An organic electroluminescent device

Abstract

The application belongs to the technical field of display, and particularly relates to an organic electroluminescent device. The organic electroluminescent device provided by the application comprises at least two organic light-emitting layers between a cathode and an anode, and a charge generation layer is arranged between the two organic light-emitting layers. The charge generation layer comprises a structure shown in formula (1), and the coordination ability with a metal dopant is improved by further limiting the types of substituents, so that the stability of the charge generation layer is enhanced, and the matching degree with adjacent energy levels is improved. Meanwhile, the organic light-emitting layer comprises a structure shown in formula (2), which is helpful to reduce the interface charge accumulation and non-radiative recombination, and can match the charge injection behavior of the charge generation layer. The two structures synergistically optimize the charge injection, transmission and recombination processes in the device, so that the organic electroluminescent device has a lower driving voltage, a higher light-emitting efficiency and a longer service life.

Description

Technical Field

[0001] This invention belongs to the field of display technology, and specifically relates to an organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are semiconductor devices that achieve photoelectric conversion based on a charge injection excitation mechanism. Their typical structure consists of an anode, a cathode, and a sandwich functional system: the anode is a metal oxide layer with hole transport characteristics, the cathode is a low work function metal material, and the sandwich functional layer system usually consists of a carrier injection layer, a transport layer, an exciton confinement layer, and a bipolar light-emitting dielectric layer.

[0003] In operation, holes migrate to the luminescent region through the hole injection layer, while electrons are transported to the region through the electron injection layer. When these two types of charge carriers recombine in the luminescent medium, they form excitons in an excited state. These excited excitons release energy through radiative transitions, and their energy conversion efficiency directly determines the luminescent performance of the device.

[0004] The choice of material system is a core factor affecting device performance. An ideal light-emitting material needs to possess high stability, an energy level structure that matches adjacent functional layers, and balanced carrier mobility characteristics. However, the performance of existing organic electroluminescent materials is poor, resulting in high device driving voltage, low current efficiency, and short operating lifetime. These technical bottlenecks severely restrict the industrial application of OLEDs. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor performance of existing organic electroluminescent materials, which leads to high driving voltage, low current efficiency and short device life, and to provide an organic electroluminescent device.

[0006] In the definition of substituent terms in this invention: 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 substituent Rc mentioned above 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, 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, the 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 two adjacent substituents Rc can exist independently or fused with the functional group to which they are attached to form a ring.

[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 term "cycloalkyl" refers to a cyclic alkyl group consisting of at least 3 carbon atoms. Further, C3-C60 cycloalkyl refers to a monocyclic or polycyclic hydrocarbon derived from a main cyclic chain of 3 to 60 carbon atoms, preferably 3 to 40 carbon atoms, and even more preferably 3 to 20 carbon atoms. The cycloalkyl group includes, but is not limited to, cyclopropyl, cyclobutyl, adamantyl, etc.

[0014] In this invention, the term "heterocyclic alkyl" includes one or more of O, S, Se, N, and Si as heteroatoms. C1-C60 cycloalkyl refers to a monocyclic or polycyclic hydrocarbon derived from a main chain of 1 to 60 carbon atoms, preferably 3 to 40 carbon atoms, and even more preferably 3 to 20 carbon atoms. Here, "polycyclic" refers to a group in which a heterocyclic alkyl group is directly attached to or fused with another cyclic group. Furthermore, the other cyclic group can also be a heterocyclic alkyl group, such as cycloalkyl, aryl, heteroaryl, etc.

[0015] In this invention, the term "alkoxy group" refers to a monovalent functional group attached to the parent molecule via an oxygen atom (-O-), and its general formula is optionally -OR, where R represents an alkyl group, including straight-chain, branched, or cyclic structures. For example, R can be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc.

[0016] In this invention, the term "alkylthio" refers to a monovalent functional group in which a sulfur atom (-S-) is attached to a parent molecule. Its general formula is optionally -SR, where R represents an alkyl group, including straight-chain, branched, or cyclic structures. For example, R can be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc.

[0017] In this invention, the term "alicyclic" refers to an alicyclic hydrocarbon that does not have an aromatic or heteroaromatic ring in the ring system. The alicyclic hydrocarbon is a carbon ring composed of three or more carbon atoms. The two adjacent carbon atoms in the ring can be connected by a single bond, a double bond, or a triple bond. The number of rings can be one or more. Alicyclic hydrocarbons include, but are not limited to, cyclopropane, cyclobutane, cyclohexane, cyclopentane, adamantane, norbornane, cyclopentene, cyclopentadiene, cyclohexene, and cyclohexadiene.

[0018] 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.

[0019] In this invention, the terms "heteroaryl" and "hybrid heteroaryl" include monocyclic, polycyclic, or fused-ring heteroaryl groups, wherein the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen, sulfur, and selenium. 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, tetrazolyl, pyridinyl, and others. Pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, dibenzofuranyl, dibenzothiopheneyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisooxazolyl, benzooxazolyl, isoindolyl, indolyl, indazoleyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxalinyl, carbazoleyl, phenoxazinyl, phenthiazinyl, phenanthidyl, benzom-dioxacyclopentenyl, Dihydroacridinyl and its derivatives, etc.; heteroaryl groups include, but are not limited to, imidinyl, phenylthioyl, pyrrolyl, imidazolyl, pyrazolyl, imidazolyl, imidazithiazolyl, isothiazolyl, isoxazolyl, imidazithiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridinyl, pyridazinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, dibenzofuranyl Furanyl, dibenzothiophene, benzimidazolyl, benzithiazolyl, benzisisothiazolyl, benzisisooxazolyl, benzisoxazolyl, isoindolyl, indolyl, indazolyl, benzisthiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxolinyl, carbazolyl, phenoxazinyl, phenthiazinyl, phenanthridineyl, benzism-dioxacyclopentenyl, dihydroacridylyl, and their derivatives, etc.

[0020] In this invention, the term "single bond" refers to the connection between two adjacent groups.

[0021] In this invention, unless otherwise specified, the substituents do not fuse with the group to which they belong.

[0022] In this invention, if the group is not specified as substituted or unsubstituted, it means that it has not been substituted.

[0023] In this invention, It refers to the chemical bond that connects with other groups.

[0024] In this invention, the non-positioning connecting key involves a single bond extending from the ring system. "This means that one end of the linking bond can be connected to any position in the ring system that the bond passes through, and the other end is connected to the rest of the compound molecule."

[0025] The solution adopted in this invention is as follows: An organic electroluminescent device includes: a cathode; an anode disposed opposite to the cathode; and at least two organic light-emitting layers between the cathode and the anode. Among them, there is a charge generation layer between two adjacent organic light-emitting layers, the charge generation layer includes the structure shown in formula (1), and the organic light-emitting layer includes the structure shown in formula (2).

[0026] In formula (1), Ra and Rb are selected from the structure shown in formula (1-1) and the other is selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl. R 1 Selected from hydrogen or deuterium; n1 is an integer selected from 0 to 4;

[0027] In equation (1-1), L 1 and L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene; Ar 1 Selected from substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups; R 2 Selected from hydrogen or deuterium; n2 is selected from integers between 0 and 8;

[0028] In equation (2), X is selected from O or S; Ring Q is selected from substituted or unsubstituted benzene rings; R 3 and R 4 Each is independently selected from hydrogen or deuterium; Ar 2 Selected from substituted or unsubstituted C6-C30 aryl groups; L 3 and L 4 Each is independently selected from single-bonded, substituted, or unsubstituted C6-C30 arylene groups; n3 is an integer selected from 0 to 8. n4 is selected from integers between 0 and 10; In this embodiment, the substituted benzene ring, the substituted C6-C30 aryl group, the substituted C3-C30 heteroaryl group, the substituted C6-C30 arylene group, and the substituted C3-C30 heteroarylene group are each independently substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C18 alkyl, C6-C30 aryl, and C3-C30 heteroaryl.

[0029] Optional, X is selected from O; Optional, X is selected from S; Optionally, n1 is selected from 0, 1, 2, 3, 4; Optionally, n2 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8; Optionally, n3 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8; Optionally, n4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; Preferably, the compound shown in formula (1) is represented by the following chemical formula:

[0030] In the formula, Ra, Rb, R 1 R 2 n1, n2, L 1 L 2 Ar 1 Defined as described above.

[0031] Preferred, L 1 and L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C3-C20 heteroarylene; The substituted C6-C20 arylene and the substituted C3-C20 heteroarylene are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C20 alkyl, C6-C20 aryl, and C3-C20 heteroaryl.

[0032] Preferred, L 1 and L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C18 arylene, substituted or unsubstituted C3-C18 heteroarylene; The substituted C6-C18 arylene and the substituted C3-C18 heteroarylene are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C18 alkyl, C6-C18 aryl, and C3-C18 heteroaryl.

[0033] Preferred, L 1 and L 2Each is independently selected from single-bonded, substituted or unsubstituted C6-C15 arylene, substituted or unsubstituted C3-C15 heteroarylene; The substituted C6-C15 arylene and the substituted C3-C15 heteroarylene are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C15 alkyl, C6-C15 aryl, and C3-C15 heteroarylene.

[0034] Preferred, L 1 and L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C12 arylene, substituted or unsubstituted C3-C12 heteroarylene; The substituted C6-C12 arylene and the substituted C3-C12 heteroarylene are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C12 alkyl, C6-C12 aryl, and C3-C12 heteroarylene.

[0035] Preferred, L 1 and L 2 Each group D is independently selected from single-bonded, substituted, or unsubstituted groups, and said group D is selected from the group consisting of: ; Wherein, the substituted group D is substituted by at least one selected from the group consisting of: deuterium, tert-butyl, cyano, phenyl, naphthyl, biphenyl, terphenyl, phenylnaphthyl, naphthylphenyl, binaphthyl, pyridyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothiophene.

[0036] Preferably, Ra and Rb are each independently selected from substituted or unsubstituted C6-C20 aryl groups and substituted or unsubstituted C3-C20 heteroaryl groups; The substituted C6-C20 aryl group and the substituted C3-C20 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C20 aryl, C3-C20 heteroaryl.

[0037] Preferably, Ra and Rb are each independently selected from substituted or unsubstituted C6-C18 aryl groups and substituted or unsubstituted C3-C18 heteroaryl groups; The substituted C6-C18 aryl group and the substituted C3-C18 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C18 aryl, C3-C18 heteroaryl.

[0038] Preferably, Ra and Rb are each independently selected from substituted or unsubstituted C6-C15 aryl groups and substituted or unsubstituted C3-C15 heteroaryl groups; The substituted C6-C15 aryl group and the substituted C3-C15 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C15 aryl, C3-C15 heteroaryl.

[0039] Preferably, Ra and Rb are each independently selected from substituted or unsubstituted C6-C12 aryl groups and substituted or unsubstituted C3-C12 heteroaryl groups; The substituted C6-C12 aryl group and the substituted C3-C12 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C12 aryl, C3-C12 heteroaryl.

[0040] Preferably, Ra and Rb are each independently selected from substituted or unsubstituted groups F, said groups F being selected from the group consisting of: ; Wherein, the substituted group F is substituted by at least one selected from the group consisting of: deuterium, halogen, cyano, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, phenylnaphthyl, naphthylphenyl, binaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothiophene.

[0041] Preferred, Ar 1 Selected from substituted or unsubstituted C6-C20 aryl groups and substituted or unsubstituted C3-C20 heteroaryl groups; The substituted C6-C20 aryl group and the substituted C3-C20 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C20 aryl, C3-C20 heteroaryl.

[0042] Preferred, Ar 1 Selected from substituted or unsubstituted C6-C18 aryl groups and substituted or unsubstituted C3-C18 heteroaryl groups; The substituted C6-C18 aryl group and the substituted C3-C18 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C18 aryl, C3-C18 heteroaryl.

[0043] Preferred, Ar 1 Selected from substituted or unsubstituted C6-C15 aryl groups and substituted or unsubstituted C3-C15 heteroaryl groups; The substituted C6-C15 aryl group and the substituted C3-C15 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C15 aryl, C3-C15 heteroaryl.

[0044] Preferred, Ar 1 Selected from substituted or unsubstituted C6-C12 aryl groups and substituted or unsubstituted C3-C12 heteroaryl groups; The substituted C6-C12 aryl group and the substituted C3-C12 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C12 aryl, C3-C12 heteroaryl.

[0045] Preferred, Ar 1 The group G is selected from substituted or unsubstituted groups, wherein the group G is selected from the group consisting of: ; Wherein, the substituted group G is substituted by at least one selected from the group consisting of: deuterium, halogen, cyano, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, phenylnaphthyl, naphthylphenyl, binaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothiophene.

[0046] Preferably, the structure shown in formula (1) comprises the following compounds: .

[0047] Preferably, the compound shown in formula (2) is represented by the following chemical formula:

[0048] In the formula, X and R 3 R 4 Ar 2 L 3 L 4 The definitions of n1, n2, and n3 are as described above.

[0049] Preferably, the compound shown in formula (2) is represented by the following chemical formula: ; In the formula, X and R 3 R 4 Ar 2 L 3 L 4 The definitions of n1, n2, and n3 are as described above.

[0050] Preferred, L 3 and L 4 Each is independently selected from single-bonded, substituted, or unsubstituted C6-C20 arylene groups; The substituted C6-C20 arylene groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C18 alkyl, C6-C20 aryl.

[0051] Preferred, L 3 and L 4 Each is independently selected from single-bonded, substituted, or unsubstituted C6-C18 arylene groups; The substituted C6-C18 arylene groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C18 alkyl, C6-C18 aryl.

[0052] Preferred, L 3 and L 4 Each is independently selected from single-bonded, substituted, or unsubstituted C6-C15 arylene groups; The substituted C6-C15 arylene groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C15 alkyl, C6-C15 aryl.

[0053] Preferred, L 3 and L 4 Each is independently selected from single-bonded, substituted, or unsubstituted C6-C12 arylene groups; The substituted C6-C12 arylene groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C12 alkyl, C6-C12 aryl.

[0054] Preferred, L 3 and L 4 Each H is independently selected from single-bonded, substituted, or unsubstituted groups, wherein the groups H are selected from the group consisting of: ; Wherein, the substituted group H is substituted by at least one selected from the group consisting of: deuterium, tert-butyl, cyano, phenyl, naphthyl, biphenyl, terphenyl, phenylnaphthyl, naphthylphenyl, and binaphthyl.

[0055] Preferred, Ar 2 Selected from substituted or unsubstituted C6-C20 aryl groups; The substituted C6-C20 aryl groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C20 alkyl, and C6-C20 aryl.

[0056] Preferred, Ar 2 Selected from substituted or unsubstituted C6-C18 aryl groups; The substituted C6-C18 aryl groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C18 alkyl, C6-C18 aryl.

[0057] Preferred, Ar 2 Selected from substituted or unsubstituted C6-C15 aryl groups; The substituted C6-C15 aryl groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C15 alkyl, C6-C15 aryl.

[0058] Preferred, Ar 2 Selected from substituted or unsubstituted C6-C12 aryl groups; The substituted C6-C12 aryl groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C12 alkyl, C6-C12 aryl.

[0059] Preferred, Ar 2 The group L is selected from substituted or unsubstituted groups, wherein the group L is selected from the group consisting of: ; Wherein, the substituted group L is substituted by at least one selected from the group consisting of: deuterium, halogen, cyano, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, phenylnaphthyl, naphthylphenyl, and binaphthyl.

[0060] Preferably, the structure shown in formula (2) comprises the following compounds: .

[0061] It is understandable that in this invention, Indicates the connection location.

[0062] It is understood that the number of substituents is not limited in this invention, and the number of substituents can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc. For example, when the substituent is deuterium, it can be fully deuterated, semi-deuterated, or 1, 2, 3, 4... deuterium substitutions.

[0063] Preferably, the charge generation layer comprises an n-type charge generation layer and a p-type charge generation layer, wherein the n-type charge generation layer comprises a structure as shown in formula (1).

[0064] Preferably, the n-type charge generation layer further comprises a metal dopant; the metal dopant is one or a combination of at least two of alkali metals, alkaline earth metals and rare earth metals, or a combination of at least two of metal alloys containing alkali metals, alkaline earth metals and rare earth metals.

[0065] Preferably, the metal dopant is selected from Li, Mg, or Yb, or any combination thereof.

[0066] There are no special restrictions on the p-type charge generation layer; it can be set in a conventional manner in the field and matched with the above-mentioned n-type charge generation layer.

[0067] Preferably, the p-type charge generation layer can be composed of HAT-CN and TCTA, and the present invention does not make any special setting on their ratio.

[0068] Preferably, the organic electroluminescent device comprises two organic light-emitting layers, the first organic light-emitting layer being closer to the anode and the second organic light-emitting layer being closer to the cathode, and the charge-generating layer being located between the first organic light-emitting layer and the second organic light-emitting layer; Preferably, the organic electroluminescent device includes an anode, a hole injection layer, a first hole transport layer, a first electron blocking layer, a first organic light-emitting layer, a first hole blocking layer, a first electron transport layer, an n-type charge generation layer, a p-type charge generation layer, a second hole transport layer, a second electron blocking layer, a second organic light-emitting layer, a second hole blocking layer, a second electron transport layer, an electron injection layer, and a cathode, all stacked together.

[0069] Preferably, the first organic light-emitting layer or the second organic light-emitting layer includes a blue light-emitting layer, a red light-emitting layer, or a green light-emitting layer; Preferably, the first organic light-emitting layer or the second organic light-emitting layer includes a blue light-emitting layer.

[0070] Preferably, the blue light emitting layer comprises the structure shown in formula (2); Preferably, the blue light-emitting layer further comprises the structure shown in formula (3):

[0071] In equation (3), Y is selected from O or S; Rc and Rd are each independently selected from hydrogen or methyl, and at least one of Rc and Rd is selected from methyl. R 5 To R 8 Each group is independently selected from hydrogen, deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 heterocycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamine, substituted or unsubstituted C3-C30 heteroarylamine, wherein multiple R 3 or multiple R 4 or multiple R 5 or multiple R 6 They can connect with each other to form substituted or unsubstituted C3-C30 aliphatic rings, or substituted or unsubstituted C6-C30 aromatic rings; n5 to n8 are each independent integers selected from 0 to 4; Among them, substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C2-C30 heterocycloalkyl, substituted C1-C30 alkoxy, substituted C1-C30 alkylthio, substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C6-C30 arylamine, substituted C3-C30 heteroarylamine, substituted C3-C30 aliphatic ring, substituted C6-C30 Each aromatic ring is independently substituted by at least one of the following groups: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, C1-C30 alkyl, C3-C30 cycloalkyl, C2-C30 heterocycloalkyl, C1-C30 alkoxy, C1-C30 alkylthio, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 aromaticamine, C3-C30 heteroaryl.

[0072] Optionally, n5 is selected from 0, 1, 2, 3, 4; Optionally, n6 is selected from 0, 1, 2, 3, 4; Optionally, n7 is selected from 0, 1, 2, 3, 4; Optionally, n8 is selected from 0, 1, 2, 3, 4.

[0073] Preferably, the compound represented by formula (3) is represented by the following chemical formula: ; In the formula, R 5 To R 8 n5 to n8 are defined as described above.

[0074] Preferred, R 5 To R 8 Each group is independently selected from hydrogen, deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylthio, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, substituted or unsubstituted C6-C20 arylamine, substituted or unsubstituted C3-C20 heteroarylamine, wherein multiple R 5 or multiple R 6 or multiple R 7 or multiple R 8 They can connect with each other to form substituted or unsubstituted C3-C20 aliphatic rings, or substituted or unsubstituted C6-C20 aromatic rings; Among them, substituted C1-C20 alkyl, substituted C3-C20 cycloalkyl, substituted C2-C20 heterocycloalkyl, substituted C1-C20 alkoxy, substituted C1-C20 alkylthio, substituted C6-C20 aryl, substituted C3-C20 heteroaryl, substituted C6-C20 arylamine, substituted C3-C20 heteroarylamine, substituted C3-C20 aliphatic ring, substituted C6-C20 Each aromatic ring is independently substituted by at least one of the following groups: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C1-C20 alkoxy, C1-C20 alkylthio, C6-C20 aryl, C3-C20 heteroaryl, C6-C20 aromaticamine, C3-C20 heteroaromaticamine.

[0075] Preferred, R 5 To R 8 Each group is independently selected from hydrogen, deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C2-C18 heterocycloalkyl, substituted or unsubstituted C1-C18 alkoxy, substituted or unsubstituted C1-C18 alkylthio, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C3-C18 heteroaryl, substituted or unsubstituted C6-C18 arylamine, substituted or unsubstituted C3-C18 heteroarylamine, wherein multiple R 5 or multiple R6 or multiple R 7 or multiple R 8 They can connect with each other to form substituted or unsubstituted C3-C18 aliphatic rings, or substituted or unsubstituted C6-C18 aromatic rings; Among them, substituted C1-C18 alkyl, substituted C3-C18 cycloalkyl, substituted C2-C18 heterocycloalkyl, substituted C1-C18 alkoxy, substituted C1-C18 alkylthio, substituted C6-C18 aryl, substituted C3-C18 heteroaryl, substituted C6-C18 arylamine, substituted C3-C18 heteroarylamine, substituted C3-C18 alicyclic, substituted C6-C18 Each aromatic ring is independently substituted by at least one of the following groups: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, C1-C18 alkyl, C3-C18 cycloalkyl, C2-C18 heterocycloalkyl, C1-C18 alkoxy, C1-C18 alkylthio, C6-C18 aryl, C3-C18 heteroaryl, C6-C18 aromaticamine, C3-C18 heteroaromaticamine.

[0076] Preferred, R 5 To R 8 Each group is independently selected from hydrogen, deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C15 heterocycloalkyl, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted C1-C15 alkylthio, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C3-C15 heteroaryl, substituted or unsubstituted C6-C15 arylamine, substituted or unsubstituted C3-C15 heteroarylamine, wherein multiple R 5 or multiple R 6 or multiple R 7 or multiple R 8 They can connect with each other to form substituted or unsubstituted C3-C15 aliphatic rings, or substituted or unsubstituted C6-C15 aromatic rings; Among them, substituted C1-C15 alkyl, substituted C3-C15 cycloalkyl, substituted C2-C15 heterocycloalkyl, substituted C1-C15 alkoxy, substituted C1-C15 alkylthio, substituted C6-C15 aryl, substituted C3-C15 heteroaryl, substituted C6-C15 arylamine, substituted C3-C15 heteroarylamine, substituted C3-C15 aliphatic ring, substituted C6-C15 Each aromatic ring is independently substituted by at least one of the following groups: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, C1-C15 alkyl, C3-C15 cycloalkyl, C2-C15 heterocycloalkyl, C1-C15 alkoxy, C1-C15 alkylthio, C6-C15 aryl, C3-C15 heteroaryl, C6-C15 aromaticamine, C3-C15 heteroaryamine.

[0077] Preferred, R 5 To R 8 Each group is independently selected from hydrogen, deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C3-C12 heteroaryl, substituted or unsubstituted C6-C12 arylamine, substituted or unsubstituted C3-C12 heteroarylamine, wherein multiple R 5 or multiple R 6 or multiple R 7 or multiple R 8 They can connect with each other to form substituted or unsubstituted C3-C12 aliphatic rings, or substituted or unsubstituted C6-C12 aromatic rings; Among them, substituted C1-C12 alkyl, substituted C3-C12 cycloalkyl, substituted C2-C12 heterocyclic alkyl, substituted C1-C12 alkoxy, substituted C1-C12 alkylthio, substituted C6-C12 aryl, substituted C3-C12 heteroaryl, substituted C6-C12 arylamine, substituted C3-C12 heteroarylamine, substituted C3-C12 aliphatic ring, substituted C6-C12 Each aromatic ring is independently substituted by at least one of the following groups: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 heterocycloalkyl, C1-C12 alkoxy, C1-C12 alkylthio, C6-C12 aryl, C3-C12 heteroaryl, C6-C12 aromaticamine, C3-C12 heteroarylamine.

[0078] Preferred, R 5 To R 8Each group is independently selected from hydrogen, deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, or substituted or unsubstituted groups K: ; Each of the groups K is independently substituted by at least one selected from the group consisting of: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, phenyl, naphthyl, biphenyl; Among them, multiple R 3 or multiple R 4 or multiple R 5 or multiple R 6 They can connect with each other to form substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclohexane, or substituted or unsubstituted benzene rings; Wherein, the substituted cyclopropane, substituted cyclobutane, substituted cyclohexane, and substituted benzene ring are each independently substituted by at least one selected from the group consisting of: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, phenyl, naphthyl, and biphenyl.

[0079] Preferably, the structure shown in formula (3) comprises the following compounds: .

[0080] Preferably, the anode comprises an anode material, preferably a material with a large work function that facilitates hole injection into the first 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.

[0081] More preferably, the anode is selected as indium tin oxide (ITO).

[0082] Preferably, the hole injection layer is used to enhance the ability to inject holes into the first 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: .

[0083] Preferably, the first hole transport layer or the second hole transport layer comprises compounds selected from the following compounds or any combination thereof: .

[0084] Preferably, the first electron blocking layer or the second electron blocking layer comprises the following structure: .

[0085] Preferably, the first hole-blocking layer or the second hole-blocking layer comprises the following structure: .

[0086] Preferably, the first electron transport layer or the second electron transport layer is composed of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBI) and lithium octahydroxyquinoline (LiQ).

[0087] .

[0088] Preferably, the electron injection layer is used to enhance the ability to inject electrons into the second electron transport layer. The electron injection layer may include inorganic materials such as alkali metal sulfides and alkali metals, or may include complexes of alkali metals and organic materials. More preferably, the electron injection layer may include ytterbium (Yb).

[0089] Preferably, the cathode may comprise a cathode material that has a small work function and 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.

[0090] It should be noted that the above-mentioned organic electroluminescent devices are fabricated using conventional methods in the art, such as depositing layers on a substrate.

[0091] The present invention also provides an application of the above-described organic electroluminescent compound, or the above-described n-type charge generating layer, or the above-described organic electroluminescent device 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.

[0092] The present invention also provides an organic electroluminescent product, which includes the above-described organic electroluminescent device.

[0093] The present invention also provides an electronic device comprising the above-described organic electroluminescent compound.

[0094] Preferably, the electronic devices include perovskite photovoltaic devices, perovskite light-emitting devices, display devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic photodetectors, organic photoreceptors, organic field quenching devices, luminescent electrochemical cells, and organic laser diodes.

[0095] The above can be combined freely.

[0096] The beneficial effects of this invention are: The organic electroluminescent device provided by this invention comprises at least two organic light-emitting layers located between a cathode and an anode, and a charge-generating layer is disposed between the two organic light-emitting layers. The charge-generating layer comprises the structure shown in formula (1), which enhances the coordination ability with metal dopants by further limiting the types of substituents, thereby enhancing the stability of the charge-generating layer and improving its matching degree with adjacent energy levels. At the same time, the organic light-emitting layer comprises the structure shown in formula (2), which helps to reduce interfacial charge accumulation and nonradiative recombination, and can match the charge injection behavior of the charge-generating layer. The two work synergistically to optimize the charge injection, transport and recombination process inside the device, thereby enabling the organic electroluminescent device to have a lower driving voltage, higher luminous efficiency and longer lifespan. Attached Figure Description

[0097] 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.

[0098] Figure 1 This is a structural diagram of the stacked organic electroluminescent device in the device embodiment of the present invention; 1-Anode, 2-Hole injection layer, 3-First hole transport layer, 4-First electron blocking layer, 5-First organic light-emitting layer, 6-First hole blocking layer, 7-First electron transport layer, 8-n-type charge generation layer, 9-p-type charge generation layer, 10-Second hole transport layer, 11-Second electron blocking layer, 12-Second organic light-emitting layer, 13-Second hole blocking layer, 14-Second electron transport layer, 15-Electron injection layer, 16-Cathode. Detailed Implementation

[0099] 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.

[0100] 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.

[0101] When referring to material ratios, unless otherwise specified, the ratio refers to volume ratio.

[0102] The method for synthesizing the compound shown in formula (1) is as follows: The synthetic method of the compound represented by formula (1-2) is shown below: ; The synthetic methods for the compounds represented by formula (1-3) are as follows: .

[0103] Example: Synthesis of intermediate C1-A:

[0104] In a 2L three-necked flask, under nitrogen protection, add raw material C1-a (248.06 mmol), raw material C1-b (248.06 mmol), potassium carbonate (620.15 mmol), tetrahydrofuran (440 mL), and 70 mL of [unspecified substance]. The reaction was carried out overnight at C. After the reaction was completed, the mixture was extracted with dichloromethane, and the organic phase was dried with anhydrous sodium sulfate to remove the organic solvent, yielding intermediate Cl-A-1 (yield 89.66%).

[0105] In a 1L three-necked flask, under nitrogen protection, intermediate Cl-A-1 (210.00 mmol), phosphorus oxychloride (315.00 mmol), and 600 mL of anhydrous dioxane were added, along with 105 mL of [unspecified substance]. The reaction was carried out overnight at C. After the reaction was completed, the product was extracted with dichloromethane, the organic layer was dried with anhydrous magnesium sulfate, and the organic solvent was removed by vacuum distillation. The crude product was filtered through a column chromatography column with a mixed solvent (dichloromethane: tetrahydrofuran = 4:1, v:v) to give intermediate C1-A (yield 79.8%).

[0106] The synthesis method of intermediate Cn-A is the same as that of intermediate C1-A, except that the relevant raw materials are replaced. The raw materials and yields of intermediate Cn-A are shown in Table 1.

[0107] Table 1. Raw material list for the synthesis of intermediate Cn-A

[0108] Synthesis of intermediate C1-B:

[0109] In a 2L three-necked flask, under nitrogen protection, the following ingredients were added: C1-c (248.06 mmol), C1-d (248.06 mmol), potassium carbonate (620.15 mmol), dioxane (440 mL), water (110 mL), and tetraphenylphosphine palladium (2.481 mmol). 90 μL of the solution was added. The reaction was carried out overnight at C. After the reaction was completed, the mixture was extracted with dichloromethane, the organic phase was dried with anhydrous sodium sulfate to remove the organic solvent, ethanol was added and stirred for 1 h, and the mixture was filtered to obtain intermediate Cl-B-1 (yield 89.61%).

[0110] In a 1L three-necked flask, under nitrogen protection, intermediate C1-B-1 (210.00 mmol), NBS (N-bromosuccinimide, 315.00 mmol), 600 mL of tetrahydrofuran, and 70 mL of [unspecified substance] were added. The reaction was carried out overnight at C. After the reaction was completed, the mixture was extracted with dichloromethane, the organic layer was dried with anhydrous magnesium sulfate to remove the organic solvent, and ethanol was added and slurry was added to obtain intermediate C1-B-2 (yield 91.8%).

[0111] In a 1L three-necked flask, under nitrogen protection, intermediate C1-B-2 (210.00 mmol), bis-pinacol borate (315.00 mmol), anhydrous dioxane (600 mL), 1,1'-bisdiphenylphosphine ferrocene palladium dichloride (2.1 mmol), potassium acetate (525.00 mmol), and 105 The reaction was carried out overnight at C. After the reaction was completed, water was added to quench the reaction, and the product was extracted with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate to remove the organic solvent. The crude product was passed through a fast column with a mixed solvent (dichloromethane: tetrahydrofuran = 1:1, v:v), and n-hexane was added to slurry to give intermediate C1-B (yield 82.8%).

[0112] The synthesis method of intermediate Cn-B is the same as that of intermediate C1-B, except that the relevant raw materials are replaced. The raw materials and yields of intermediate Cn-B are shown in Table 2.

[0113] Table 2. Raw material list for the synthesis of intermediate Cn-B

[0114] Synthesis Example 1-1 This embodiment provides a method for synthesizing compound C-1, and the synthetic route is shown in the following reaction formula:

[0115] In a 250 mL three-necked flask, under nitrogen protection, add intermediate C1-A (28.00 mmol), intermediate C1-B (28.00 mmol), dioxane:water = 4:1 (160 mL: 40 mL), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (0.140 mmol), potassium carbonate (70.00 mmol), and 95... The reaction was carried out overnight at C. After the reaction was completed, the product was extracted with dichloromethane, the organic phase was passed through a silica gel column, dried over anhydrous sodium sulfate, the solvent was removed, the product was slurried with ethanol, filtered, and the solid was recrystallized twice with toluene to give product C-1 (yield 68.8%).

[0116] Elemental analysis: C 39 H 26N2, theoretical value: C, 89.63; H, 5.01; N, 5.36; measured value: C, 89.66; H, 5.01; N, 5.34; HRMS (ESI) m / z (M+): theoretical value: 522.21, measured value: 523.23.

[0117] Synthesis Examples 1-2

[0118] The synthesis method of compound C-7 is the same as that of compound C-1, except that starting material C7-B is used to replace starting material C1-B to obtain compound C-7, with a yield of 77.6%. Elemental analysis: C 43 H 28 N2, theoretical value: C, 90.18; H, 4.93; N, 4.89; measured value: C, 90.19; H, 4.94; N, 4.87; HRMS (ESI) m / z (M+): theoretical value: 572.23, measured value: 573.25.

[0119] Synthesis Examples 1-3

[0120] The synthesis method of compound C-23 is the same as that of compound C-1, except that starting material C23-B is used to replace starting material C1-B to obtain compound C-23 with a yield of 77.6%. Elemental analysis: C 42 H 27 N3, theoretical value: C, 87.93; H, 4.74; N, 7.32; measured value: C, 87.95; H, 4.73; N, 7.31; HRMS (ESI) m / z (M+): theoretical value: 573.22, measured value: 574.11.

[0121] Synthesis Examples 1-4

[0122] The synthesis method of compound C-24 is the same as that of compound C-1, except that starting material C24-B is used to replace starting material C1-B to obtain compound C-24 with a yield of 76.6%. Elemental analysis: C 45 H 28 N2O, theoretical values: C, 88.21; H, 4.61; N, 4.57; O, 2.61; measured values: C, 88.22; H, 4.62; N, 4.55; HRMS (ESI) m / z (M+): theoretical value: 612.22, measured value: 613.24.

[0123] Synthesis Examples 1-5

[0124] The synthesis method of compound C-28 is the same as that of compound C-1, except that starting material C28-B is used to replace starting material C1-B to obtain compound C-28 with a yield of 78.3%. Elemental analysis: C 43 H 21 D7N2, theoretical values: C, 89.08; H, 6.08; N, 4.83; measured values: C, 89.09; H, 6.09; N, 4.81; HRMS (ESI) m / z (M+): theoretical value: 579.27, measured value: 580.22.

[0125] Synthesis Examples 1-6

[0126] The synthesis method of compound C-29 is the same as that of compound C-1, except that starting material C29-A is used to replace starting material C1-A to obtain compound C-29 with a yield of 76.6%. Elemental analysis: C 39 H 26 N2, theoretical value: C, 89.63; H, 5.01; N, 5.36; measured value: C, 89.65; H, 5.00; N, 5.34; HRMS (ESI) m / z (M+): theoretical value: 522.21, measured value: 523.11.

[0127] Synthesis Examples 1-7

[0128] The synthesis method of compound C-35 is the same as that of compound C-1, except that starting material C35-A replaces starting material C1-A, and starting material C7-B replaces starting material C1-B, to obtain compound C-35 with a yield of 74.5%. Elemental analysis: C 43 H 28 N2, theoretical values: C, 90.18; H, 4.93; N, 4.89; measured values: C, 90.18; H, 4.92; N, 4.88; HRMS (ESI) m / z (M+): theoretical value: 572.23, measured value: 573.08.

[0129] Synthesis Examples 1-8

[0130] The synthesis method of compound C-36 is the same as that of compound C-1, except that starting material C29-A replaces starting material C1-A, and starting material C36-B replaces starting material C1-B, to obtain compound C-36 with a yield of 68.7%. Elemental analysis: C 47 H 30 N2, theoretical value: C, 90.65; H, 4.86; N, 4.50; measured value: C, 90.67; H, 4.85; N, 4.49; HRMS (ESI) m / z (M+): theoretical value: 622.24, measured value: 623.15.

[0131] Synthesis Examples 1-9

[0132] The synthesis method of compound C-43 is the same as that of compound C-1, except that starting material C43-A replaces starting material C1-A, and starting material C7-B replaces starting material C1-B, to obtain compound C-43 with a yield of 78.8%. Elemental analysis: C 46 H 29 N3, theoretical value: C, 88.58; H, 4.69; N, 6.74; measured value: C, 88.61; H, 4.68; N, 6.72; HRMS (ESI) m / z (M+): theoretical value: 623.24, measured value: 624.04.

[0133] Synthesis Examples 1-10

[0134] The synthesis method of compound C-47 is the same as that of compound C-1, except that starting material C47-A replaces starting material C1-A, and starting material C7-B replaces starting material C1-B, to obtain compound C-47 with a yield of 88.3%. Elemental analysis: C 42 H 27 N3, theoretical value: C, 87.93; H, 4.74; N, 7.32; measured value: C, 87.96; H, 4.72; N, 7.31; HRMS (ESI) m / z (M+): theoretical value: 573.22, measured value: 574.18.

[0135] Synthesis Examples 1-11

[0136] The synthesis method of compound C-51 is the same as that of compound C-1, except that starting material C29-A replaces starting material C1-A, and starting material C23-B replaces starting material C1-B, to obtain compound C-51 with a yield of 81.8%. Elemental analysis: C 42 H 27 N3, theoretical value: C, 87.93; H, 4.74; N, 7.32; measured value: C, 87.95; H, 4.73; N, 7.31; HRMS (ESI) m / z (M+): theoretical value: 573.22, measured value: 574.02.

[0137] Synthesis Examples 1-12

[0138] The synthesis method of compound C-53 is the same as that of compound C-1, except that starting material C29-A replaces starting material C1-A, and starting material C53-B replaces starting material C1-B, to obtain compound C-53 with a yield of 83.8%. Elemental analysis: C 45 H 28 N2O, theoretical values: C, 88.21; H, 4.61; N, 4.57; O, 2.61; measured values: C, 88.23; H, 4.62; N, 4.53; HRMS (ESI) m / z (M+): theoretical value: 612.22, measured value: 613.25.

[0139] Synthesis Examples 1-13

[0140] The synthesis method of compound C-58 is the same as that of compound C-1, except that starting material C58-A replaces starting material C1-A, and starting material C58-B replaces starting material C1-B, to obtain compound C-58 with a yield of 81.8%. Elemental analysis: C 43 D 28 N2. Theoretical values: C, 85.95; H, 9.39; N, 4.66; Measured values: C, 85.97; H, 9.38; N, 4.65; HRMS (ESI) m / z [M+H] + Theoretical value: 600.40, measured value: 601.32.

[0141] The synthesis method of the compound shown in formula (2) is as follows:

[0142] Example: Synthesis of intermediate H1-A:

[0143] In a 1L three-necked flask, under nitrogen protection, add raw material H1-a (210.00 mmol), bis-pinacol borate (315.00 mmol), 600 mL of anhydrous dioxane, 2.1 mmol of 1,1'-bisdiphenylphosphine ferrocene palladium dichloride, and 525.00 mmol of potassium acetate. The reaction was carried out overnight at C. After the reaction was completed, water was added to quench the reaction, and the product was extracted with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate to remove the organic solvent. The crude product was passed through a fast column with a mixed solvent (dichloromethane: tetrahydrofuran = 1:1, v:v), and n-hexane was added to slurry to give intermediate H1-A (yield 88.8%).

[0144] The synthesis methods for intermediates H2-A to Hn-A are the same as those for intermediate H1-A, except that the relevant raw materials are replaced. The raw materials for the synthesis of Hn-A are shown in Table 3.

[0145] Table 3. Raw material list for the synthesis of intermediate Hn-A

[0146] Synthesis of intermediate H5-A:

[0147] In a 2L three-necked flask, under nitrogen protection, intermediate H1-A (248.06 mmol), starting material H5-b (248.06 mmol), potassium carbonate (620.15 mmol), dioxane (440 mL), water (110 mL), tetraphenylphosphine palladium (2.481 mmol), and 90 μL were added. The reaction was carried out overnight at C. After the reaction was completed, the mixture was extracted with dichloromethane, the organic phase was dried with anhydrous sodium sulfate to remove the organic solvent, ethanol was added and stirred for 1 h, and the mixture was filtered to obtain intermediate H5-A-1 (yield 88.66%).

[0148] In a 1L three-necked flask, under nitrogen protection, intermediate H5-A-1 (210.00 mmol), bis-pinacol borate (315.00 mmol), anhydrous dioxane (600 mL), 1,1'-bisdiphenylphosphine ferrocene palladium dichloride (2.1 mmol), potassium acetate (525.00 mmol), and 105 The reaction was carried out overnight at C. After the reaction was completed, water was added to quench the reaction, and the product was extracted with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate to remove the organic solvent. The crude product was passed through a fast column with a mixed solvent (dichloromethane: tetrahydrofuran = 1:1, v:v), and n-hexane was added to slurry to give intermediate H5-A (yield 81.8%).

[0149] The synthesis method of intermediate Hn-A is the same as that of intermediate H5-A, the difference being the substitution of relevant raw materials. The raw materials for the synthesis of intermediate Hn-A are shown in Table 4.

[0150] Table 4. Raw materials for the synthesis of intermediate Hn-A

[0151] Synthesis of intermediate H61-B:

[0152] In a 500 mL three-necked flask, H1-B (18.00 mmol), trifluoromethanesulfonic acid (36.00 mmol), and deuterium benzene (100 mL) were added, and the mixture was refluxed for 36 h. After the reaction was completed, the organic solvent was removed by vacuum distillation, and the crude product was purified by column chromatography (dichloromethane:n-hexane = 3:1, v:v) to give compound H61-B (yield 89.8%).

[0153] The synthesis methods of intermediates H74-A, H74-B, and H88-A are the same as those of intermediate H61-B, except that the relevant raw materials are replaced. The raw materials for the synthesis of intermediates H74-A, H74-B, and H88-A are shown in Table 5.

[0154] Table 5. Raw materials for the synthesis of intermediates H74-A, H74-B, and H88-A

[0155] Synthesis Example 2-1 This embodiment provides a method for synthesizing compound H-1, and the synthetic route is shown in the following reaction formula:

[0156] In a 250 mL three-necked flask, under nitrogen protection, add starting material H1-A (28.00 mmol), intermediate H1-B (28.00 mmol), dioxane:water = 4:1 (160 mL: 40 mL), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (0.140 mmol), potassium carbonate (70.00 mmol), and 95... The reaction was carried out overnight at C. After the reaction was completed, sufficient water was added to quench the reaction. The crude product solid was obtained by filtration. The solid was passed through a fast column chromatography with chlorobenzene. The solvent was removed and crystallized from the column chromatography solution. The product H-1 was purified by recrystallization of o-dichlorobenzene (yield 68.8%).

[0157] Elemental analysis: C 36 H 22 O, theoretical value: C, 91.89; H, 4.71; O, 3.40; measured value: C, 91.90; H, 4.71; HRMS (ESI) m / z (M+): theoretical value: 470.17, measured value: 471.11.

[0158] Synthesis Example 2-2 Compound H-14 was synthesized using the method described in Example 1, except that starting material H14-A was used instead of starting material H1-A, and starting material H14-B was used instead of starting material H1-B. The synthetic route is shown below:

[0159] Compound H-14 was obtained in 77.6% yield. Elemental analysis: C 40 H 24 O, theoretical value: C, 92.28; H, 4.65; O, 3.07; measured value: C, 92.29; H, 4.65; HRMS (ESI) m / z (M+): theoretical value: 520.18, measured value: 521.19.

[0160] Synthesis Examples 2-3 Compound H-27 was synthesized using the method described in Example 1, except that reactant H27-A was used instead of reactant H1-A, and reactant H27-B was used instead of reactant H1-B. The synthetic route is shown below:

[0161] Compound H-27 was obtained in 78.6% yield. Elemental analysis: C 40 H 24 O, theoretical value: C, 92.28; H, 4.65; O, 3.07; measured value: C, 92.29; H, 4.64; HRMS (ESI) m / z (M+): theoretical value: 520.18, measured value: 521.08.

[0162] Synthesis Examples 2-4 Compound H-44 was synthesized using the same method as in Example 1, except that reactant H44-A was used instead of reactant H1-A, and reactant H44-B was used instead of reactant H1-B. The synthetic route is shown below:

[0163] Compound H-44 was obtained in 76.6% yield. Elemental analysis: C 42 H 26 O, theoretical value: C, 92.28; H, 4.79; O, 2.93; measured value: C, 92.29; H, 4.79; HRMS (ESI) m / z (M+): theoretical value: 546.20, measured value: 547.02.

[0164] Synthesis Examples 2-5 Compound H-53 was synthesized using the same method as in Example 1, except that reactant H53-A replaced reactant H1-A, and reactant H53-B replaced reactant H1-B. The synthetic route is shown below:

[0165] Compound H-53 was obtained in 78.3% yield. Elemental analysis: C 48 H 30 O, theoretical value: C, 92.58; H, 4.86; O, 2.57; measured value: C, 92.59; H, 4.84; HRMS (ESI) m / z (M+): theoretical value: 622.23, measured value: 623.12.

[0166] Synthesis Examples 2-6 Compound H-55 was synthesized using the method described in Example 1, except that reactant H55-A was used instead of reactant H1-A, and reactant H55-B was used instead of reactant H1-B. The synthetic route is shown below:

[0167] Compound H-55 was obtained in 76.6% yield. Elemental analysis: C 56 H 34 O, theoretical value: C, 93.05; H, 4.74; O, 2.21; measured value: C, 93.08; H, 4.75; HRMS (ESI) m / z (M+): theoretical value: 722.26, measured value: 723.28.

[0168] Synthesis Examples 2-7 Compound H-60 ​​was synthesized using the synthetic method of Example 1, except that reactant H60-A was used instead of reactant H1-A, and reactant H60-B was used instead of reactant H1-B. The synthetic route is shown below:

[0169] Compound H-60 ​​was obtained in 74.5% yield. Elemental analysis: C 46 H 28 O, theoretical value: C, 92.59; H, 4.73; O, 2.68; measured value: C, 92.59; H, 4.72; HRMS (ESI) m / z (M+): theoretical value: 596.21, measured value: 597.02.

[0170] Synthesis Examples 2-8 Compound H-61 was synthesized using the method described in Example 2, except that starting material H61-B was used instead of starting material H1-B. The synthetic route is shown below:

[0171] Compound H-61 was obtained in 68.7% yield. Elemental analysis: C 36 H 13 D9O, theoretical values: C, 90.15; H, 6.51; O, 3.34; measured values: C, 90.18; H, 6.50; HRMS (ESI) m / z (M+): theoretical value: 479.22, measured value: 480.06.

[0172] Synthesis Examples 2-9 Compound H-74 was synthesized using the same method as in Example 1, except that reactant H74-1 replaced reactant H1-A, and reactant H74-B replaced reactant Cl-B. The synthetic route is shown in the following reaction formula:

[0173] Compound H-74 was obtained in 78.8% yield. Elemental analysis: C 36 HD 21 O, theoretical value: C, 87.94; H, 8.81; O, 3.25; measured value: C, 87.98; H, 8.80; HRMS (ESI) m / z (M+): theoretical value: 491.30, measured value: 492.24.

[0174] Synthesis Examples 2-10 This embodiment provides a method for synthesizing compound H-88, and the synthetic route is shown in the following reaction formula:

[0175] In a 1L three-necked flask, under nitrogen protection, intermediate H88-a (210.00 mmol), bis-pinacol borate (315.00 mmol), anhydrous dioxane (600 mL), 1,1'-bisdiphenylphosphine ferrocene palladium dichloride (2.1 mmol), potassium acetate (525.00 mmol), and 105 The reaction was carried out overnight at C. After the reaction was completed, water was added to quench the reaction, and the product was extracted with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate to remove the organic solvent. The crude product was passed through a fast column in a mixed solvent (dichloromethane: tetrahydrofuran = 1:1, v:v), and n-hexane was added to slurry to obtain intermediate H88-A (yield 80.2%).

[0176] In a 250 mL three-necked flask, under nitrogen protection, add raw material H88-A (28.00 mmol), intermediate H88-B (28.00 mmol), dioxane:water = 4:1 (160 mL: 40 mL), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (0.140 mmol), potassium carbonate (70.00 mmol), and 95... The reaction was carried out overnight at C. After the reaction was completed, the product was extracted with DCM, the organic phase was passed through a fast column, concentrated under reduced pressure, and then slurried with ethanol to obtain product H88-1 (yield 86.6%).

[0177] In a 250 mL three-necked flask, under nitrogen protection, add intermediate H88-1 (24.00 mmol), H88-C (28.00 mmol), dioxane:water = 4:1 (160 mL: 40 mL), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.240 mmol), potassium carbonate (60.00 mmol), and 95 The reaction was carried out overnight at C. After the reaction was completed, sufficient water was added to quench the reaction. The crude product solid was filtered and passed through a DCM fast column. The column chromatography solution was desolventized and crystallized. The product H-88 was purified by slurrying of tetrahydrofuran (68.8% yield).

[0178] Elemental analysis: C 36 H5D 17 O, theoretical value: C, 88.66; H, 8.05; O, 3.28; measured value: C, 88.67; H, 8.05; HRMS (ESI) m / z (M+): theoretical value: 487.27, measured value: 488.18.

[0179] The synthesis method of the compound shown in formula (3) is as follows: .

[0180] Example: Synthesis Example 3-1 This embodiment provides the synthesis of compound D-1, and the specific synthetic route is shown below:

[0181] Under nitrogen protection, compounds D1-a (22.0 mmol), D1-b (22.0 mmol), Pd2(dba)3 (0.44 mmol), X-phos (1.32 mmol), and sodium tert-butoxide (66.0 mmol) were dissolved in 100 mL of toluene in a 250 mL four-necked flask at room temperature. The mixture was refluxed and stirred at 100 °C for 6 h, and the reaction was quenched with water. The mixture was extracted with dichloromethane and separated by column chromatography to obtain D1-1 (yield 88%). Under nitrogen protection, D1-1 (12.0 mmol), compound D1-c (12.0 mmol), Pd2(dba)3 (0.24 mmol), X-phos (0.36 mmol), and sodium tert-butoxide (30.0 mmol) were dissolved in 100 mL of toluene in a 250 mL three-necked flask. The mixture was refluxed and stirred at 100 °C for 3 h, and the reaction was quenched with water. The mixture was extracted with dichloromethane and separated by column chromatography to obtain D1-2 (yield 80%). Under nitrogen protection, D1-2 (6 mmol) and 40 mL of anhydrous tert-butylbenzene were added to a 100 mL three-necked flask. After cooling to -60 °C, a pentane solution of tert-butyllithium (12 mL, 1.3 M, 15 mmol) was slowly added dropwise. After the addition was complete, the temperature was raised to -30 °C and the reaction was carried out for 2 h. Then, boron tribromide (15 mL, 1.0 M, 15 mmol) was slowly added and the mixture was stirred for another 2 h. N,N-diisopropylethylamine (15 mmol) was slowly added under constant temperature, and the reaction was carried out at 120 °C for another 5 h. After cooling to room temperature, the solvent was quenched with deionized water and evaporated under vacuum. D-1 was obtained by column chromatography (yield 30%).

[0182] Elemental analysis: C 49 H 55 BN2S. Theoretical values: C, 82.33; H, 7.76; B, 1.51; N, 3.92; S, 4.48; Measured values: C, 82.34; H, 7.77; B, 1.52; N, 3.91; S, 4.46. HRMS (ESI) m / z [M+H]+: Theoretical value: 714.42; Measured value: 715.44.

[0183] Synthesis Example 3-2 This embodiment provides the synthesis of compound D-11, and the specific synthetic route is shown below:

[0184] The synthesis method of compound D-11 is the same as that of compound D-1, except that the starting material D11-a is replaced by the starting material D11-a and the starting material D11-c is replaced by the starting material D1-c, to obtain compound D-11 with a yield of 36%.

[0185] Elemental analysis: C 69 H 80 BN3S. Theoretical values: C, 83.35; H, 8.11; B, 1.09; N, 4.23; S, 3.22; Measured values: C, 83.37; H, 8.12; B, 1.08; N, 4.22; S, 3.21. HRMS (ESI) m / z [M+H]+: Theoretical value: 993.62; Measured value: 994.52.

[0186] Synthesis Examples 3-3 This embodiment provides the synthesis of compound D-20, and the specific synthetic route is shown below:

[0187] The synthesis method of compound D-20 is the same as that of compound D-1, except that the starting material D20-a is used to replace the starting material D1-a, and the starting material D20-c is used to replace the starting material D1-c, to obtain compound D-20 with a yield of 34%.

[0188] Elemental analysis: C 54 H 63 BN2S. Theoretical values: C, 82.84; H, 8.11; B, 1.38; N, 3.58; S, 4.09; Measured values: C, 82.86; H, 8.12; B, 1.37; N, 3.57; S, 4.08. HRMS (ESI) m / z [M+H]+: Theoretical value: 782.48; Measured value: 783.43.

[0189] Synthesis Examples 3-4 This embodiment provides the synthesis of compound D-36, and the specific synthetic route is shown below:

[0190] The synthesis method of compound D-36 is the same as that of compound D-1, except that the starting material D11-a is replaced by the starting material D1-a and the starting material D36-c is replaced by the starting material D1-c, to obtain compound D-36 with a yield of 34%.

[0191] Elemental analysis: C 71 H 76 BN3S. Theoretical values: C, 84.08; H, 7.55; B, 1.07; N, 4.14; S, 3.16; Measured values: C, 84.09; H, 7.56; B, 1.08; N, 4.12; S, 3.15. HRMS (ESI) m / z [M+H]+: Theoretical value: 1013.59; Measured value: 1014.53.

[0192] Synthesis Examples 3-5 This embodiment provides the synthesis of compound D-60, and the specific synthetic route is shown below:

[0193] The synthesis method of compound D-60 is the same as that of compound D-1, except that the starting material D11-a is replaced by the starting material D1-a and the starting material D60-c is replaced by the starting material D1-c, to obtain compound D-60 with a yield of 32%.

[0194] Elemental analysis: C 73 H 72 BN3S. Theoretical values: C, 84.78; H, 7.02; B, 1.05; N, 4.06; S, 3.10; Measured values: C, 84.79; H, 7.03; B, 1.06; N, 4.05; S, 3.09. HRMS (ESI) m / z [M+H]+: Theoretical value: 1033.55; Measured value: 1034.51.

[0195] Synthesis Examples 3-6 This embodiment provides the synthesis of compound D-75, and the specific synthetic route is shown below:

[0196] The synthesis method of compound D-75 is the same as that of compound D-1, except that the starting material D75-b is used to replace the starting material D1-b, and the starting material D75-c is used to replace the starting material D1-c, to obtain compound D-75 with a yield of 32%.

[0197] Elemental analysis: C 71 H 76BN3S. Theoretical values: C, 84.08; H, 7.55; B, 1.07; N, 4.14; S, 3.16; Measured values: C, 84.09; H, 7.57; B, 1.06; N, 4.13; S, 3.15. HRMS (ESI) m / z [M+H]+: Theoretical value: 1013.59; Measured value: 1014.52.

[0198] Synthesis Examples 3-7 This embodiment provides the synthesis of compound D-88, and the specific synthetic route is shown below:

[0199] The synthesis method of compound D-88 is the same as that of compound D-1, except that the starting material D75-b is used to replace the starting material D1-b, and the starting material D20-c is used to replace the starting material D1-c, to obtain compound D-88 in 35% yield.

[0200] Elemental analysis: C 55 H 57 BN2S. Theoretical values: C, 83.73; H, 7.28; B, 1.37; N, 3.55; S, 4.06; Measured values: C, 83.75; H, 7.29; B, 1.36; N, 3.54; S, 4.05. HRMS (ESI) m / z [M+H]+: Theoretical value: 788.43; Measured value: 789.41.

[0201] Synthesis Examples 3-8 This embodiment provides the synthesis of compound D-104, and its specific synthetic route is shown below:

[0202] The synthesis method of compound D-104 is the same as that of compound D-1, except that the raw material D20-a is replaced with raw material D1-a, raw material D75-b is replaced with raw material D1-b, and raw material D36-c is replaced with raw material D1-c, to obtain compound D-104 with a yield of 36%.

[0203] Elemental analysis: C 74 H 74 BN3S. Theoretical values: C, 84.79; H, 7.12; B, 1.03; N, 4.01; S, 3.06; Measured values: C, 84.81; H, 7.13; B, 1.02; N, 4.00; S, 3.05. HRMS (ESI) m / z [M+H]+: Theoretical value: 1047.57; Measured value: 1048.53.

[0204] Synthesis Examples 3-9 This embodiment provides the synthesis of compound D-124, and its specific synthetic route is shown below:

[0205] The synthesis method of compound D-124 is the same as that of compound D-1, except that the starting material D75-b is used to replace the starting material D1-b and the starting material D60-c is used to replace the starting material D1-c, so as to obtain compound D-124 with a yield of 32%.

[0206] Elemental analysis: C 75 H 68 BN3S. Theoretical values: C, 85.45; H, 6.50; B, 1.03; N, 3.99; S, 3.04; Measured values: C, 85.47; H, 6.51; B, 1.02; N, 3.98; S, 3.03. HRMS (ESI) m / z [M+H]+: Theoretical value: 1053.52; Measured value: 1054.50.

[0207] Synthesis Examples 3-10 This embodiment provides the synthesis of compound D-146, and the specific synthetic route is shown below:

[0208] The synthesis method of compound D-146 is the same as that of compound D-1, except that the starting material D1-b is replaced by starting material D146-b and starting material D1-c is replaced by starting material D146-c, to obtain compound D-146 in 35% yield.

[0209] Elemental analysis: C 65 H 71 BN2S. Theoretical values: C, 84.57; H, 7.75; B, 1.17; N, 3.03; S, 3.47; Measured values: C, 84.59; H, 7.76; B, 1.16; N, 3.02; S, 3.46. HRMS (ESI) m / z [M+H]+: Theoretical value: 922.54; Measured value: 923.51.

[0210] Synthesis Examples 3-11 This embodiment provides the synthesis of compound D-162, and the specific synthetic route is shown below:

[0211] The synthesis method of compound D-162 is the same as that of compound D-1, except that the raw material D20-a is used to replace the raw material D1-a, the raw material D146-b is used to replace the raw material D1-b, and the raw material D162-c is used to replace the raw material D1-c, so as to obtain compound D-162 in 38% yield.

[0212] Elemental analysis: C 72 H 78 BN3S. Theoretical values: C, 84.10; H, 7.65; B, 1.05; N, 4.09; S, 3.12; Measured values: C, 84.12; H, 7.66; B, 1.04; N, 4.08; S, 3.11. HRMS (ESI) m / z [M+H]+: Theoretical value: 1027.60; Measured value: 1028.62.

[0213] Synthesis Examples 3-12 This embodiment provides the synthesis of compound D-217, and the specific synthetic route is shown below:

[0214] The synthesis method of compound D-217 is the same as that of compound D-1, except that the starting material D217-b is replaced with the starting material D1-b, and the starting material D217-c is replaced with the starting material D1-c, to obtain compound D-217 with a yield of 41%.

[0215] Elemental analysis: C 37 H 31 BN2S. Theoretical values: C, 81.31; H, 5.72; B, 1.98; N, 5.13; S, 5.87; Measured values: C, 81.33; H, 5.73; B, 1.97; N, 5.12; S, 5.86. HRMS (ESI) m / z [M+H]+: Theoretical value: 546.23; Measured value: 547.21.

[0216] Synthesis Examples 3-13 This embodiment provides the synthesis of compound D-221, and its specific synthetic route is shown below:

[0217] The synthesis method of compound D-221 is the same as that of compound D-1, except that the starting material D221-b is replaced with the starting material D1-b and the starting material D217-c is replaced with the starting material D1-c, to obtain compound D-221 with a yield of 36%.

[0218] Elemental analysis: C 40 H 29BN2S. Theoretical values: C, 82.76; H, 5.04; B, 1.86; N, 4.83; S, 5.52. Measured values: C, 82.78; H, 5.05; B, 1.85; N, 4.82; S, 5.51. HRMS (ESI) m / z [M+H]+: Theoretical value: 580.21; Measured value: 581.16.

[0219] Component example: The materials used to prepare the following device embodiments or device comparative examples are shown in Table 6 below.

[0220] Table 6. Some compounds used in the device examples or device comparative examples

[0221] Device Example 1 This embodiment provides an organic electroluminescent device, such as... Figure 1 As shown, it includes, in sequence, an anode 1, a hole injection layer 2, a first hole transport layer 3, a first electron blocking layer 4, a first organic light-emitting layer 5, a first hole blocking layer 6, a first electron transport layer 7, an n-type charge generation layer 8, a p-type charge generation layer 9, a second hole transport layer 10, a second electron blocking layer 11, a second organic light-emitting layer 12, a second hole blocking layer 13, a second electron transport layer 14, an electron injection layer 15, and a cathode 16. Its device structure is as follows: anode (indium tin oxide (ITO)), hole injection layer (HIL), first hole transport layer (HTL-1), first electron blocking layer (EBL-1), first organic light-emitting layer (EML-1), first hole blocking layer (HBL-1), first electron transport layer (ETL-1), n-type charge generation layer (CGL-n), p-type charge generation layer (CGL-p), second hole transport layer (HTL-2), second electron blocking layer (EBL-2), second organic light-emitting layer (EML-2), second hole blocking layer (HBL-2), second electron transport layer (ETL-2), electron injection layer (EIL), and cathode.

[0222] The fabrication of the above-mentioned organic electroluminescent device includes the following steps: 1) Substrate cleaning: 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.

[0223] 2) Preparation of the organic layer: 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) / first hole transport layer (HTL-1) / first electron blocking layer (EBL-1) / first organic light-emitting layer (EML-1) / first hole blocking layer (HBL-1) / first electron transport layer (ETL-1) / n-type charge generation layer (CGL-n) / p-type charge generation layer (CGL-p) / second hole transport layer (HTL-2) / second electron blocking layer (EBL-2) / second organic light-emitting layer (EML-2) / second hole blocking layer (HBL-2) / second electron transport layer (ETL-2) / electron injection layer (EIL) / cathode (Mg:Ag mass ratio is 1:9) are deposited sequentially on the ITO anode film.

[0224] in: The anode is indium tin oxide (ITO, 10 nm thick); The hole injection layer (HIL) is made of HAT-CN:TCTA (10nm thick); the mass ratio of HAT-CN to TCTA is 3:97. The material of the first hole transport layer (HTL-1) is TCTA (20nm thick); The material of the first electron blocking layer (EBL-1) is mCP (5nm thick); The first organic light-emitting layer (EML-1) is made of H-1 and DR-1 in a mass ratio of 95:5 (thickness 20nm); The material of the first hole blocking layer (HBL-1) is BCP (5nm thick); The first electron transport layer (ETL-1) is made of TPBI and LiQ in a mass ratio of 9:1 (thickness 25nm); The n-type charge generation layer (CGL-n) is composed of compounds C-1 and Yb (10 nm thick); The p-type charge generation layer (CGL-p) is made of HAT-CN and TCTA in a mass ratio of 8:2 (thickness 10nm); The material of the second hole transport layer (HTL-2) is TCTA (20nm thick); The material of the second electron blocking layer (EBL-2) is mCP (5nm thick); The second organic light-emitting layer (EML-2) is made of H-1 and DR-1 in a mass ratio of 95:5 (thickness 20nm); The material of the second hole blocking layer (HBL-2) is BCP (5nm thick); The second electron transport layer (ETL-2) is made of TPBI and LiQ in a mass ratio of 9:1 (thickness 25nm); The electron injection layer (EIL) is made of Yb (1 nm thick); The cathode is made of Mg and Ag in a mass ratio of 1:9 (thickness 11 nm).

[0225] Device Examples 2 to Device Examples 18 Device Examples 2 to 18 each provide an organic electroluminescent device, the preparation method of which is the same as that of Device Example 1. The difference is that the compounds in the first organic light-emitting layer, the second organic light-emitting layer and the n-type charge generation layer in Device Example 1 are replaced, as shown in Table 7.

[0226] Device Comparison Examples 1 to 4 This comparative example provides an organic electroluminescent device, which is prepared in the same way as the device in Example 1. The only difference is that the compounds of the first organic light-emitting layer, the second organic light-emitting layer, and the n-type charge generation layer in the device in Example 1 are replaced. Please refer to Table 7 for details.

[0227] Table 7 Composition and mass ratio of the first organic light-emitting layer, the second organic light-emitting layer, and the n-type charge generation layer

[0228] The organic electroluminescent devices prepared in Device Examples 1-18 and Device Comparative Examples 1-4 in the device examples were tested.

[0229] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR625 spectral scanning luminance meter and a Keithley K 2400 digital source meter system; Test conditions: Photoelectric property test conditions: current density 10 mA / cm² 2 , room temperature.

[0230] Lifetime test: Current density 10mA / cm 2 The time (in hours) is recorded when the device brightness drops to 95% of its original brightness.

[0231] Among them, the lifetime, current efficiency and lifetime of device comparative example 1 are set to 100. The test results of lifetime and current efficiency of device examples 1-18 and device comparative examples 2-4 relative to device comparative example 1 are shown in Table 8. The test results of driving voltage of device examples 1-18 and device comparative examples 1-4 are also shown in Table 8.

[0232] Table 8. Device performance parameters for Device Examples 1-18 and Device Comparative Examples 1-4

[0233] 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 organic electroluminescent device, characterized in that, The organic electroluminescent device includes: a cathode; an anode disposed opposite to the cathode; and at least two organic light-emitting layers between the cathode and the anode; in, Between two adjacent organic light-emitting layers there is a charge-generating layer, the charge-generating layer having the structure shown in formula (1), and the organic light-emitting layer having the structure shown in formula (2); In formula (1), Ra and Rb are selected from the structure shown in formula (1-1) and the other is selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl. R 1 Selected from hydrogen or deuterium; n1 is an integer selected from 0 to 4; In equation (1-1), L 1 and L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene; Ar 1 Selected from substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups; R 2 Selected from hydrogen or deuterium; n2 is an integer selected from 0 to 8; In equation (2), X is selected from O or S; Ring Q is selected from substituted or unsubstituted benzene rings; R 3 and R 4 Each is independently selected from hydrogen or deuterium; Ar 2 Selected from substituted or unsubstituted C6-C30 aryl groups; L 3 and L 4 Each is independently selected from single-bonded, substituted, or unsubstituted C6-C30 arylene groups; n3 is an integer selected from 0 to 8; n4 is selected from integers between 0 and 10; In this embodiment, the substituted benzene ring, the substituted C6-C30 aryl group, the substituted C3-C30 heteroaryl group, the substituted C6-C30 arylene group, and the substituted C3-C30 heteroarylene group are each independently substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C18 alkyl, C6-C30 aryl, and C3-C30 heteroaryl.

2. The organic electroluminescent device according to claim 1, characterized in that, The compound shown in formula (1) is represented by the following chemical formula: In the formula, Ra, Rb, R 1 R 2 n1, n2, L 1 L 2 Ar 1 The definition is as described in claim 1.

3. An organic electroluminescent device according to claim 1, characterized in that, L 1 and L 2 Each is independently selected from single-bonded, substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C3-C20 heteroarylene; Wherein, the substituted C6-C20 arylene and the substituted C3-C20 heteroarylene are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C20 alkyl, C6-C20 aryl, C3-C20 heteroaryl. And / or, Ra and Rb are each independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl; Wherein, the substituted C6-C20 aryl and the substituted C3-C20 heteroaryl are substituted by at least one selected from the group consisting of: deuterium, halogen, cyano, C1-C6 alkyl, C6-C20 aryl, C3-C20 heteroaryl; And / or, Ar 1 Selected from substituted or unsubstituted C6-C20 aryl groups and substituted or unsubstituted C3-C20 heteroaryl groups; The substituted C6-C20 aryl group and the substituted C3-C20 heteroaryl group are substituted by at least one of the following groups: deuterium, halogen, cyano, C1-C6 alkyl, C6-C20 aryl, C3-C20 heteroaryl.

4. An organic electroluminescent device according to claim 1, characterized in that, The structure shown in formula (1) contains the following compounds: 。 5. An organic electroluminescent device according to claim 1, characterized in that, The compound shown in formula (2) is represented by the following chemical formula: In the formula, X and R 3 R 4 Ar 2 L 3 L 4 n3 and n4 are defined as described in claim 1.

6. An organic electroluminescent device according to claim 1, characterized in that, L 3 and L 4 Each is independently selected from single-bonded, substituted, or unsubstituted C6-C20 arylene groups; Each of the substituted C6-C20 arylene groups is independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C18 alkyl, C6-C20 aryl. And / or, Ar 2 Selected from substituted or unsubstituted C6-C20 aryl groups; The substituted C6-C20 aryl groups are each independently substituted by at least one group selected from the group consisting of: deuterium, halogen, cyano, C1-C20 alkyl, and C6-C20 aryl.

7. An organic electroluminescent device according to claim 1, characterized in that, The structure shown in formula (2) contains the following compounds: 。 8. An organic electroluminescent device according to claim 1, characterized in that, The charge generation layer includes an n-type charge generation layer and a p-type charge generation layer, and the n-type charge generation layer has a structure as shown in formula (1).

9. An organic electroluminescent device according to claim 1, characterized in that, The organic electroluminescent device includes two organic light-emitting layers: a first organic light-emitting layer near the anode and a second organic light-emitting layer near the cathode; the charge-generating layer is located between the first and second organic light-emitting layers. And / or, the organic electroluminescent device includes a stacked anode, a hole injection layer, a first hole transport layer, a first electron blocking layer, a first organic light-emitting layer, a first hole blocking layer, a first electron transport layer, an n-type charge generation layer, a p-type charge generation layer, a second hole transport layer, a second electron blocking layer, a second organic light-emitting layer, a second hole blocking layer, a second electron transport layer, an electron injection layer, and a cathode.

10. An organic electroluminescent device according to claim 9, characterized in that, The first organic light-emitting layer or the second organic light-emitting layer includes a blue light-emitting layer, and the blue light-emitting layer further includes the structure shown in formula (3): In equation (3), Y is selected from O or S; Rc and Rd are each independently selected from hydrogen or methyl, and at least one of Rc and Rd is selected from methyl; R 5 To R 8 Each group is independently selected from hydrogen, deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 heterocycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamine, substituted or unsubstituted C3-C30 heteroarylamine, wherein multiple R 3 or multiple R 4 or multiple R 5 or multiple R 6 They can connect with each other to form substituted or unsubstituted C3-C30 aliphatic rings, or substituted or unsubstituted C6-C30 aromatic rings; n5 to n8 are each independent integers selected from 0 to 4; Among them, substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C2-C30 heterocycloalkyl, substituted C1-C30 alkoxy, substituted C1-C30 alkylthio, substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C6-C30 arylamine, substituted C3-C30 heteroarylamine, substituted C3-C30 aliphatic ring, substituted C6-C30 Each aromatic ring is independently substituted by at least one of the following groups: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, C1-C30 alkyl, C3-C30 cycloalkyl, C2-C30 heterocycloalkyl, C1-C30 alkoxy, C1-C30 alkylthio, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 aromaticamine, C3-C30 heteroaryl.

11. An organic electroluminescent device according to claim 1, characterized in that, The compound shown in formula (3) is represented by the following chemical formula: ； In the formula, Y and R 5 To R 8 n5 to n8 are defined as described in claim 10.

12. An organic electroluminescent device according to claim 1, characterized in that, R 5 To R 8 Each group is independently selected from hydrogen, deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylthio, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, substituted or unsubstituted C6-C20 arylamine, substituted or unsubstituted C3-C20 heteroarylamine, wherein multiple R 5 or multiple R 6 or multiple R 7 or multiple R 8 They can connect with each other to form substituted or unsubstituted C3-C20 aliphatic rings, or substituted or unsubstituted C6-C20 aromatic rings; Among them, substituted C1-C20 alkyl, substituted C3-C20 cycloalkyl, substituted C2-C20 heterocycloalkyl, substituted C1-C20 alkoxy, substituted C1-C20 alkylthio, substituted C6-C20 aryl, substituted C3-C20 heteroaryl, substituted C6-C20 arylamine, substituted C3-C20 heteroarylamine, substituted C3-C20 aliphatic ring, substituted C6-C20 Each aromatic ring is independently substituted by at least one of the following groups: deuterium, carboxyl, nitro, cyano, amino, halogen, silyl, C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C1-C20 alkoxy, C1-C20 alkylthio, C6-C20 aryl, C3-C20 heteroaryl, C6-C20 aromaticamine, C3-C20 heteroaromaticamine.

13. An organic electroluminescent device according to claim 1, characterized in that, The structure shown in formula (3) contains the following compounds: 。

Images