amount of Pd(PPh3)4 was 1 mol% of p-chlorobromobenzene.

[0099] 100 mmol of M1, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane were added to a reaction flask, and 1 mol% of Pd(PPh3)4 was added. 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, and the mixture was filtered and washed with water. The obtained solid was purified by recrystallization from toluene to obtain white powder M2. Among them, the addition amount of Pd(PPh3)4 was 1 mol% of M1.

[0100] 100 mmol of p-chlorobromobenzene, 100 mmol of pyridine-3-boronic 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(PPh3)4) was added. 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, and the mixture was filtered and washed with water. The obtained solid was purified by recrystallization from toluene to obtain white powder M3. Among them, the addition amount of Pd(PPh3)4 was 1 mol% of p-chlorobromobenzene.

[0101] Add 100 mmol of M3, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M4. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M3.

[0102] Add 100 mmol of 2,9-dichloro-1,10-phenanthroline, 100 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M5. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2,9-dichloro-1,10-phenanthroline.

[0103] Add 100 mmol of M2, 100 mmol of M5, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF) and 200 mL of water into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder A4. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M2.

[0104] 1 H NMR (400 MHz, Chloroform) δ 9.24 (s, 1H), 8.69 (d, J = 8.0 Hz, 3H), 8.43 - 8.31 (m, 5H), 7.97 (d, J = 7.6 Hz, 2H), 7.88 (d, J = 7.2 Hz, 1H), 7.82 - 7.73 (m, 4H), 7.61 - 7.43 (m, 8H), 7.34 (d, J = 7.6 Hz, 2H), 7.25 (d, J = 7.6 Hz, 2H).

[0105] Synthesis Example 3

[0106] Synthesis of Compound A6:

[0107]

[0108] Add 100 mmol of 2-bromo-5-chloropyridine, 100 mmol of diphenylphosphine oxide, 41.4 g of potassium carbonate (300 mmol), 800 mL of toluene into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 80 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M1. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2-bromo-5-chloropyridine.

[0109] Add 100 mmol of M1, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M2. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M1.

[0110] Add 100 mmol of 2,9-dichloro-1,10-phenanthroline, 100 mmol of 4-(triphenylsilyl)phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M3. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2,9-dichloro-1,10-phenanthroline.

[0111] Add 100 mmol of M2, 100 mmol of M3, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF) and 200 mL of water into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder A6. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M2.

[0112] 11H NMR (400 MHz, Chloroform) δ 9.52 (s, 1H), 8.47 (d, J = 5.6 Hz, 2H), 8.41 (d, J = 6.4 Hz, 1H), 8.36 (d, J = 6.4 Hz, 1H), 8.25 (d, J = 7.6 Hz, 2H), 7.85 - 7.76 (m, 5H), 7.65 (t, J = 8.4 Hz, 3H), 7.59 - 7.43 (m, 13H), 7.41 - 7.30 (m, 10H).

[0113] Synthesis Example 4

[0114] Synthesis of Compound A9:

[0115]

[0116] 100 mmol of p-chlorobromobenzene, 100 mmol of diphenylphosphine oxide, 41.4 g of potassium carbonate (300 mmol), 800 mL of toluene were added to a reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was carried out at 80 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature. Water was added, and the mixture was filtered and washed with water. The obtained solid was purified by recrystallization with toluene to obtain white powder M1. Among them, the addition amount of Pd(PPh3)4 was 1 mol% of p-chlorobromobenzene.

[0117] 100 mmol of M1, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane were added to a reaction flask, and 1 mol% of Pd(PPh3)4 was added. 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, and the mixture was filtered and washed with water. The obtained solid was purified by recrystallization with toluene to obtain white powder M2. Among them, the addition amount of Pd(PPh3)4 was 1 mol% of M1.

[0118] 100 mmol of 2-bromo-5-chloropyridine, 100 mmol of M2, 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(PPh3)4) was added. 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, and the mixture was filtered and washed with water. The obtained solid was purified by recrystallization with toluene to obtain white powder M3. Among them, the addition amount of Pd(PPh3)4 was 1 mol% of p-chlorobromobenzene.

[0119] Add 100 mmol of M3, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M4. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M3.

[0120] Add 100 mmol of 4-chlorobromobenzene, 100 mmol of methyl(phenyl)phosphine oxide, 41.4 g of potassium carbonate (300 mmol), 800 mL of toluene into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 80 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M5. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 4-chlorobromobenzene.

[0121] Add 100 mmol of M5, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M6. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M5.

[0122] Add 100 mmol of 2,9-dichloro-1,10-phenanthroline, 100 mmol of M6, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M7. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2,9-dichloro-1,10-phenanthroline.

[0123] Add 100 mmol of M4, 100 mmol of M7, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF) and 200 mL of water into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder A9. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M4.

[0124] 1 H NMR (400 MHz, Chloroform) δ 9.34 (s, 1H), 8.42 - 8.31 (m, 7H), 8.01 (d, J = 8.0 Hz, 2H), 7.97 (d, J = 8.4 Hz, 3H), 7.85 - 7.68 (m, 8H), 7.58 - 7.45 (m, 10H), 7.35 (d, J = 10.0 Hz, 1H), 1.98 (s, 3H).

[0125] Synthesis Example 5

[0126] Synthesis of Compound A14:

[0127]

[0128] Add 100 mmol of 2-bromo-5-chloropyridine, 100 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of toluene into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 80 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M1. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of p-chlorobromobenzene.

[0129] Add 100 mmol of M1, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M2. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M1.

[0130] Add 100 mmol of p-chlorobromobenzene, 100 mmol of M2, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF) and 200 mL of water into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M3. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of p-chlorobromobenzene.

[0131] Add 100 mmol of M3, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M4. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M3.

[0132] Add 100 mmol of p-chlorobromobenzene, 100 mmol of diethylphosphine oxide, 41.4 g of potassium carbonate (300 mmol), 800 mL of toluene into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 80 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M5. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of p-chlorobromobenzene.

[0133] Add 100 mmol of M5, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M6. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M5.

[0134] Add 100 mmol of 2,9-dichloro-1,10-phenanthroline, 100 mmol of M6, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF, and 200 mL of water into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M7. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2,9-dichloro-1,10-phenanthroline.

[0135] Add 100 mmol of M4, 100 mmol of M7, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder A14. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M4.

[0136] 1 H NMR (400 MHz, Chloroform) δ 8.93 (s, 1H), 8.69 (d, J = 8.0 Hz, 2H), 8.39 (d, J = 7.2 Hz, 2H), 8.33 (d, J = 7.6 Hz, 2H), 8.16 (d, J = 8.0 Hz, 2H), 8.01 (d, J = 7.6 Hz, 1H), 7.91 (t, J = 8.0 Hz, 2H), 7.64 - 7.47 (m, 4H), 7.44 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 2.65 - 2.52 (m, 4H), 1.38 - 1.25 (m, 6H).

[0137] Synthesis Example 6

[0138] Synthesis of Compound A25:

[0139]

[0140] Add 100 mmol of 2-bromo-5-chloropyridine, 100 mmol of diphenylphosphine oxide, 41.4 g of potassium carbonate (300 mmol), 800 mL of toluene into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 80 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M1. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2-bromo-5-chloropyridine.

[0141] Add 100 mmol of M1, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M2. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M1.

[0142] Add 100 mmol of 5-chlorophenanthroline, 100 mmol of 4-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF) and 200 mL of water into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M3. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 5-chlorophenanthroline.

[0143] Add 100 mmol of M3, 100 mmol of bis(pinacolato)diboron, 41.4 g of potassium carbonate (300 mmol), 800 mL of dioxane into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 100 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M4. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M3.

[0144] Add 100 mmol of 2,9-dichloro-1,10-phenanthroline, 100 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 mL of THF and 200 mL of water into a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a white powder M5. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of 2,9-dichloro-1,10-phenanthroline.

[0145] Add 100 mmol of M2, 100 mmol of M5, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF) and 200 mL of water into a reaction flask, and add 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a white powder A25. Among them, the addition amount of Pd(PPh3)4 is 1 mol% of M2.

[0146] 1 H NMR (400 MHz, Chloroform) δ 9.52 (s, 1H), 8.80 (d, J = 8.0 Hz, 1H), 8.68 (t, J = 8.0 Hz, 3H), 8.48 (d, J = 6.8 Hz, 2H), 8.38 (d, J = 6.4 Hz, 1H), 8.34 (d, J = 6.4 Hz, 1H), 8.11 (t, J = 7.6 Hz, 2H), 7.95 (s, 1H), 7.85 - 7.76 (m, 5H), 7.70 (d, J = 8.4 Hz, 1H), 7.58 - 7.46 (m, 7H), 7.41 - 7.25 (m, 5H).

[0147] Other compounds of the present invention can be synthesized by selecting appropriate raw materials according to the idea of the above synthesis examples, or any other appropriate methods and raw materials can be selected for synthesis.

[0148] Example 1

[0149] Ultrasonically treat a glass substrate coated with an ITO transparent conductive layer with a thickness of 150 nm in a commercial cleaning agent, rinse it in deionized water, ultrasonically remove oil in an acetone-ethanol mixed solvent, bake it in a clean environment until all moisture is removed, clean it with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam to obtain a glass substrate with an anode;

[0150] Then, place the above-mentioned glass substrate with an anode in a vacuum chamber, evacuate to less than 10-5 Torr. On the anode layer film of the glass substrate with an anode, a first hole injection layer is vacuum-evaporated. The material of the first hole injection layer includes a hole injection layer material HT-11 and a p-type dopant p-1, and the evaporation is carried out by the method of multi-source co-evaporation. Among them, 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 total evaporation film thickness is 10 nm; the hole injection layer material HT-11 and the p-type dopant p-1 are as follows:

[0151]

[0152] Then, a hole transport layer material HT-5 is vacuum-evaporated on the first hole injection layer as the first hole transport layer. Among them, the evaporation rate is 0.1 nm / s, and the evaporation film thickness is 80 nm. The hole transport layer material HT-5 is as follows:

[0153]

[0154] Then, a first light-emitting layer is vacuum-evaporated on the first hole transport layer. The first light-emitting layer includes a light-emitting layer host material BH-2 and a light-emitting layer guest material BD-1, and the evaporation is carried out by the method of multi-source co-evaporation. Among them, the evaporation rate of the light-emitting layer host material BH-2 is adjusted to 0.1 nm / s, and the evaporation rate of the light-emitting layer guest material BD-1 is 3% of the evaporation rate of the light-emitting layer host material BH-2. The evaporation film thickness is 30 nm; the light-emitting layer host material BH-2 and the light-emitting layer guest material BD-1 are as follows:

[0155]

[0156] Then, a first electron transport layer is vacuum-evaporated on the first light-emitting layer. The material of the first electron transport layer is compound ET30 and LiQ. Among them, the evaporation rate of compound ET30 is 0.1 nm / s, and the evaporation rate ratio of compound ET30 and LiQ is 7:3. The total evaporation film thickness is 30 nm; compound ET30 and LiQ are as follows:

[0157]

[0158] The above first hole injection layer, first hole transport layer, first light-emitting layer and first electron transport layer together form a first light-emitting unit;

[0159] On the first electron transport layer which is the uppermost layer in the first light-emitting unit, compound A1 provided by the present invention and ytterbium (Yb) are evaporated to form a charge generation layer. Among them, the evaporation rate of compound A1 is 0.01 nm / s, and the evaporation rate ratio of compound A1 and Yb is 99:1. The total evaporation film thickness is 10 nm;

[0160] A second hole injection layer is vapor-deposited on the charge generation layer. The material of the second hole injection layer includes hole injection layer material HT-11 and p-type dopant p-1. Among them, the vapor deposition rate of the hole injection layer material HT-11 is adjusted to 0.1 nm / s, and the vapor deposition rate ratio of the hole injection layer material HT-11 to the p-type dopant p-1 is 99:1. The total vapor deposition film thickness is 10 nm;

[0161] Then, the hole transport layer material HT-5 is vacuum vapor-deposited on the second hole injection layer as the second hole transport layer. Among them, the vapor deposition rate is 0.1 nm / s, and the vapor deposition film thickness is 80 nm;

[0162] Then, a second light-emitting layer is vacuum vapor-deposited on the second hole transport layer. The second light-emitting layer includes a light-emitting layer host material BH-2 and a light-emitting layer guest material BD-1, and vapor deposition is carried out by the method of multi-source co-evaporation. Among them, the vapor deposition rate of the light-emitting layer host material BH-2 is adjusted to 0.1 nm / s, the vapor deposition rate of the light-emitting layer guest material BD-1 is 3% of the vapor deposition rate of the light-emitting layer host material BH-2, and the total vapor deposition film thickness is 30 nm;

[0163] Then, a second electron transport layer is vacuum vapor-deposited on the second light-emitting layer. The electron transport material is compound ET30 and LiQ. Among them, the vapor deposition rate of compound ET30 is 0.1 nm / s, and the vapor deposition rate ratio of compound ET30 to LiQ is 7:3. The total vapor deposition film thickness is 30 nm;

[0164] The above second hole injection layer, second hole transport layer, second light-emitting layer and second electron transport layer together form a second light-emitting unit;

[0165] Then, LiF with a thickness of 0.5 nm is vacuum vapor-deposited on the uppermost second electron transport layer in the second light-emitting unit as the electron injection layer. Among them, the vapor deposition rate is 0.1 nm / s;

[0166] Finally, an Al layer with a thickness of 150 nm is vacuum vapor-deposited on the electron injection layer as the cathode electrode of the organic electroluminescent device. Among them, the vapor deposition rate is 0.1 nm / s.

[0167] Example 2-6

[0168] Except that the charge generation layer materials are replaced by A4, A6, A9, A14, A25 instead of A1 respectively, the rest are the same as in Example 1.

[0169] Example 7

[0170] Except that the first electron transport layer is removed and the thickness of the charge generation layer of the present invention is increased to 20 nm, and the ratio to metal Yb remains unchanged at (99:1), the rest are the same as in Example 1.

[0171] Comparative Example 1

[0172] Except that the charge generation layer material is selected as CGL00R1 to replace A1, the rest is the same as in Example 1;

[0173]

[0174] Comparative Example 2

[0175] Except that the charge generation layer material is selected as CGL00R6 to replace A1, the rest is the same as in Example 1;

[0176]

[0177] The following performance measurements were carried out on the organic electroluminescent devices prepared by the above process:

[0178] At the same brightness, a digital source meter and a luminance meter were used to measure the driving voltage, current efficiency and device lifetime of the organic electroluminescent devices prepared in Examples 1 to 7 and Comparative Examples 1 to 2. 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 / m 2 was measured as the driving voltage, and the current density at this time was also measured; the ratio of brightness to current density was the current efficiency; the LT95 lifetime test was as follows: using a luminance meter at 1000 cd / m 2 brightness, keeping a constant current, measuring the time when the brightness of the organic electroluminescent device dropped to 950 cd / m 2 in hours. The results are shown in Table 1.

[0179] Table 1. Performance Results of Organic Electroluminescent Devices

[0180]

[0181]

[0182] As can be seen from Table 1, for the organic electroluminescent devices prepared in Examples 1 to 6, compounds A1, A4, A6, A9, A14, and A25 provided by the present invention were used as the first charge generation layer materials. Compared with using known materials in the prior art as the charge generation layer materials of the organic electroluminescent devices in Comparative Example 1 and Comparative Example 2, the organic electroluminescent devices of the present invention have a lower driving voltage, a higher current efficiency, and a longer LT95 life. As can be seen from Example 7, when the first electron transport layer is removed and the first charge generation layer material is thickened to be used as electron transport, an efficient electron transport effect can still be maintained, and the device maintains a low voltage, high efficiency, and long life. Thus, it shows that when the compound of formula (I) is used as the charge generation material for organic electroluminescent devices, the driving voltage can be effectively reduced, the current efficiency can be improved, and the service life of the device can be extended. The materials of the present invention have a significant performance improvement especially in improving the efficiency of organic electroluminescent devices and extending the life of organic electroluminescent devices, and organic electroluminescent devices with good performance can be obtained.

[0183] The above are only the preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.

Claims

1. A phosphine-substituted phenanthroline compound, characterized in that, Its structure is shown in formula (I):: Wherein, R 1 、R 2 、R 3 、R 4 are each independently selected from C1-C5 alkanes, C3-C6 cycloalkanes, C6-C 30 aryl which is unsubstituted or substituted by Rc, C3-C 30 heteroaryl; L 1 、L 2 、L 3 Each independently selected from a chemical bond, a C6-C arylene group which is unsubstituted or substituted by Rc, 30 a C3-C heteroarylene group which is unsubstituted or substituted by Rc; 30 ​ X 1 -X 5 each independently selected from N or C, and at least one is N; m and n are each independently selected from 0 and 1, and m + n ≥ 1; The heteroatoms on the heteroaryl or heteroarylene are each independently selected from O, S or N; The substituents Rc of each group are each independently selected from hydrogen, deuterium, halogen, nitro, cyano, C1-C4 alkyl, phenyl, biphenyl, terphenyl, pyridyl, pyrimidinyl or naphthyl.

2. The compound according to claim 1, characterized in that, The R 1 , R 2 , R 3 , R 4 are each independently selected from unsubstituted or Rc-substituted C6-C 18 aryl, unsubstituted or Rc-substituted C3-C 18 heteroaryl; and / or, The said L 1 、L 2 、L 3 are each independently selected from a chemical bond, a C6-C arylene group which is unsubstituted or substituted by Rc 18 and a C3-C heteroarylene group which is unsubstituted or substituted by Rc 30 .

3. The compound according to claim 1, characterized in that, The R 1 , R 2 , R 3 , R 4 are each independently selected from methyl, ethyl, isopropyl, and groups of the following compounds that are unsubstituted or substituted with Rc: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, dibenzofuran, dibenzothiophene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirofluorene.

4. The compound according to claim 1, characterized in that, The said L 1 , L 2 , L 3 Each independently selected from a chemical bond, a group of the following compounds which is unsubstituted or substituted by Rc: phenyl, pyridyl, pyrimidinyl, quinoxalinyl, quinazolinyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, anthryl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl.

5. The compound according to claim 1, characterized in that, The compound of formula (I) is selected from the compounds shown in A1 to A30 below:

6. An organic electroluminescent device, characterized in that, Comprising a charge generation layer and an electron transport layer, the charge generation layer material comprising the compound according to any one of claims 1 to 5.

7. The organic electroluminescent device according to claim 6, characterized in that, The charge generation layer material includes metal Li or Yb, and based on the mass of the charge generation layer material, the mass percentage content of the metal Li or Yb is 0.5% - 2.5%.

8. The organic electroluminescent device according to claim 6, characterized in that, The thickness of the charge generation layer is 10 nm - 30 nm, and the thickness of the electron transport layer is 10 nm - 40 nm.

9. A display device, characterized in that, It comprises the organic electroluminescent device according to any one of claims 6 - 8.

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