Arylamine compound and use thereof

Abstract

The application belongs to the technical field of display, and particularly relates to arylamine and application thereof. The organic compound provided by the application is based on the mother nucleus in the structure, and different substituent groups are combined to effectively control the change of LUMO energy level of the whole compound, better realize the ability of the light-emitting auxiliary layer to block electrons, and further make the organic electroluminescent device containing the organic compound have lower driving voltage, higher light-emitting efficiency and longer service life.

Description

Technical Field

[0001] This invention belongs to the field of display technology, specifically relating to an aromatic amine compound and its applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are devices that convert electrical energy into light by applying electricity to organic light-emitting materials. They generally have a structure comprising an anode, a cathode, and an organic layer between the anode and cathode. The organic layer of an organic OLED can consist of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (containing a host material and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The materials used in the organic layer are classified according to their function as hole injection materials, hole transport materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, and electron injection materials. In these organic OLEDs, due to the application of voltage, holes are injected from the anode into the light-emitting layer, and electrons are injected from the cathode into the light-emitting layer. The recombination of holes and electrons forms high-energy excitons. With this energy, the organic light-emitting compound reaches an excited state, and light is emitted by the energy generated when the excited state of the organic light-emitting compound returns to its ground state.

[0003] Organic light-emitting materials are the core of organic electroluminescent devices and the most important factor determining the luminous efficiency of these devices. However, OLEDs made from current organic light-emitting materials still require further reductions in driving voltage, current efficiency, and lifetime improvement during use. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing organic light-emitting materials used in organic electroluminescent devices, such as the need to reduce the driving voltage, improve current efficiency and lifetime, and to provide an aromatic amine compound and its application.

[0005] In the definition of substituent terms in this invention:

[0006] The term "organic electroluminescent material" in this invention disclosure refers to a material that can be used in organic electroluminescent devices and may contain at least one compound. If desired, the organic electroluminescent material may be contained in any layer constituting the organic electroluminescent device. For example, the organic electroluminescent material may be a hole injection material, a hole transport material, a hole assist material, a light-emitting assist material, an electron blocking material, a light-emitting material (containing a host material and a dopant material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0007] The term "multiple organic electroluminescent materials" in this invention disclosure refers to one or more organic electroluminescent materials comprising a combination of at least two compounds, said materials may be contained in any layer constituting an organic electroluminescent device. It may mean both materials contained before (e.g., before vapor deposition) and materials contained after (e.g., after vapor deposition) the organic electroluminescent device. For example, multiple organic electroluminescent materials may be a combination of at least two compounds, said materials may contain at least one of the following: a hole injection layer, a hole transport layer, a hole auxiliary layer, a light-emitting auxiliary layer, a light-emitting layer, an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The at least two compounds may be contained in the same layer or different layers, and may be mixed-evaporated or co-evaporated, or may be evaporated individually.

[0008] In this invention, the descriptive terms “each…independently selected”, “each…independently constitute”, and “each…independently constitute” are interchangeable and should be interpreted broadly. They can mean that the specific options expressed by the same symbols in different groups do not affect each other, or that the specific options expressed by the same symbols in the same group do not affect each other.

[0009] In this invention, the term "substituent" has its usual meaning as known in the art, referring to a chemical moiety covalently attached to or, where appropriate, fused to a parent nucleus group.

[0010] In this invention, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have substituents (hereinafter, for ease of description, substituents are collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl group having a substituent Rc or an unsubstituted aryl group. The aforementioned substituent, i.e., Rc, can be, for example, deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, or C1-C60 heteroaryl. Optionally, it can be, for example, deuterium, a halogen group, cyano, alkyl, haloalkyl, trialkylsilyl, deuterated alkyl, aryl, heteroaryl, etc. Of course, the number of substituents Rc can be one or more. When two substituents Rc are attached to the same atom, these two substituents Rc can exist independently or be connected to each other to form a ring with the atom; when two adjacent substituents Rc exist on a functional group, the adjacent substituents Rc can exist independently or fuse with the functional group to which they are attached to form a ring. "Unsubstituted" is defined as follows: it refers to being substituted by a hydrogen atom, and the hydrogen atoms in this invention include protium, deuterium, and tritium.

[0011] In this invention, C1-C60, C3-C60, and C6-C60 define the range of carbon atoms, where the number of carbon atoms is any integer within the defined range. For example, C6-C60 aryl means that the number of carbon atoms representing the aryl group can be any integer within the range of 6-60, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, and 60.

[0012] In this invention, the term "alkyl" refers, whether as part of other terms or used alone, to a saturated hydrocarbon group, which may be straight-chain or branched. The term "C1-C60 alkyl" is derived from a monovalent substituent of a straight-chain or branched saturated hydrocarbon having 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and more preferably 1 to 20 carbon atoms. Examples of such substituents include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0013] In this invention, the terms "aryl" and "arylene" include monocyclic, polycyclic, or fused-ring aryl groups, wherein the rings may be interrupted by short non-aromatic units, and may contain a spirostructure. Aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracene, fluorene, and spirodifluorene. Arylene groups include, but are not limited to, phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthraceneene, fluorene, and spirodifluorene. Arylene refers to a divalent or polyvalent group formed by the further loss of one or more hydrogen atoms from an aryl group.

[0014] In this invention, the term "heteroaryl" includes monocyclic, polycyclic, or fused-ring heteroaryl groups, wherein the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen, and sulfur. Heteroaryl groups in this invention include, but are not limited to, furanyl, phenylthio, pyrroleyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetraazinyl, triazolyl, tetraazolyl, furazolidyl, pyridinyl, pyrazinyl, and pyrimidine. Pyridyl, benzofuranyl, benzothiophene, isobenzofuranyl, dibenzofuranyl, dibenzothiophene, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisooxazolyl, benzooxazolyl, isoindolyl, indolyl, indazole, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxalolinyl, carbazole, phenoxazinyl, phenthiazinyl, phenanthidyl, benzo-m-dioxacyclopentenyl, dihydroacridyl And their derivatives, etc.; heteroaryl groups include, but are not limited to, pyrifos, pyrrolizyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridinyl, pyridazinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, dibenzofuranyl Furanyl, dibenzothiophene, benzimidazolyl, benzithiazolyl, benzisisothiazolyl, benzisisooxazolyl, benzisoxazolyl, isoindolyl, indolyl, ininzolyl, benzisazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxolinyl, carbazolyl, phenoxazinyl, phenoxazinyl, phenanthridineyl, benzo[m]dioxacyclopentenyl, dihydroacridyl, and their derivatives, etc. As used herein, the term "substituted" means that a hydrogen atom in the compound is replaced by another substituent. This position is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. When two or more substituents are present, the two or more substituents can be the same or different.

[0015] In this invention, the term "halogen" refers to an atom selected from fluorine, chlorine, bromine, and iodine.

[0016] In this invention, unless otherwise stated, hydrogen atoms include protium, deuterium, and tritium.

[0017] In this invention, the definition of a group specifies a range of carbon atoms, and the number of carbon atoms is any integer within the defined range, such as C6-C60 aryl. The number of carbon atoms representing an aryl group can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25, 30, 35, 40, 45, 50, 55 or 60, etc.

[0018] In this invention, unless otherwise specified, the substituents do not fuse with the group to which they belong.

[0019] In this invention, if the group is not specified as substituted or unsubstituted, it means that it has not been substituted.

[0020] In this invention, *- refers to a chemical bond that connects to other groups.

[0021] In this invention, the non-positional linker bond, which involves a single bond "*-" extending from the ring system, indicates that one end of the linker bond can connect to any position in the ring system traversed by the bond, and the other end connects to the rest of the compound molecule.

[0022] In this invention, * represents a connection site.

[0023] The solution adopted in this invention is as follows:

[0024] This application provides an aromatic amine compound having the structure shown in formula (1):

[0025]

[0026] In the formula,

[0027] X is selected from O or S;

[0028] L is selected from substituted or unsubstituted C6-C60 arylene groups;

[0029] R is selected from hydrogen, deuterium, cyano, hydroxyl, nitro, amido, hydrazine, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C1-C60 heteroaryl.

[0030] a is an integer selected from 0 to 7;

[0031] The substituents in the substituted C6-C60 aryl, substituted C1-C60 alkyl, substituted C3-C60 cycloalkyl, substituted C6-C60 aryl, and substituted C1-C60 heteroaryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C60 alkyl, C6-C60 aryl, and C1-C60 heteroaryl groups.

[0032] Preferably, the compound has the following structure:

[0033]

[0034] Preferably, L is selected from substituted or unsubstituted C6-C50 arylene groups;

[0035] The substituents in the substituted C6-C50 arylene are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C60 alkyl, C6-C60 aryl, and C1-C60 heteroaryl.

[0036] Preferably, L is selected from substituted or unsubstituted C6-C25 arylene groups;

[0037] The substituents in the substituted C6-C25 arylene are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl.

[0038] Preferably, L is selected from the group consisting of:

[0039]

[0040] Preferably, R is selected from hydrogen, deuterium, cyano, hydroxyl, nitro, amido, hydrazine, substituted or unsubstituted C1-C50 alkyl, substituted or unsubstituted C3-C50 cycloalkyl, substituted or unsubstituted C6-C50 aryl, or substituted or unsubstituted C1-C50 heteroaryl.

[0041] The substituents in the substituted C1-C50 alkyl, substituted C3-C50 cycloalkyl, substituted C6-C50 aryl, or substituted C1-C50 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl.

[0042] Preferably, R is selected from hydrogen, deuterium, cyano, hydroxyl, nitro, amido, hydrazine, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C25 aryl, or substituted or unsubstituted C1-C25 heteroaryl.

[0043] The substituents in the substituted C1-C25 alkyl, substituted C3-C25 cycloalkyl, substituted C6-C25 aryl, or substituted C1-C25 heteroaryl are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl.

[0044] Preferably, R is selected from the group consisting of hydrogen, deuterium, cyano, hydroxyl, nitro, amido, hydrazine, and the following groups:

[0045]

[0046]

[0047] Preferably, a is an integer selected from 0 to 7. Preferably, a is an integer selected from 0 to 6. Preferably, a is an integer selected from 0 to 5. Preferably, a is an integer selected from 0 to 4. Preferably, a is an integer selected from 0 to 3.

[0048] Preferably, 'a' is selected from an integer between 0 and 2.

[0049] Preferably, the compound is selected from one of the following structures:

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058] This invention provides a method for synthesizing the above-mentioned aromatic amine compounds, the synthesis method of which is described in reaction formulas 1 and 2 below. Reaction formula 1:

[0059]

[0060] Reaction 2:

[0061]

[0062] The present invention provides a light-emitting auxiliary layer material, wherein the light-emitting auxiliary layer material comprises the above-mentioned aromatic amine compound.

[0063] The present invention provides an organic electroluminescent device, wherein the organic electroluminescent device comprises the above-mentioned light-emitting auxiliary layer material or the above-mentioned aromatic amine compound.

[0064] Preferably, the organic electroluminescent device includes a first electrode, a second electrode disposed opposite to the first electrode, and at least one organic layer between the first electrode and the second electrode, wherein the organic layer comprises the aforementioned light-emitting auxiliary layer material or the aforementioned aromatic amine compound.

[0065] Optionally, the organic layer may consist of a single-layer structure or a multi-layer structure consisting of two or more layers.

[0066] Optionally, the organic electroluminescent device includes one or more of the following sequentially arranged layers: a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, and an electron injection layer.

[0067] Optionally, the organic layer includes a light-emitting auxiliary layer, which contains the aforementioned light-emitting auxiliary layer material or the aforementioned aromatic amine compound.

[0068] Optionally, the first electrode is an anode, which comprises anode materials, preferably materials with a large work function that facilitate hole injection into the hole transport layer. For example, the anode material may include: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline, but is not limited thereto.

[0069] Optionally, the hole injection layer is used to enhance the ability to inject holes into the hole transport layer. The hole injection layer can be selected from benzidine derivatives, starburst-like aryl amine compounds, phthalocyanine derivatives, or other materials; the present invention does not impose any special limitations on this. The material of the hole injection layer can, for example, be selected from the following compounds or any combination thereof:

[0070]

[0071]

[0072] Optionally, the hole transport layer may include one or more hole transport materials. The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer. The material of the hole transport layer may be selected from carbazole polymers, carbazole-linked triarylamine compounds, or other types of compounds. This invention does not impose any special limitations on this. For example, the material of the hole transport layer may be selected from the following compounds or any combination thereof:

[0073]

[0074]

[0075] Optionally, the light-emitting layer is a material capable of receiving holes and electrons from the hole transport layer and electron transport layer respectively, and combining them to emit light in the visible light region. The light-emitting layer can be composed of a single light-emitting material, or it can include a host material and a guest material. For example, the light-emitting layer includes a host material and a guest material. Holes injected into the light-emitting layer and then electrons injected into the light-emitting layer can recombine in the light-emitting layer to form excitons. The excitons transfer energy to the host material, and the host material transfers energy to the guest material, thereby causing the guest material to emit light. The host material of the light-emitting layer can include metal chelate compounds, bis(phenylacetyl) derivatives, aromatic amine derivatives, dibenzofuran derivatives, and other types of materials. The guest material of the light-emitting layer can include compounds with condensed aryl rings or their derivatives, compounds with heteroaryl rings or their derivatives, aromatic amine derivatives, or other types of materials. This application does not limit its application or its reverse application. The guest material is also called a dopant or dopant, and can be divided into fluorescent dopant and phosphorescent dopant according to the type of light emission.

[0076] Optionally, the electron transport layer can be a single-layer structure or a multi-layer structure, and may include one or more electron transport materials. The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light-emitting layer, and suppresses hole transfer from the light-emitting layer. The electron transport material is suitably one that can effectively receive electron injection from the cathode and transfer electrons to the light-emitting layer, and has a high electron mobility. The electron transport layer may be selected from, but is not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavonoid-metal complexes, etc., but is not limited to these.

[0077] Optionally, the electronic transport layer includes, but is not limited to, the following structures:

[0078]

[0079]

[0080] Optionally, the electron injection layer is used to enhance the ability to inject electrons into the electron transport layer. The electron injection layer may include fluorenone, anthraquinone dimethane, biphenylquinone, thiamethane dioxide, azole, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenemethane, anthrone, and their derivatives; inorganic materials such as alkali metal sulfides and alkali metal halides; or may include complexes of alkali metals and organic compounds.

[0081] Optionally, the cathode is a material with a small work function that facilitates electron injection into the functional layers. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or multilayer materials such as LiF / Al, Liq / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca.

[0082] This invention provides the application of the aromatic amine compound as described above, the light-emitting auxiliary layer material as described above, or the organic electroluminescent device as described above in optical fiber equipment, lighting equipment, electrophotographic photosensitive equipment, photoelectric converters, organic solar cells, switching element equipment, organic light-emitting field-effect transistors, image sensors, or dye lasers.

[0083] The above methods can be combined freely.

[0084] The beneficial effects of this invention are:

[0085] The organic compound provided by this invention, based on the core in the structure of formula (1), can be combined with different substituents to effectively control the change of LUMO energy level as a whole, better realize the ability of the light-emitting auxiliary layer to block electrons, and thus enable the organic electroluminescent device containing the organic compound to have a lower driving voltage, higher luminous efficiency and longer lifetime. Attached Figure Description

[0086] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0087] Figure 1 This is a structural diagram of the organic electroluminescent device of the present invention;

[0088] Reference numerals: 1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-light-assisted layer, 6-light-emitting layer, 7-electron transport layer, 8-electron injection layer, 9-cathode. Detailed Implementation

[0089] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0090] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0091] Synthesis Examples

[0092] Synthesis of intermediate M1:

[0093]

[0094] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add the following ingredients sequentially: MA-1 (1.2 mmol), 4-(1-naphthyl)phenylboronic acid (MB-1) (1.0 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), and 1,4-dioxane / water (10 mL / 2 mL). Heat to 90 °C and react for 5 hours. After the reaction is complete, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate M1-1 (yield 88%).

[0095] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M1-1 (1 mmol), 1-(4-bromophenyl)naphthalene (MC-1) (1.05 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate M-1 (yield 82%).

[0096] Synthesis of intermediates M2 to M7:

[0097] Intermediates M2 to M7 were synthesized using the same method as intermediate M1, with the difference being the substitution of related raw materials. For details, please refer to Table 1 for the raw material table of intermediates M2 to M7. Elemental analysis of intermediates M1 to M7 is detailed in Table 2.

[0098] Table 1. Raw material list for the synthesis of intermediates M2 to M7

[0099]

[0100]

[0101] Table 2 Elemental Analysis of Intermediates M1 to M7

[0102]

[0103]

[0104] Synthesis Example 1

[0105] This embodiment provides the synthesis of N-1, and its synthetic route is shown below:

[0106]

[0107] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M1 (1 mmol), 4-chlorodibenzofuran (N1-A) (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is completed, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then recrystallize the crude product twice with toluene and tetrahydrofuran, respectively, to obtain compound N-1 (yield 65%).

[0108] Elemental analysis: C 50 H 33 NO; Theoretical values: C, 90.47; H, 5.01; N, 2.11; O, 2.41; Measured values: C, 90.45; H, 5.02; N, 2.12; HRMS(ESI) m / z [M+H] + Theoretical value: 663.82; Measured value: 664.85.

[0109] Synthesis Example 2

[0110] This embodiment provides the synthesis of N-2, and its synthetic route is shown below:

[0111]

[0112] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M1 (1 mmol), N2-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, and wash twice with ethanol. The crude product is then purified twice by recrystallization from toluene and tetrahydrofuran, respectively, to obtain compound N-2 (yield 61%).

[0113] Elemental analysis: C 56 H 37 NO; Theoretical values: C, 90.90; H, 5.04; N, 1.89; O, 2.16; Measured values: C, 90.93; H, 5.02; N, 1.88; HRMS(ESI) m / z [M+H] + Theoretical value: 739.92; Measured value: 740.95.

[0114] Synthesis Example 3

[0115] This embodiment provides the synthesis of N-7, and its synthetic route is shown below:

[0116]

[0117] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M1 (1 mmol), N7-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, and wash twice with ethanol. The crude product is then purified twice by recrystallization from toluene and tetrahydrofuran, respectively, to obtain compound N-7 (yield 70%).

[0118] Elemental analysis: C 60 H 39 NO; Theoretical values: C, 91.23; H, 4.98; N, 1.77; O, 2.03; Measured values: C, 91.21; H, 4.99; N, 1.78; HRMS(ESI) m / z [M+H] + Theoretical value: 789.98; Measured value: 790.95.

[0119] Synthesis Example 4

[0120] This embodiment provides the synthesis of N-15, and its synthetic route is shown below:

[0121]

[0122] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M1 (1 mmol), N15-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is completed, cool to room temperature, filter, wash the filter cake twice with deionized water, and wash twice with ethanol. The crude product is then purified twice by recrystallization from toluene and tetrahydrofuran, respectively, to obtain compound N-15 (yield 68%).

[0123] Elemental analysis: C 66 H 43 NO; Theoretical values: C, 91.53; H, 5.00; N, 1.62; O, 1.85; Measured values: C, 91.55; H, 5.01; N, 1.59; HRMS(ESI) m / z [M+H] + Theoretical value: 866.08; Measured value: 867.11.

[0124] Synthesis Example 5

[0125] This embodiment provides the synthesis of N-24, and its synthetic route is shown below:

[0126]

[0127] Take a 100 mL three-necked round-bottom flask, add a stir bar and a reflux tube, and under nitrogen protection, add intermediate M2 (1 mmol), N24-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then recrystallize the crude product twice with toluene and tetrahydrofuran, respectively, to obtain compound N-24 (yield 65%).

[0128] Elemental analysis: C 60 H 39 NO; Theoretical value: C, 91.23; H, 4.98; N, 1.77; O, 2.03; Measured value: C, 91.21; H, 4.99; N, 1.78; HRMS(ESI)m / z[M+H]+: Theoretical value: 789.98; Measured value: 790.95.

[0129] Synthesis Example 6

[0130] This embodiment provides the synthesis of N-30, and its synthetic route is shown below:

[0131]

[0132] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M2 (1 mmol), NA-30 (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is completed, cool to room temperature, filter, wash the filter cake twice with deionized water, and wash twice with ethanol. The crude product is then purified twice by recrystallization from toluene and tetrahydrofuran, respectively, to obtain compound N-30 (yield 67%).

[0133] Elemental analysis: C 56 H 37 NO; Theoretical values: C, 90.90; H, 5.04; N, 1.89; O, 2.16; Measured values: C, 90.93; H, 5.02; N, 1.88; HRMS(ESI) m / z [M+H] + Theoretical value: 739.92; Measured value: 740.95.

[0134] Synthesis Example 7

[0135] This embodiment provides the synthesis of N-34, and its synthetic route is shown below:

[0136]

[0137] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M3 (1 mmol), N1-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, and wash twice with ethanol. The crude product is then purified twice by recrystallization from toluene and tetrahydrofuran, respectively, to obtain compound N-34 (yield 67%).

[0138] Elemental analysis: C 56 H 37 NO; Theoretical values: C, 90.90; H, 5.04; N, 1.89; O, 2.16; Measured values: C, 90.93; H, 5.02; N, 1.88; HRMS(ESI) m / z [M+H]+ Theoretical value: 739.92; Measured value: 740.95.

[0139] Synthesis Example 8

[0140] This embodiment provides the synthesis of N-44, and its synthetic route is shown below:

[0141]

[0142] Take a 100 mL three-necked round-bottom flask, add a stir bar and a reflux tube, and under nitrogen protection, add intermediate M4 (1 mmol), N44-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then recrystallize the crude product twice with toluene and tetrahydrofuran, respectively, to obtain compound N-44 (yield 63%).

[0143] Elemental analysis: C 66 H 43 NO; Theoretical values: C, 91.53; H, 5.00; N, 1.62; O, 1.85; Measured values: C, 91.55; H, 5.01; N, 1.59; HRMS(ESI) m / z [M+H] + Theoretical value: 866.08; Measured value: 867.11.

[0144] Synthesis Example 9

[0145] This embodiment provides the synthesis of N-57, and its synthetic route is shown below:

[0146]

[0147] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M5 (1 mmol), N57-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is completed, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then recrystallize the crude product twice with toluene and tetrahydrofuran, respectively, to obtain compound N-57 (yield 67%).

[0148] Elemental analysis: C 62 H 41NO; Theoretical values: C, 91.26; H, 5.06; N, 1.72; O, 1.96; Measured values: C, 91.27; H, 5.05; N, 1.72; HRMS(ESI) m / z [M+H] + Theoretical value: 816.02; Measured value: 817.05.

[0149] Synthesis Example 10

[0150] This embodiment provides the synthesis of N-90, and its synthetic route is shown below:

[0151]

[0152] Take a 100 mL three-necked round-bottom flask and place a stir bar and a reflux tube on top. Under nitrogen protection, add intermediate M6 (1 mmol), N90-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is completed, cool to room temperature, filter, wash the filter cake twice with deionized water, and wash twice with ethanol. The crude product is then purified twice by recrystallization from toluene and tetrahydrofuran, respectively, to obtain compound N-90 (yield 61%).

[0153] Elemental analysis: C 66 H 43 NO; Theoretical values: C, 91.53; H, 5.00; N, 1.62; O, 1.85; Measured values: C, 91.55; H, 5.01; N, 1.59; HRMS(ESI) m / z [M+H] + Theoretical value: 866.08; Measured value: 867.11.

[0154] Synthesis Example 11

[0155] This embodiment provides the synthesis of N-103, and its synthetic route is shown below:

[0156]

[0157] Take a 100 mL three-necked round-bottom flask, add a stir bar and a reflux tube, and under nitrogen protection, add intermediate M1 (1 mmol), N103-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then recrystallize the crude product twice with toluene and tetrahydrofuran, respectively, to obtain compound N-103 (yield 66%).

[0158] Elemental analysis: C 56 H 37 NS; Theoretical values: C, 88.97; H, 4.93; N, 1.85; S, 4.24; Measured values: C, 88.95; H, 4.94; N, 1.86; S, 4.24; HRMS(ESI) m / z [M+H] + Theoretical value: 755.98; Measured value: 756.95.

[0159] Synthesis Example 12

[0160] This embodiment provides the synthesis of N-130, and its synthetic route is shown below:

[0161]

[0162] Take a 100 mL three-necked round-bottom flask, add a stir bar and a reflux tube, and under nitrogen protection, add intermediate M7 (1 mmol), N130-A (1.1 mmol), tris(dibenzylacetone)palladium (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL) in sequence. Heat to 110 °C and react for 5 hours. After the reaction is complete, cool to room temperature, filter, wash the filter cake twice with deionized water, wash twice with ethanol, and then recrystallize the crude product twice with toluene and tetrahydrofuran, respectively, to obtain compound N-130 (yield 72%).

[0163] Elemental analysis: C 66 H 43 NS; Theoretical values: C, 89.86; H, 4.91; N, 1.59; S, 3.63; Measured values: C, 89.88; H, 4.90; N, 1.58; S, 3.63; HRMS(ESI) m / z [M+H] + Theoretical value: 882.14; Measured value: 883.17.

[0164] Device Examples and Device Comparisons

[0165] Device Example 1

[0166] This embodiment provides an organic electroluminescent device, such as... Figure 1 As shown, the device includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting auxiliary layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8, and a cathode 9, which are sequentially stacked on a substrate 1. The device structure is: anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting auxiliary layer (Prime) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0167] The specific preparation process is as follows:

[0168] 1) Substrate cleaning:

[0169] The glass substrate coated with transparent ITO was ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of acetone and ethanol 1:1), baked in a clean environment until all moisture was removed, and then cleaned with ultraviolet light and ozone.

[0170] 2) Preparation of organic layer:

[0171] The ITO transparent substrate was transferred to an evaporation equipment and vacuumed to 1×10⁻⁶. -6 Up to 2×10 -4 Pa, hole injection layer (HIL) / hole transport layer (HTL) / light-emitting auxiliary layer (Prime) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al) are sequentially deposited on the anode film.

[0172] in:

[0173] The hole injection layer (HIL) is a mixture of HAT-CN and HT-1, with a mass ratio of HAT-CN to HT-1 of 3:97. The hole injection layer thickness is 10 nm, and the total evaporation rate is 0.1 nm / s.

[0174] The hole transport layer (HTL) is made of HT-1 material, has a thickness of 80 nm, and a total evaporation rate of 0.1 nm / s.

[0175] The material of the light-emitting auxiliary layer (Prime) is compound N-1 obtained in synthesis example 1, the thickness of the light-emitting auxiliary layer is 10 nm, and the total evaporation rate is 0.1 nm / s;

[0176] The light-emitting layer (EML) is vacuum-deposited using a co-evaporation method. The material of the light-emitting layer includes a host material and a guest material, wherein the host material is BH-1 and the guest material is BD-1. The mass ratio of BH-1 to BD-1 is 96:4. The thickness of the light-emitting layer is 30 nm, and the total evaporation rate is 0.1 nm / s.

[0177] The electron transport layer (ETL) is a binary mixture of ET and LiQ in a mass ratio of 1:1, with a thickness of 30 nm and a total evaporation rate of 0.1 nm / s.

[0178] The electron injection layer (EIL) is made of LiQ, with a thickness of 1 nm and a total evaporation rate of 0.1 nm / s.

[0179] The cathode is made of aluminum with a thickness of 40 nm and a deposition rate of 1 nm / s.

[0180] Device Example 2

[0181] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-2 obtained in synthesis embodiment 2.

[0182] Device Example 3

[0183] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-7 obtained in synthesis embodiment 3.

[0184] Device Example 4

[0185] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-15 obtained in synthesis embodiment 4.

[0186] Device Example 5

[0187] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-24 obtained in synthesis embodiment 5.

[0188] Device Example 6

[0189] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-30 obtained in synthesis embodiment 6.

[0190] Device Example 7

[0191] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-34 obtained in synthesis embodiment 7.

[0192] Device Example 8

[0193] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-44 obtained in synthesis embodiment 8.

[0194] Device Example 9

[0195] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-57 obtained in synthesis embodiment 9.

[0196] Device Example 10

[0197] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-90 obtained in synthesis embodiment 10.

[0198] Device Example 11

[0199] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-103 obtained in synthesis embodiment 11.

[0200] Device Example 12

[0201] This device embodiment provides an organic electroluminescent device, which differs from device embodiment 1 only in that the material of the light-emitting auxiliary layer (Prime) is compound N-130 obtained in synthesis embodiment 12.

[0202] Device Comparison Example 1

[0203] This invention provides an organic electroluminescent device as a comparative example. The only difference between this device and device embodiment 1 is that the material of the light-emitting auxiliary layer (Prime) is compound REF-1, and its structure is as follows:

[0204]

[0205] Device Comparison Example 2

[0206] This invention provides an organic electroluminescent device as a comparative example. The only difference between this device and device embodiment 1 is that the material of the light-emitting auxiliary layer (Prime) is compound REF-2, and its structure is as follows:

[0207]

[0208] Device Comparison Example 3

[0209] This invention provides an organic electroluminescent device as a comparative example. The only difference between this device and device example 1 is that the material of the light-emitting auxiliary layer (Prime) is compound REF-3, and its structure is as follows:

[0210]

[0211] The materials used to prepare the above-mentioned device embodiments or device comparative examples are shown in Table 3 below.

[0212] Table 3. Some compounds used in device examples or device comparison examples.

[0213]

[0214] Device Test Examples

[0215] The organic electroluminescent devices obtained in the above-mentioned device examples 1-12 and device comparison examples 1-3 were tested.

[0216] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0217] Test conditions: Photoelectric property test conditions: current density 10 mA / cm² 2 .

[0218] Lifetime test: Current density 50mA / cm 2 The recording time (in hours) is recorded when the device brightness drops to 95% of its original brightness.

[0219] The performance test results of Device Examples 1-12 and Device Comparative Examples 1-3 are shown in Table 4. In order to better reflect the performance advantages of the present invention, the lifetime T95 of Device Comparative Example 1 is set to 100 and the current efficiency of Device Comparative Example 1 is set to 100. The lifetime T95 and current efficiency of Device Examples 1-12 and Device Comparative Examples 2-3 are relative values ​​to the lifetime T95 and current efficiency of Device Comparative Example 1, as shown in Table 4.

[0220] Table 4 Performance test results of device examples 1-12 and device comparative examples 1-3

[0221]

[0222]

[0223] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An aromatic amine compound, characterized in that, It has the structure shown in equation (1): In the formula, X is selected from O or S; L is selected from substituted or unsubstituted C6-C60 arylene groups; R is selected from hydrogen, deuterium, cyano, hydroxyl, nitro, amido, hydrazine, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C1-C60 heteroaryl. a is an integer selected from 0 to 7; The substituents in the substituted C6-C60 aryl, substituted C1-C60 alkyl, substituted C3-C60 cycloalkyl, substituted C6-C60 aryl, and substituted C1-C60 heteroaryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C60 alkyl, C6-C60 aryl, and C1-C60 heteroaryl groups.

2. The aromatic amine compound according to claim 1, characterized in that, The compound has the following structure:

3. An aromatic amine compound according to claim 1 or 2, characterized in that, L is selected from substituted or unsubstituted C6-C50 arylene groups; The substituents in the substituted C6-C50 arylene are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C60 alkyl, C6-C60 aryl, and C1-C60 heteroaryl. Preferably, L is selected from substituted or unsubstituted C6-C25 arylene groups; The substituents in the substituted C6-C25 arylene are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl. Preferably, L is selected from the group consisting of:

4. An aromatic amine compound according to claim 1, 2, or 3, characterized in that, R is selected from hydrogen, deuterium, cyano, hydroxyl, nitro, amido, hydrazine, substituted or unsubstituted C1-C50 alkyl, substituted or unsubstituted C3-C50 cycloalkyl, substituted or unsubstituted C6-C50 aryl, or substituted or unsubstituted C1-C50 heteroaryl. The substituents in the substituted C1-C50 alkyl, substituted C3-C50 cycloalkyl, substituted C6-C50 aryl, or substituted C1-C50 heteroaryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C50 alkyl, C6-C50 aryl, and C1-C50 heteroaryl groups. Preferably, R is selected from hydrogen, deuterium, cyano, hydroxyl, nitro, amido, hydrazine, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C25 aryl, or substituted or unsubstituted C1-C25 heteroaryl. The substituents in the substituted C1-C25 alkyl, substituted C3-C25 cycloalkyl, substituted C6-C25 aryl, or substituted C1-C25 heteroaryl groups are selected from one or more of deuterium, halogen, cyano, hydroxyl, nitro, amido, hydrazine, C1-C25 alkyl, C6-C25 aryl, and C1-C25 heteroaryl groups. Preferably, R is selected from the group consisting of hydrogen, deuterium, cyano, hydroxyl, nitro, amido, hydrazine, and the following groups:

5. An aromatic amine compound according to any one of claims 1-4, characterized in that, a is an integer selected from 0 to 7; preferably, a is an integer selected from 0 to 6. Preferably, 'a' is selected from integers between 0 and 5; Preferably, 'a' is selected from integers between 0 and 4; Preferably, 'a' is selected from integers between 0 and 3; Preferably, 'a' is selected from an integer between 0 and 2.

6. An aromatic amine compound according to any one of claims 1-5, characterized in that, The compound has the following structure:

7. A light-emitting auxiliary layer material, characterized in that, The light-emitting auxiliary layer material comprises an aromatic amine compound as described in any one of claims 1-6.

8. An organic electroluminescent device, characterized in that, The organic electroluminescent device comprises the above-mentioned light-emitting auxiliary layer material or the above-mentioned aromatic amine compound; Preferably, the organic electroluminescent device includes a first electrode, a second electrode disposed opposite to the first electrode, and at least one organic layer between the first electrode and the second electrode, wherein the organic layer comprises an aromatic amine compound as described in any one of claims 1-6 or a light-emitting auxiliary layer material as described in claim 7.

9. An organic electroluminescent device according to claim 8, characterized in that, The organic layer includes a light-emitting auxiliary layer, which comprises an aromatic amine compound as described in any one of claims 1-6 or a light-emitting auxiliary layer material as described in claim 7.

10. The use of an aromatic amine compound as described in any one of claims 1-6, or a light-emitting auxiliary layer material as described in claim 7, or an organic electroluminescent device as described in claim 8 or 9, in fiber optic devices, lighting devices, electrophotographic photosensitive devices, photoelectric converters, organic solar cells, switching element devices, organic light-emitting field-effect transistors, image sensors, or dye lasers.

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