Arylamine derivative and organic electroluminescent device thereof

Abstract

The invention provides an arylamine derivative and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescent materials. The arylamine derivative disclosed by the invention has good hole transport capacity and proper HOMO energy level, is applied to an organic electroluminescent device as a hole transport material, is beneficial to injection and transport of holes in the device, and can prevent excitons from escaping from a light emitting layer, so that the luminous efficiency is improved, the driving voltage is reduced, and the service life is prolonged. Meanwhile, the arylamine derivative disclosed by the invention has good stability and film-forming property, and is also an excellent covering layer material. The material can be applied to the fields of display, illumination and organic solar cells.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials technology, specifically to an aromatic amine derivative and its organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a technology that uses organic materials to directly convert electrical energy into light energy. The principle is that under the influence of an external electric field, charge carriers are injected through electrodes. After passing through the organic functional layer, the charge carriers recombine in the light-emitting layer to form excitons, which then emit light through transitions. OLEDs have advantages such as wide viewing angle, fast response speed, high luminous efficiency, rich colors, low energy consumption, thinness, simple manufacturing process, and the ability to achieve flexible displays, and have been widely used in various fields such as displays and lighting.

[0003] With the continuous development of organic light-emitting diodes (OLEDs), their internal device structures are also constantly being optimized. Currently, most OLEDs adopt a sandwich structure, with organic functional layers placed between the cathode and anode. Different functional layers play different roles in the device. Based on their functions, organic functional layers can be categorized as hole injection layers, hole transport layers, light-emitting auxiliary layers, electron blocking layers, light-emitting layers, hole blocking layers, electron transport layers, electron injection layers, and capping layers. After the device structure is optimized, the selection of materials for each functional layer becomes a crucial factor affecting device performance.

[0004] Based on the different materials used in each functional layer of the device structure, organic electroluminescent materials can be divided into electrode materials and their modification materials, electron transport layer materials, hole transport layer materials, luminescent materials and their auxiliary materials, etc. Among them, hole transport materials still have some problems, such as low thermal stability, low hole transport efficiency, and energy level mismatch, which have become the main factors affecting the performance of organic electroluminescent devices. A good hole transport material should have good film-forming properties, forming a pinhole-free, uniform amorphous film, and good thermal stability after film formation to avoid crystallization caused by heat during operation, which would damage the material layer contact surface and affect device efficiency and lifespan. On the other hand, it needs to have high hole mobility and suitable HOMO energy levels to match the ITO work function, with a small potential barrier value to facilitate effective hole injection during operation. At the same time, the hole transport material should also have low affinity to facilitate hole injection, low ionization potential to block electrons in the luminescent layer, and high excitation energy to prevent exciton energy transfer. In addition, the light extraction efficiency of the capping material for organic electroluminescent devices is not high, which directly leads to a decrease in the luminous efficiency of the device. Moreover, some capping materials absorb less ultraviolet light from the external environment, which also shortens the lifespan of the device.

[0005] Therefore, developing hole transport materials with good hole transport capabilities, suitable HOMO energy levels, high thermal stability, and film-forming properties, as well as high-performance capping materials, are important issues that urgently need to be addressed. Summary of the Invention

[0006] To address the problems existing in the prior art, the present invention provides an aromatic amine derivative and its organic electroluminescent device.

[0007] This invention provides an aromatic amine derivative, represented by the following formula 1.

[0008] Wherein, Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 are the same or different and are selected from one of the following: substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C2-C60 heteroaryl groups, fused cycloalkanes of substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic groups, and fused cycloalkanes of substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroaromatic groups. At least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is selected from the groups shown in Formula 1-c below.

[0009] The x that are the same or different are selected from CH or N; The Y is selected from O or S; The R d The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R d They bond together to form substituted or unsubstituted rings; The s1 is selected from 0, 1, 2, 3, 4 or 5; The L is selected from the group shown in formula 1-a or 1-b below.

[0010] The " "Indicates L" 10 L 20 L 30 Connection sites; X is selected from O, S, CR1R2 or NR3; The same or different R1 and R2 are selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R1 and R2 are bonded to each other to form a substituted or unsubstituted ring; The R3 is selected from one of the following: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl. The z that are the same or different are selected from CH or N; The R a R b The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R a or two adjacent R b They bond together to form substituted or unsubstituted rings; The n1 is selected from 0, 1, 2, 3 or 4; the n2 is selected from 0, 1 or 2; The same or different v is selected from CH or N; The R c The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R c They bond together to form substituted or unsubstituted rings; The m1 is selected from 0, 1, 2, 3, 4 or 5; The L 10 L 20 L 30 The same or different is selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic ring fused cycloyl group, substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroarylene ring fused cycloyl group; The L1, L2, L3, L4, L5, and L6 are the same or different from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic rings in a fused cycloalcoholic group, or substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroarylene rings in a fused cycloalcoholic group.

[0011] Beneficial effects: The aromatic amine derivative of Formula 1 of this invention possesses excellent hole transport capability and suitable HOMO orbital energy levels. When used as a hole transport material in organic electroluminescent devices, it not only improves the injection and transport efficiency of holes within the device but also effectively blocks electrons within the light-emitting layer, increasing the recombination efficiency of electrons and holes, thereby improving the luminous efficiency of the device and reducing its driving voltage. Simultaneously, the aromatic amine derivative of Formula 1 of this invention also exhibits good film-forming properties and thermal stability, effectively extending the device's lifespan.

[0012] In addition, the aromatic amine derivatives of Formula 1 of the present invention have high glass transition temperature and good film-forming properties. When used as a capping layer material in organic electroluminescent devices, they can help reduce total emission at the interface between the ITO thin film and the glass substrate and between the glass substrate and air, reduce total reflection loss and waveguide loss in the device, improve light extraction efficiency, and thus improve the luminous efficiency of organic electroluminescent devices. Detailed Implementation

[0013] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. After reading the present invention, any modifications of the present invention in various equivalent forms by those skilled in the art will fall within the scope of protection claimed in this application.

[0014] In the compounds of the present invention, any atom not specified as a particular isotope is included as any stable isotope of that atom, and includes atoms at both their natural and non-natural isotopic abundances.

[0015] The halogens described in this invention include fluorine, chlorine, bromine, and iodine.

[0016] In this invention, "unsubstituted ZZ group" in "substituted or unsubstituted ZZ group" means that the hydrogen atom of the "ZZ group" is not substituted by a substituent. For example, "unsubstituted aryl group" in "substituted or unsubstituted C6-C60 aryl group" means that the hydrogen atom of the "aryl group" is not substituted by a substituent. And so on.

[0017] In this invention, "CXX~CYY" in "substituted or unsubstituted CXX~CYY ZZ group" represents the number of carbon atoms in the unsubstituted "ZZ group". When the "ZZ group" has a substituent, it does not include the number of carbon atoms in the substituent. For example, in "substituted or unsubstituted C6~C60 aryl group", "C6~C60" represents the number of carbon atoms in the unsubstituted "aryl group". When the "aryl group" has a substituent, it does not include the number of carbon atoms in the substituent. In "fused cycloalcoholic group of substituted or unsubstituted C3~C25 alicyclic ring and C6~C30 aromatic ring", "C3~C25" represents the number of carbon atoms in the unsubstituted "alicyclic ring". When the "alicyclic ring" has a substituent, it does not include the number of carbon atoms in the substituent; "C6~C30" represents the number of carbon atoms in the unsubstituted "aromatic ring". When the "aromatic ring" has a substituent, it does not include the number of carbon atoms in the substituent. And so on.

[0018] In this specification, when a substituent or linking site lies within a bond that extends through two or more rings, it indicates that the substituent or linking site can be linked to any one of the two or more rings, specifically to any one of the corresponding optional sites within the rings. For example, Can represent or ; Can represent , , And so on.

[0019] In this invention, when the position of the substituent on the aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional sites on the aromatic ring. For example, Can represent , , ; Can represent , , ; Can represent , , , , , , , , , And so on.

[0020] In this invention, "forming a ring by bonding two adjacent groups" refers to the formation of a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle by bonding adjacent groups together and optionally aromatizing them. The hydrocarbon ring can be an aliphatic or aromatic hydrocarbon ring. The heterocycle can be an aliphatic or aromatic heterocycle. The aliphatic hydrocarbon ring can be a saturated or unsaturated aliphatic hydrocarbon ring, and the aliphatic heterocycle can be a saturated or unsaturated aliphatic heterocycle. The hydrocarbon ring and heterocycle can be monocyclic or polycyclic groups. Furthermore, the ring formed by bonding adjacent groups can be connected to another ring to form a spirostructure. Specific examples are shown below:

[0021]

[0022] In this invention, the rings formed by the connection can be three-membered rings, four-membered rings, five-membered rings, six-membered rings, seven-membered rings, eight-membered rings, fused rings, spirocyclic rings, etc., such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, quinoline, isoquinoline, quinazoline, quinoxaline, fluorene, dibenzofuran, dibenzothiophene, carbazole, etc., but are not limited to these.

[0023] In this invention, "substituted or unsubstituted" means that at least one hydrogen atom on a group is replaced by a substituent. When multiple hydrogen atoms are replaced by multiple substituents, the multiple substituents may be the same or different. The position of the hydrogen atoms replaced by the substituents can be arbitrary. The substituents represented by "substituted or unsubstituted" in the above-mentioned terms include the following groups: deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C2-C15 heterocyclic, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heteroaryl, fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C6-C20 aromatic rings, fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C2-C20 heteroaryl rings, etc. Preferred groups include: deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, camphenyl, isocamphenyl, fentanyl, phenyl, biphenyl, naphthyl, phenanthrene, triphenylene, anthracene, pyrene, phenanthrene, fluoranyl, benzocyclopropane, benzocyclobutane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, benzene The substituents include cyclobutenyl, indene, dihydronaphthyl, fluorenyl, spirodifluorenyl, benzofuranyl, dibenzofuranyl, benzothiopheneyl, dibenzothiopheneyl, indolyl, carbazoleyl, benzodioxonyl, benzodisulfideyl, dihydroisobenzofuranyl, dihydrobenzofuranyl, dihydrobenzothiopheneyl, dihydroisobenzothiopheneyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, etc. Furthermore, each of the above substituents can be substituted or unsubstituted. Two adjacent substituents can bond to form a ring.

[0024] The alkyl group described in this invention refers to a hydrocarbon group formed by removing one hydrogen atom from an alkane molecule. The alkyl group can be a straight-chain alkyl group or a branched alkyl group. When the chain alkyl group described in this invention has three or more carbon atoms, it includes its isomers; for example, propyl includes n-propyl and isopropyl; butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl, and so on. Examples of alkyl groups include, but are not limited to, the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc., but are not limited thereto. The alkyl group has a carbon number of C1 to C30, preferably C1 to C25, preferably C1 to C20, preferably C1 to C15, and even more preferably C1 to C10.

[0025] The cycloalkyl group described in this invention refers to a hydrocarbon group formed by removing one hydrogen atom from a cycloalkane molecule. The cycloalkyl group includes monocyclic cycloalkyl, polycyclic cycloalkyl, and bridged cycloalkyl groups. Examples of cycloalkyl groups include, but are not limited to, the following groups: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornel, camphenyl, fentanyl, isocamphenyl, etc., but are not limited thereto. The cycloalkyl group has 3 to 30 carbon atoms, preferably 3 to 25, preferably 3 to 20, preferably 3 to 15, and more preferably 3 to 10.

[0026] The aryl group referred to in this invention refers to the general term for a monovalent group remaining after removing a hydrogen atom from the aromatic carbon atom of an aromatic compound molecule. The aryl group includes monocyclic aryl, polycyclic aryl, fused-ring aryl, or combinations thereof. Examples of the aryl group include, but are not limited to, the following groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, anthracene, triphenylene, fluorene, benzo[a]fluorene, spirodifluorene, spiroanthracenefluorene, pyrene, phenyl, fluoranthracene, etc., but are not limited thereto. The aryl group has a carbon number of C6 to C30, preferably C6 to C25, and even more preferably C6 to C20.

[0027] The heteroaryl group described in this invention refers to a monovalent group in which at least one carbon atom of an aryl group is replaced by a heteroatom. The heteroatom is selected from O, S, N, Si, B, P, etc., but is not limited thereto. Examples of heteroaryl groups include, but are not limited to, the following groups: benzofuranyl, naphthofuranyl, phenanthrofuranyl, dibenzofuranyl, benzodibenzofuranyl, benzothiophene, naphthothiophene, phenanthiophene, dibenzothiophene, benzodibenzothiophene, indolyl, naphthoindolyl, carbazoyl, benzocarbazoyl, spirofluorenexanthracene, spirofluorenethionanthracene, spirofluoreneazanthracene, dihydrobenzofuranyl, dihydrobenzothiophene, phenoxazinyl, phenthiazinyl, dihydroacridyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, etc., but are not limited thereto. The heteroaryl group has a carbon number of C2 to C60, preferably C2 to C30, more preferably C2 to C25, and even more preferably C3 to C20.

[0028] The fused alicyclic and aromatic ring groups described in this invention refer to the general term for monovalent groups formed by fusion of an alicyclic and an aromatic ring and the removal of one hydrogen atom. Examples of fused alicyclic and aromatic ring groups include, but are not limited to, the following groups: benzocyclopropane, benzocyclobutane, benzocyclobutenyl, dihydroindene, indene, tetrahydronaphthyl, dihydronaphthyl, benzocycloheptane, benzocycloheptenyl, etc., but are not limited thereto. The alicyclic ring has 3 to 25 carbon atoms, preferably 3 to 20, preferably 3 to 15, even more preferably 3 to 10, and more preferably 3 to 8. The aromatic ring has 6 to 30 carbon atoms, preferably 6 to 25, preferably 6 to 18, even more preferably 6 to 12, and more preferably 6 to 10.

[0029] The fused cyclic group of alicyclic and heteroaromatic rings described in this invention refers to the general term for a monovalent group remaining after alicyclic and heteroaromatic rings are fused together and one hydrogen atom is removed. Examples of fused cyclic groups of alicyclic and aromatic rings include, but are not limited to, the following groups: pyridocyclobutane, pyridocyclopentane, pyridocyclohexane, pyridocyclopentenyl, pyridocyclohexenyl, pyrimidinocyclopentane, pyrimidinocyclohexane, etc., but are not limited thereto. The alicyclic ring has 3 to 25 carbon atoms, preferably 3 to 20, preferably 3 to 15, and even more preferably 3 to 10. The heteroaromatic ring has 2 to 30 carbon atoms, preferably 2 to 25, preferably 2 to 18, preferably 2 to 12, and even more preferably 2 to 10.

[0030] The arylene group referred to in this invention refers to the general term for a monovalent group remaining after removing a hydrogen atom from the aromatic carbon atom of an aromatic compound molecule. The arylene group includes monocyclic arylene, polycyclic arylene, fused-ring arylene, or combinations thereof. Examples of the arylene group include, but are not limited to, the following groups: phenylene, biphenylene, terphenylene, naphthylene, phenanthrene, fluorene, benzo[a]fluorene, dibenzo[a]fluorene, naphthylene, spirodifluorene, etc., but are not limited thereto. The arylene group has a carbon number of C6 to C30, preferably C6 to C25, more preferably C6 to C20, and more preferably C6 to C18.

[0031] The heteroaryl group described in this invention refers to a divalent group in which at least one carbon atom of the aryl group is replaced by a heteroatom. The heteroatom is selected from O, S, N, Si, B, P, etc., but is not limited thereto. The heteroaryl group includes monocyclic heteroaryl, polycyclic heteroaryl, fused-ring heteroaryl, or combinations thereof. Examples of the heteroaryl group include, but are not limited to, the following groups: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolineyl, quinazolinyl, etc., but are not limited thereto. The number of carbon atoms in the heteroaryl group is C2 to C30, preferably C2 to C25, and more preferably C2 to C20.

[0032] The fused alicyclic and aromatic ring groups described in this invention refer to the general term for divalent groups remaining after removing two hydrogen atoms from the fused alicyclic and aromatic rings. Examples of fused alicyclic and aromatic ring groups include, but are not limited to, the following groups: benzo[a]cyclopropane, benzo[a]cyclobutane, dihydroindene, indene, tetrahydronaphthyl, dihydronaphthyl, benzo[a]cycloheptane, benzo[a]cyclobutenyl, benzo[a]cycloheptenyl, etc., but are not limited thereto. The alicyclic ring has 3 to 25 carbon atoms, preferably 3 to 20, preferably 3 to 15, and even more preferably 3 to 8. The aromatic ring has 6 to 30 carbon atoms, preferably 6 to 20, preferably 6 to 18, and even more preferably 6 to 10.

[0033] The fused alicyclic and heteroaromatic ring groups described in this invention refer to the general term for divalent groups remaining after removing two hydrogen atoms from the fused alicyclic and heteroaromatic rings. Examples of fused alicyclic and heteroaromatic ring groups include, but are not limited to, the following groups: pyridinocyclobutyl, pyridinocyclopentyl, pyridinocyclohexyl, pyridinocyclopentenyl, etc., but are not limited thereto. The alicyclic ring has 3 to 25 carbon atoms, preferably 3 to 20, preferably 3 to 15, and even more preferably 3 to 8. The heteroaromatic ring has 2 to 30 carbon atoms, preferably 2 to 20, preferably 2 to 18, and even more preferably 2 to 10.

[0034] This invention provides an aromatic amine derivative, represented by the following formula 1.

[0035] Wherein, Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 are the same or different and are selected from one of the following: substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C2-C60 heteroaryl groups, fused cycloalkanes of substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic groups, and fused cycloalkanes of substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroaromatic groups. At least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is selected from the groups shown in Formula 1-c below.

[0036] The x that are the same or different are selected from CH or N; The Y is selected from O or S; The R dThe same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R d They bond together to form substituted or unsubstituted rings; The s1 is selected from 0, 1, 2, 3, 4 or 5; The L is selected from the group shown in formula 1-a or 1-b below.

[0037] The " "Indicates L" 10 L 20 L 30 Connection sites; X is selected from O, S, CR1R2 or NR3; The same or different R1 and R2 are selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R1 and R2 are bonded to each other to form a substituted or unsubstituted ring; The R3 is selected from one of the following: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl. The z that are the same or different are selected from CH or N; The R a R b The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R a or two adjacent R b They bond together to form substituted or unsubstituted rings; The n1 is selected from 0, 1, 2, 3 or 4; the n2 is selected from 0, 1 or 2; The same or different v is selected from CH or N; The R cThe same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R c They bond together to form substituted or unsubstituted rings; The m1 is selected from 0, 1, 2, 3, 4 or 5; The L 10 L 20 L 30 The same or different is selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic ring fused cycloyl group, substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroarylene ring fused cycloyl group; The L1, L2, L3, L4, L5, and L6 are the same or different from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic rings in a fused cycloalcoholic group, or substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroarylene rings in a fused cycloalcoholic group.

[0038] Preferably, formula 1-c is selected from one of the following groups:

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] The Y is selected from O or S; The s1 is selected from 0, 1, 2, 3, 4 or 5; the s2 is selected from 0, 1, 2, 3 or 4; the s3 is selected from 0, 1, 2 or 3; the s4 is selected from 0, 1 or 2; the s5 is selected from 0 or 1; the s6 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the s7 is selected from 0, 1, 2, 3, 4, 5 or 6; the s8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; and the s9 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0047] More preferably, formula 1-c is selected from one of the following groups:

[0048]

[0049]

[0050]

[0051] Preferably, the R d The same or different from one or a combination thereof selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, or two adjacent R groups, or two adjacent R groups. d They bond with each other to form substituted or unsubstituted benzene rings.

[0052] Preferably, R1 and R2, whether identical or different, are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, and quinoxalinyl, or R1 and R2 are bonded to each other to form substituted or unsubstituted rings.

[0053] Preferably, the R3 groups, whether identical or different, are selected from one or a combination of methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, and quinoxalinyl groups, and the above groups may be substituted with one or more deuterium groups.

[0054] Preferably, formula 1-a is selected from one of the following groups:

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070] The n1 is selected from 0, 1, 2, 3 or 4; the n2 is selected from 0, 1 or 2; the n3 is selected from 0, 1, 2, 3, 4, 5 or 6; the n4 is selected from 0, 1, 2 or 3; the n5 is selected from 0, 1, 2, 3, 4 or 5; the n6 is selected from 0 or 1; and the n7 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

[0071] More preferably, formula 1-a is selected from one of the following groups:

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] .

[0080] Preferably, the R a R b The same or different from one or a combination thereof selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, or adjacent R a Adjacent R b They bond with each other to form substituted or unsubstituted benzene rings.

[0081] Preferably, formula 1-b is selected from one of the following groups:

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] The m1 is selected from 0, 1, 2, 3, 4 or 5; the m2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m3 is selected from 0, 1, 2, 3 or 4; the m4 is selected from 0, 1, 2 or 3; the m5 is selected from 0, 1, 2, 3, 4, 5 or 6; and the m6 is selected from 0, 1 or 2.

[0088] More preferably, formula 1-b is selected from one of the following groups:

[0089]

[0090]

[0091]

[0092]

[0093] The R c The same or different are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl.

[0094] More preferably, the L is selected from one of the following groups:

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] The R a R b The same or different are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, pyridyl, pyrimidinyl, pyrimidinyl The R c The same or different are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, pyridyl, pyrimidinyl, and pyrimidinyl.

[0105] Most preferably, the L is selected from one of the following groups:

[0106]

[0107]

[0108]

[0109] The R a R b The same or different are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, and naphthyl; The R c The same or different are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl.

[0110] Preferably, at least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is selected from the groups shown in 1-c, and the remaining groups are independently selected from one or a combination of the groups shown below.

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118] The R i The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R i They bond together to form substituted or unsubstituted rings; The R t The same or different is selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; The R4 is selected from one of the following: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl. The R5 and R6 are the same or different and are selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R5 and R6 are bonded to each other to form a substituted or unsubstituted ring; r1 is selected from 0, 1, 2, 3, 4, or 5; r2 is selected from 0, 1, 2, 3, or 4; r3 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; r4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; r5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; r6 is selected from 0, 1, 2, or 3; r7 is selected from 0, 1, or 2; r8 is selected from 0, 1, 2, 3, 4, 5, or 6; r9 is selected from 0 or 1. t1 is selected from 0, 1, or 2; t2 is selected from 0, 1, 2, 3, or 4; t3 is selected from 0, 1, 2, 3, 4, 5, or 6; t4 is selected from 0, 1, 2, 3, 4, or 5; t5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; t6 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; t7 is selected from 0, 1, 2, or 3.

[0119] Preferably, the R4 groups, whether identical or different, are selected from methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, and quinoxalinyl, and the above groups may be substituted with one or more deuterium groups.

[0120] Preferably, R5 and R6 are the same or different and are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, or adjacent R5 and R6 are bonded to each other to form substituted or unsubstituted rings.

[0121] More preferably, at least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is selected from the groups shown in 1-c, and the remaining groups are independently selected from one or a combination of the groups shown below.

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] The R iThe same or different from one or a combination thereof selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, or two adjacent R groups, or two adjacent R groups. i They bond with each other to form substituted or unsubstituted benzene rings; The R t The same or different are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl.

[0129] The at least one group selected from Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is one, two, three, four, five, or six groups selected from Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6.

[0130] Preferably, at least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is selected from the group shown in Formula 1-c, including: one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 selected from the group shown in Formula 1-c, specifically, Ar1, Ar2, Ar3, Ar4, Ar5, or Ar6 is selected from the group shown in Formula 1-c; two of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 are selected from the group shown in Formula 1-c, specifically, Ar1 and Ar2, Ar1 and Ar3, Ar1 and Ar5, Ar3 and Ar4, Ar3 and Ar5, or Ar5 and Ar6 are selected from the group shown in Formula 1-c; three of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 are selected from the group shown in Formula 1-c, specifically, Ar1, Ar2 and Ar3, Ar1, Ar2 and Ar5, Ar1, Ar3 and Ar4, Ar1, Ar3 and Ar5, Ar1, Ar5 and Ar6, Ar3, Ar4 Ar5, or Ar3, Ar5 and Ar6 are selected from the groups shown in Formula 1-c; four of Ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are selected from the groups shown in Formula 1-c, specifically, Ar1, Ar2, Ar3 and Ar4, Ar1, Ar2, Ar3 and Ar5, Ar1, Ar2, Ar5 and Ar6, Ar1, Ar3, Ar4 and Ar5, or Ar3, Ar4, Ar5 and Ar6 are selected from the groups shown in Formula 1-c; five of Ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are selected from the groups shown in Formula 1-c, specifically, Ar1, Ar2, Ar3, Ar4 and Ar5, or Ar1, Ar3, Ar4, Ar5 and Ar6 are selected from the groups shown in Formula 1-c; six of Ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are selected from the groups shown in Formula 1-c, specifically, Ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are selected from the groups shown in Formula 1-c.

[0131] Preferably, the L 10 L 20 L 30 The same or different groups are selected from single bonds, or one or a combination of the groups shown below.

[0132]

[0133]

[0134]

[0135]

[0136] The R sThe same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R s They bond together to form substituted or unsubstituted rings; The R k The same or different is selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl; The value of e1 is selected from 0, 1, 2, 3, or 4; the value of e2 is selected from 0, 1, 2, 3, 4, 5, or 6; the value of e3 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; the value of e4 is selected from 0, 1, 2, or 3; the value of e5 is selected from 0, 1, or 2; the value of e6 is selected from 0 or 1; the value of e7 is selected from 0, 1, 2, 3, 4, or 5; the value of e8 is selected from 0, 1, 2, 3, 4, 5, 6, or 7. The j1 is selected from 0, 1 or 2; the j2 is selected from 0, 1, 2, 3 or 4; the j3 is selected from 0, 1, 2, 3, 4, 5 or 6; the j4 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0137] More preferably, the R s The same or different from one or a combination thereof selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, or two adjacent R groups, or two adjacent R groups. s They bond with each other to form substituted or unsubstituted benzene rings.

[0138] More preferably, the R k The same or different are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexyl, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl.

[0139] The most preferred option is the L 10 Selected from single bonds; the L 20 Selected from single bonds; the L 30 Selected from single keys.

[0140] Preferably, L1, L2, L3, L4, L5, and L6, whether identical or different, are selected from single bonds, or from one or a combination of the following groups.

[0141]

[0142] The s that are the same or different are selected from CR e Or N; The R e Selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R e They bond together to form substituted or unsubstituted rings; Z is selected from O, S, CR7R8 or NR9; The R7 and R8 are the same or different and are selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R7 and R8 are bonded to each other to form a substituted or unsubstituted ring; The R9 is selected from one of the following: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl.

[0143] Preferably, L1, L2, L3, L4, L5, and L6, whether identical or different, are selected from single bonds, or from one or a combination of the following groups.

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151] The R x The same or different is selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl; The i1 is selected from 0, 1, 2, 3, or 4; the i2 is selected from 0, 1, 2, 3, 4, 5, or 6; the i3 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; the i4 is selected from 0, 1, 2, or 3; the i5 is selected from 0, 1, or 2; the i6 is selected from 0 or 1; the i7 is selected from 0, 1, 2, 3, 4, or 5; and the i8 is selected from 0, 1, 2, 3, 4, 5, 6, or 7. c1 is selected from 0, 1 or 2; c2 is selected from 0, 1, 2, 3 or 4; c3 is selected from 0, 1, 2, 3, 4, 5 or 6; c4 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0152] Preferably, the R e The same or different from one or a combination thereof selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, or two adjacent R groups, or two adjacent R groups. e They bond with each other to form substituted or unsubstituted benzene rings.

[0153] Preferably, the R x The same or different are selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, trifluoromethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexyl, dihydroindyl, tetrahydronaphthyl, benzocycloheptane, indyl, dihydronaphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl.

[0154] Preferably, the aromatic amine derivative is selected from any one of the structures shown below.

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401] .

[0402] The above lists some specific chemical structures of the aromatic amine derivatives shown in Formula 1 of this invention. However, this invention is not limited to these listed chemical structures. Any structure based on Formula 1 with substituents as defined above should be included.

[0403] In addition, the present invention also provides an organic electroluminescent device containing the aromatic amine derivative of the present invention described above.

[0404] Preferably, the organic electroluminescent device includes an anode, a cathode, and an organic layer, wherein the organic layer is located between the cathode and the anode or outside one or more electrodes of the anode and the cathode, and the organic layer contains the aromatic amine derivatives of the present invention described above.

[0405] Preferably, the organic layer includes a hole transport layer containing the aromatic amine derivatives of the present invention described above.

[0406] Preferably, the hole transport layer includes a first hole transport layer and a second hole transport layer, the first hole transport layer is located between the hole injection layer and the light-emitting layer, the second hole transport layer is located between the first hole transport layer and the light-emitting layer, and at least one of the first hole transport layer and the second hole transport layer contains the aromatic amine derivative of the present invention described above.

[0407] Preferably, the organic layer includes a capping layer containing the aromatic amine derivatives of the present invention described above.

[0408] The organic functional layer of the organic electroluminescent device of the present invention may include a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, etc. The organic functional layer may be formed by a single-layer structure or by a multi-layer structure with multiple organic layers stacked on top of each other. Each organic functional layer may also contain one or more materials.

[0409] This invention does not particularly limit the materials of the thin films in the organic electroluminescent device; substances known in the art can be used. The organic functional layers of the aforementioned organic electroluminescent device and the electrodes on both sides of the device are described below: The anode of this invention is preferably a material with good electrical conductivity and a high work function, including, but not limited to, metal oxides, metal alloys, metals, and conductive polymers. Specific examples of the anode material may include, but are not limited to, gold (Au), silver (Ag), platinum (Pt), palladium (Pd), indium zinc oxide (IZO), indium tin oxide (ITO), zinc oxide (ZnO), indium tin oxide / silver / indium tin oxide (ITO / Ag / ITO), aluminum / nickel (Al / Ni), polyaniline, etc.

[0410] The hole injection layer of the present invention preferably contains materials with good hole injection capability, including triarylamine compounds, porphyrin compounds, styrene compounds, polythiophene and its derivatives, phthalocyanine derivatives, etc., but is not limited thereto. Specific examples of the hole injection materials may include N,N'-bis[4-di(m-tolyl)aminophenyl]-N,N'-diphenylbenzidine (DNTPD), 4,4',4"-tris(N-(1-naphthyl)-N-phenylamino)triphenylamine (1-TNATA), 4,4',4'-tris[2-naphthylphenylamino]triphenylamine (2-TNATA), 1,4,5,8,9,11-hexaazabenzonitrile (HAT-CN), molybdenum trioxide (MoO3), copper phthalocyanine (CuPC), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT / PSS), etc., but are not limited thereto.

[0411] The hole transport layer of the present invention preferably uses materials with strong hole transport performance, including aromatic amine derivatives, carbazole derivatives, polymers, etc., but not limited thereto. Specific examples of the hole transport materials may include N4,N4'-di(biphenyl-4-yl)-N4,N4'-diphenylbiphenyl-4,4'-diamine (TPD-10), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), 1,3,5-tris(9-carbazoleyl)benzene (TCB), 4,4',4''-tris(carbazole-9-yl)triphenylamine (TCTA), etc., but are not limited thereto. Aromatic amine derivatives of Formula 1 of the present invention are preferred.

[0412] The electron blocking layer of the present invention is preferably made of a material with good electron blocking ability, including aromatic amine derivatives, carbazole derivatives, etc., but not limited thereto. Specific examples of the electron blocking material may include N,N'-bis(naphthyl-1-yl)-N,N'-diphenyl-benzidine (NPD), N,N-bis([1,1'-biphenyl]-4-)-(9H-carbazole-9-yl)-[1,1'-biphenyl]-4-amine, etc., but are not limited thereto. Aromatic amine derivatives of Formula 1 of the present invention are preferred.

[0413] The luminescent layer of the present invention comprises a host material and a guest material. The host material of the luminescent layer of the present invention preferably uses a substance with a higher LUMO than the guest material and a lower HOMO than the guest material, including heterocyclic compounds, aromatic amine compounds, fused aromatic ring derivatives, metal complexes, silicon-containing compounds, etc., but not limited thereto. Specific examples may include 4,4'-bis(carbazole-9-yl)biphenyl (CBP), 1,3-bis(N-carbazole-yl)benzene (MCP), 1,3,5-tris(carbazole-9-yl)benzene (TCP), 9,10-bis(2-naphthyl)anthracene (ADN), 4,4',4''-tris(carbazole-9-yl)triphenylamine (TCTA), tris(8-hydroxyquinoline)aluminum (Alq3), bis(8-hydroxyquinoline)zinc (Znq2), etc., but not limited thereto.

[0414] The guest material of this invention may be a fluorescent compound, including pyrene derivatives, fluoranthene derivatives, aromatic amine derivatives, etc.; phosphorescent materials may also be used, such as iridium complexes, platinum complexes, and other metal complexes, but are not limited thereto. Specific examples may include, but are not limited to, 4,4'-bis(9-ethyl-3-carbazolevinyl)-1,1'-biphenyl (BCzVBi), tris(2-phenylpyridine)iridium (Ir(ppy)3), tris[2-(3-methyl-2-pyridyl)phenyl]iridium (Ir(3mppy)3), di(2-phenylpyridine)(acetylacetone)iridium (Ir(ppy)2(acac)), bis(2-benzo[H]quinoline-C2,N')(acetylacetone)iridium (Ir(bzq)2(acac)), di(1-phenyl-isoquinoline)(acetylacetone)iridium (Ir(piq)2(acac)), tris(1-phenyl-isoquinoline)iridium (Ir(piq)3), 2,5,8,11-tetratert-butylperylene (TBPe), etc.

[0415] The hole-blocking layer of the present invention preferably comprises a material having a strong hole-blocking ability and a suitable HOMO / LUMO energy level, including imidazoles, triazoles, phenanthroline derivatives, etc., but not limited thereto. Specific examples may include bis(2-methyl-8-hydroxyquinoline-N1,O8)-(1,1'-biphenyl-4-hydroxy)aluminum (BAlq), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), etc., but not limited thereto.

[0416] The electron transport layer of the present invention preferably has a strong electron-withdrawing ability, including metal complexes, heteroaromatic compounds, polymers, etc., but is not limited thereto. Specific examples may include 8-hydroxyquinoline aluminum (Alq3), tris(4-methyl-8-hydroxyquinoline)aluminum (Al(4-Mq)3), bis(8-hydroxyquinoline)zinc(II) (Znq), 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), 2-(4-(9,10-bis(naphthyl-2-yl)anthracene-2-phenyl)-1-phenyl)-1H-phenanthrene[9,10-d]imidazole (ADN-PAimi), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,4'-bis(4,6-diphenyl-1,3,5-triazin-2-yl)biphenyl (BTB), etc., but is not limited thereto.

[0417] The electron injection layer of the present invention is preferably made of a material with good electron injection capability, including metals, metal compounds, metal oxides, etc., but not limited thereto. Specific examples may include calcium (Ca), lithium (Li), lithium fluoride (LiF), lithium 8-hydroxyquinoline (LiQ), calcium carbonate (CaCO3), rubidium acetate (CH3COORb), lithium oxide (Li2O), etc., but are not limited thereto.

[0418] The cathode of the present invention is preferably made of a material with good electrical conductivity and a low work function, including metals, metal alloys, etc., but not limited thereto. Specific examples of the cathode material may include aluminum (Al), silver (Ag), gold (Au), lead (Pb), lithium (Li), magnesium (Mg), calcium-silver alloy (Ca / Ag), magnesium-silver alloy (Mg / Ag), lithium-aluminum alloy (Li / Al), etc., but are not limited thereto.

[0419] The capping material of the present invention preferably has a high glass transition temperature and excellent light extraction performance, including aromatic amine derivatives, metal compounds, carbazole derivatives, etc., but is not limited thereto. Specific examples may include tris(8-hydroxyquinoline)aluminum (Alq3), 4,4'-bis(carbazole-9-yl)biphenyl (CBP), N,N'-di(naphthyl-1-yl)-N,N'-diphenyl-benzidine (NPD), etc., but are not limited thereto. Aromatic amine derivatives of Formula 1 of the present invention are preferred.

[0420] There are no particular limitations on the preparation method of each thin film in the organic electroluminescent device of the present invention. Vacuum evaporation, sputtering, spin coating, spraying, screen printing, laser transfer, etc. can be used, but are not limited to these methods.

[0421] The organic electroluminescent device of the present invention is mainly used in panel display, lighting, organic solar cells, organic thin film transistors, flexible OLEDs and other fields, but is not limited thereto.

[0422] The present invention is illustrated in more detail by the following embodiments; however, the embodiments described below are merely illustrative of this specification and the scope of this specification is not limited to these embodiments.

[0423] Synthesis Examples

[0424] Raw materials and reagents: This invention does not impose any particular limitations on the raw materials or reagents used in the following synthesis examples. They can be commercially available products or prepared using methods well-known to those skilled in the art. All raw materials and reagents used in this invention are of reagent purity.

[0425] Instruments: G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer (Waters Corporation, UK); Vario ELcube organic elemental analyzer (Elementar Corporation, Germany).

[0426] There are no particular limitations on the preparation method of the aromatic amine derivatives shown in Formula 1 of this invention, and conventional methods well known to those skilled in the art can be used. For example, carbon-nitrogen coupling reactions, etc. The aromatic amine derivatives shown in Formula 1 of this invention can be prepared using the synthetic route shown below.

[0427] Synthesis of intermediates:

[0428]

[0429] Compound synthesis: Synthesis Route 1:

[0430] Synthesis Route 2:

[0431] Synthesis Route 3:

[0432] Synthesis Route 4:

[0433] The Xn is a halogen, for example, the same or different Xn are selected from Cl, Br, I.

[0434] Synthesis Example 1: Synthesis of Compound 2

[0435] Preparation of intermediate A-2: Under nitrogen protection, toluene (1000 mL), a-2 (10.24 g, 110.00 mmol), b-2 (25.64 g, 110.00 mmol), Pd(OAc)2 (0.30 g, 1.32 mmol), and sodium tert-butoxide (15.86 g, 165.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and then refluxed for 6.5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene / methanol (10:1 v / v) yielded intermediate A-2 (21.59 g, 80% yield), with a solid purity ≥99.81% as determined by HPLC. Mass spectrometry m / z: 245.1220 (theoretical value: 245.1204).

[0436] Preparation of intermediate B-2: Under nitrogen protection, toluene (300 mL), c-2 (6.77 g, 40.00 mmol), d-2 (7.88 g, 40.00 mmol), Pd(dppf)Cl2 (0.35 g, 0.48 mmol), and sodium tert-butoxide (5.77 g, 60.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and then refluxed for 4.5 hours. After the reaction was complete, the reaction solution was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from ethyl acetate yielded intermediate B-2 (8.90 g, 78% yield), with a solid purity ≥99.83% as determined by HPLC. Mass spectrometry m / z: 285.1141 (theoretical value: 285.1154).

[0437] Preparation of intermediate E-2: Under nitrogen protection, toluene (700 mL), g-2 (12.82 g, 40.00 mmol), A-2 (19.63 g, 80.00 mmol), Pd(OAc)2 (0.27 g, 1.20 mmol), sodium tert-butoxide (15.38 g, 160.00 mmol), and tri-tert-butylphosphine (3.20 mL, 1.60 mmol, in 0.5 M toluene solution) were added sequentially to a reaction flask. The mixture was stirred to dissolve and refluxed for 6 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The mixture was purified by silica gel column chromatography with n-hexane / dichloromethane (9:1 v / v) to give intermediate E-2 (19.48 g, 75% yield). The purity of the solid was ≥99.79% as determined by HPLC. Mass spectrometry m / z: 648.2341 (theoretical value: 648.2332).

[0438] Preparation of compound 2: Under nitrogen protection, toluene (200 mL), E-2 (16.23 g, 25.00 mmol), B-2 (7.13 g, 25.00 mmol), Pd2(dba)3 (0.23 g, 0.25 mmol), sodium tert-butoxide (4.81 g, 50.00 mmol), and BINAP (0.33 g, 0.50 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved and refluxed for 6.5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene yielded compound 2 (16.17 g, 72% yield), with a solid purity ≥99.97% as determined by HPLC. Mass spectrometry m / z: 897.3701 (theoretical value: 897.3719). Theoretical elemental content (%) C 66 H 47N3O: C, 88.26; H, 5.28; N, 4.68. Measured elemental content (%): C, 88.30; H, 5.32; N, 4.70.

[0439] Synthesis Example 2: Synthesis of Compound 18

[0440] Following the same preparation method as in Synthesis Example 1, b-2, c-2, and d-2 were replaced with equimolar amounts of b-18, a-2, and d-18, respectively, to obtain compound 18 (16.12 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 933.4642 (theoretical value: 933.4658). Theoretical elemental content (%) C 68 H 59 N3O: C, 87.42; H, 6.37; N, 4.50. Measured elemental content (%): C, 87.39; H, 6.40; N, 4.48.

[0441] Synthesis Example 3: Synthesis of Compound 28

[0442] Following the same preparation method as in Synthesis Example 1, b-2, c-2, and d-2 were replaced with equimolar amounts of b-28, c-28, and d-28, respectively, to obtain compound 28 (16.10 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 960.3839 (theoretical value: 960.3828). Theoretical elemental content (%) C 70 H 48 N4O: C, 87.47; H, 5.03; N, 5.83. Measured elemental content (%): C, 87.51; H, 5.05; N, 5.79.

[0443] Synthesis Example 4: Synthesis of Compound 40

[0444] Following the same preparation method as in Synthesis Example 1, b-2, c-2, and d-2 were replaced with equimolar amounts of b-40, a-2, and d-40, respectively, to obtain compound 40 (15.66 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 869.2911 (theoretical value: 869.2903). Theoretical elemental content (%) C 60 H 35N7O: C, 82.84; H, 4.06; N, 11.27. Measured elemental content (%): C, 82.79; H, 4.10; N, 11.31.

[0445] Synthesis Example 5: Synthesis of Compound 83

[0446] Following the same preparation method as in Synthesis Example 1, b-2, c-2, and d-2 were replaced with equimolar amounts of b-83, c-83, and d-83, respectively, to obtain compound 83 (16.73 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 955.4521 (theoretical value: 955.4502). Theoretical elemental content (%) C 70 H 57 N3O: C, 87.92; H, 6.01; N, 4.39. Measured elemental content (%): C, 87.89; H, 6.04; N, 4.41.

[0447] Synthesis Example 6: Synthesis of Compound 114

[0448] Preparation of intermediate A-2: Under nitrogen protection, toluene (800 mL), a-2 (8.38 g, 90.00 mmol), b-2 (20.98 g, 90.00 mmol), Pd(dppf)Cl2 (0.79 g, 1.08 mmol), and sodium tert-butoxide (12.97 g, 135.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and the mixture was refluxed for 5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene / methanol (9:1 v / v) yielded intermediate A-2 (17.66 g, 80% yield), with a solid purity ≥99.80% as determined by HPLC. Mass spectrometry m / z: 245.1215 (theoretical value: 245.1204).

[0449] Preparation of intermediate B-114: Under nitrogen protection, toluene (500 mL), c-144 (6.43 g, 60.00 mmol), d-144 (16.45 g, 60.00 mmol), Pd(OAc)2 (0.19 g, 0.84 mmol), and sodium tert-butoxide (8.65 g, 90.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and then refluxed for 5.5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene / methanol (8:1 v / v) yielded intermediate B-114 (14.06 g, 78% yield), with a solid purity ≥99.76% as determined by HPLC. Mass spectrometry m / z: 300.1255 (theoretical value: 300.1263).

[0450] Preparation of intermediate C-114: Under nitrogen protection, toluene (300 mL), e-144 (4.85 g, 40.00 mmol), f-144 (10.93 g, 40.00 mmol), Pd2(dba)3 (0.37 g, 0.40 mmol), and sodium tert-butoxide (5.77 g, 60.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and then refluxed for 4.5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene / methanol (10:1 v / v) yielded intermediate C-114 (9.65 g, 77% yield), with a solid purity ≥99.82% as determined by HPLC. Mass spectrometry m / z: 313.1450 (theoretical value: 313.1467).

[0451] Preparation of intermediate D-144: Under nitrogen protection, toluene (500 mL), g-144 (22.04 g, 60.00 mmol), A-2 (14.72 g, 60.00 mmol), Pd(OAc)2 (0.20 g, 0.90 mmol), sodium tert-butoxide (11.53 g, 120.00 mmol), and tri-tert-butylphosphine (2.40 mL, 1.20 mmol, in 0.5 M toluene solution) were added sequentially to a reaction flask. The mixture was stirred to dissolve and refluxed for 5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The mixture was purified by silica gel column chromatography with n-hexane / dichloromethane (8:1 v / v) to give intermediate D-144 (22.11 g, 76% yield). The solid purity was ≥99.84% as determined by HPLC. Mass spectrometry m / z: 483.0397 (theoretical value: 483.0389).

[0452] Preparation of intermediate E-144: Under nitrogen protection, toluene (300 mL), D-144 (19.39 g, 40.00 mmol), B-114 (12.01 g, 40.00 mmol), Pd(OAc)2 (0.13 g, 0.60 mmol), sodium tert-butoxide (7.69 g, 80.00 mmol), and BINAP (0.52 g, 0.80 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and then refluxed for 5.5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The mixture was purified by silica gel column chromatography with n-hexane / dichloromethane (6:1 v / v) to give intermediate E-144 (20.56 g, 73% yield). The purity of the solid was ≥99.86% as determined by HPLC. Mass spectrometry m / z: 703.2375 (theoretical value: 703.2390).

[0453] Preparation of compound 144: Under nitrogen protection, toluene (300 mL), E-144 (17.61 g, 25.00 mmol), C-144 (7.84 g, 25.00 mmol), Pd2(dba)3 (0.23 g, 0.25 mmol), sodium tert-butoxide (4.81 g, 50.00 mmol), and X-Phos (0.24 g, 0.50 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and the mixture was refluxed for 6 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene yielded compound 144 (16.44 g, 67% yield), with a solid purity ≥99.94% as determined by HPLC. Mass spectrometry m / z: 980.4080 (theoretical value: 980.4090). Theoretical elemental content (%) C 70 H 52 N4O2: C, 85.69; H, 5.34; N, 5.71. Measured elemental content (%): C, 85.71; H, 5.30; N, 5.68.

[0454] Synthesis Example 7: Synthesis of Compound 137

[0455] Preparation of intermediate A-137: Under nitrogen protection, toluene (500 mL), a-137 (8.11 g, 60.00 mmol), d-83 (11.82 g, 60.00 mmol), Pd(OAc)2 (0.16 g, 0.72 mmol), and sodium tert-butoxide (8.65 g, 90.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and then refluxed for 4.5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene / methanol (9:1 v / v) yielded intermediate A-137 (11.91 g, 79% yield), with a solid purity ≥99.77% as determined by HPLC. Mass spectrometry m / z: 251.1329 (theoretical value: 251.1310).

[0456] Preparation of intermediate A-2: Under nitrogen protection, toluene (600 mL), a-2 (6.52 g, 70.00 mmol), b-2 (16.32 g, 70.00 mmol), Pd(dppf)Cl2 (0.61 g, 0.84 mmol), and sodium tert-butoxide (10.09 g, 105.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and then refluxed for 5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene / methanol (9:1 v / v) yielded intermediate A-2 (13.74 g, 80% yield), with a solid purity ≥99.79% as determined by HPLC. Mass spectrometry m / z: 245.1213 (theoretical value: 245.1204).

[0457] Preparation of intermediate D-137: Under nitrogen protection, toluene (500 mL), g-137 (14.08 g, 40.00 mmol), A-137 (10.05 g, 40.00 mmol), Pd(OAc)2 (0.13 g, 0.60 mmol), sodium tert-butoxide (7.69 g, 80.00 mmol), and tri-tert-butylphosphine (1.60 mL, 0.80 mmol, in 0.5 M toluene solution) were added sequentially to a reaction flask. The mixture was stirred to dissolve and refluxed for 5.5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The mixture was purified by silica gel column chromatography with n-hexane / dichloromethane (9:1 v / v) to give intermediate D-137 (15.67 g, 75% yield). The purity of the solid was ≥99.82% as determined by HPLC. Mass spectrometry m / z: 521.1330 (theoretical value: 521.1313).

[0458] Preparation of compound 137: Under nitrogen protection, toluene (300 mL), D-137 (13.06 g, 25.00 mmol), A-2 (12.27 g, 50.00 mmol), Pd2(dba)3 (0.46 g, 0.50 mmol), sodium tert-butoxide (9.61 g, 100.00 mmol), and X-Phos (0.48 g, 1.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved and refluxed for 6 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization from toluene yielded compound 137 (16.22 g, 69% yield), with a solid purity ≥99.98% as determined by HPLC. Mass spectrometry m / z: 939.4174 (theoretical value: 939.4189). Theoretical elemental content (%) C 69 H 53 N3O: C, 88.15; H, 5.68; N, 4.47. Measured elemental content (%): C, 88.13; H, 5.72; N, 4.50.

[0459] Synthesis Example 8: Synthesis of Compound 149

[0460] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-28, c-149, d-149, and g-149, respectively, to obtain compound 149 (16.05 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 916.4198 (theoretical value: 916.4189). Theoretical elemental content (%) C 67 H 44 D5N3O: C, 87.74; H, 5.93; N, 4.58. Measured elemental content (%): C, 87.70; H, 5.89; N, 4.61.

[0461] Synthesis Example 9: Synthesis of Compound 151

[0462] Preparation of intermediate A-151: Under nitrogen protection, toluene (1000 mL), a-2 (9.31 g, 100.00 mmol), d-2 (19.70 g, 100.00 mmol), Pd(dppf)Cl2 (0.88 g, 1.20 mmol), and sodium tert-butoxide (14.41 g, 150.00 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and then refluxed for 6.5 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The mixture was recrystallized from ethyl acetate to give intermediate A-151 (16.95 g, yield 81%). The purity of the solid was ≥99.76% as determined by HPLC. Mass spectrometry m / z: 209.0852 (theoretical value: 209.0841).

[0463] Preparation of compound 151: Under nitrogen protection, toluene (800 mL), g-151 (11.62 g, 25.00 mmol), A-151 (15.69 g, 75.00 mmol), Pd(OAc)2 (0.34 g, 1.50 mmol), sodium tert-butoxide (14.41 g, 150.00 mmol), and BINAP (0.98 g, 1.50 mmol) were added sequentially to a reaction flask. The mixture was stirred until dissolved, and the mixture was refluxed for 7 hours. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The mixture was recrystallized from toluene to give compound 151 (15.51 g, yield 73%). The purity of the solid was ≥99.96% as determined by HPLC. Mass spectrometry m / z: 849.2975 (theoretical value: 849.2991). Theoretical elemental content (%) C 60 H 39 N3O3: C, 84.78; H, 4.62; N, 4.94. Measured elemental content (%): C, 84.82; H, 4.59; N, 4.96.

[0464] Synthesis Example 10: Synthesis of Compound 156

[0465] Following the same preparation method as in Synthesis Example 1, a-2, b-2, c-2, and d-2 were replaced with equimolar amounts of c-2, b-156, a-2, and b-2, respectively, to obtain compound 156 (16.65 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 937.3678 (theoretical value: 937.3668). Theoretical elemental content (%) C 68 H 47N3O2: C, 87.06; H, 5.05; N, 4.48. Measured elemental content (%): C, 87.10; H, 5.03; N, 4.52.

[0466] Synthesis Example 11: Synthesis of Compound 210

[0467] Following the same preparation method as in Synthesis Example 1, b-2, c-2, and d-2 were replaced with equimolar amounts of d-2, a-2, and d-210, respectively, to obtain compound 210 (16.42 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 965.3240 (theoretical value: 965.3254). Theoretical elemental content (%) C 68 H 43 N3O4: C, 84.54; H, 4.49; N, 4.35. Measured elemental content (%): C, 84.56; H, 4.53; N, 4.31.

[0468] Synthesis Example 12: Synthesis of Compound 233

[0469] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-233, c-233, b-28, and g-233, respectively, to obtain compound 233 (16.33 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 946.4225 (theoretical value: 946.4233). Theoretical elemental content (%) C 68 H 38 D9N3O2: C, 86.23; H, 5.96; N, 4.44. Measured elemental content (%): C, 86.19; H, 5.94; N, 4.49.

[0470] Synthesis Example 13: Synthesis of Compound 248

[0471] Following the same preparation method as in Synthesis Example 6, a-2, b-2, c-114, d-114, e-114, f-114, and g-114 were replaced with equimolar amounts of a-248, d-83, c-2, b-2, a-2, b-28, and g-248, respectively, to obtain compound 248 (15.30 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 861.3370 (theoretical value: 861.3355). Theoretical elemental content (%) C 62 H43 N3O2: C, 86.39; H, 5.03; N, 4.87. Measured elemental content (%): C, 86.43; H, 5.08; N, 4.84.

[0472] Synthesis Example 14: Synthesis of Compound 292

[0473] Following the same preparation method as in Synthesis Example 9, a-2, b-2, and g-151 were replaced with equimolar amounts of a-292, d-83, and g-292, respectively, to obtain compound 292 (15.88 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 869.3629 (theoretical value: 869.3617). Theoretical elemental content (%) C 61 H 47 N3O3: C, 84.21; H, 5.45; N, 4.83. Measured elemental content (%): C, 84.17; H, 5.47; N, 4.80.

[0474] Synthesis Example 15: Synthesis of Compound 329

[0475] Following the same preparation method as in Synthesis Example 1, d-2 and g-2 were replaced with equimolar amounts of d-83 and g-329, respectively, to obtain compound 329 (16.18 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 937.3651 (theoretical value: 937.3668). Theoretical elemental content (%) C 68 H 47 N3O2: C, 87.06; H, 5.05; N, 4.48. Measured elemental content (%): C, 87.10; H, 5.01; N, 4.51.

[0476] Synthesis Example 16: Synthesis of Compound 368

[0477] Following the same preparation method as in Synthesis Example 1, a-2, b-2, c-2, and g-2 were replaced with equimolar amounts of a-368, b-28, a-2, and g-329, respectively, to obtain compound 368 (15.26 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 871.3971 (theoretical value: 871.3983). Theoretical elemental content (%) C 62 H 33 D 10N3O2: C, 85.39; H, 6.12; N, 4.82. Measured elemental content (%): C, 85.42; H, 6.07; N, 4.78.

[0478] Synthesis Example 17: Synthesis of Compound 384

[0479] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-384, c-384, d-384, and g-384, respectively, to obtain compound 384 (15.25 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 952.3786 (theoretical value: 952.3777). Theoretical elemental content (%) C 68 H 48 N4O2: C, 85.69; H, 5.08; N, 5.88. Measured elemental content (%): C, 85.71; H, 5.12; N, 5.90.

[0480] Synthesis Example 18: Synthesis of Compound 389

[0481] Following the same preparation method as in Synthesis Example 1, a-2, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of a-389, b-28, c-389, d-389, and g-329, respectively, to obtain compound 389 (16.27 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 970.4341 (theoretical value: 970.4357). Theoretical elemental content (%) C 70 H 54 DN3O2: C, 86.57; H, 5.81; N, 4.33. Measured elemental content (%): C, 86.60; H, 5.85; N, 4.29.

[0482] Synthesis Example 19: Synthesis of Compound 393

[0483] Following the same preparation method as in Synthesis Example 1, a-2, b-2, c-2, and g-2 were replaced with equimolar amounts of a-83, b-28, a-2, and g-393, respectively, to obtain compound 393 (16.88 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 977.4930 (theoretical value: 977.4920). Theoretical elemental content (%) C 70 H 63N3O2: C, 85.94; H, 6.49; N, 4.30. Measured elemental content (%): C, 85.90; H, 6.52; N, 4.28.

[0484] Synthesis Example 20: Synthesis of Compound 445

[0485] Following the same preparation method as in Synthesis Example 1, c-2, d-2, and g-2 were replaced with equimolar amounts of a-2, d-445, and g-445, respectively, to obtain compound 445 (15.64 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 961.3649 (theoretical value: 961.3668). Theoretical elemental content (%) C 70 H 47 N3O2: C, 87.38; H, 4.92; N, 4.37. Measured elemental content (%): C, 87.43; H, 4.88; N, 4.40.

[0486] Synthesis Example 21: Synthesis of Compound 505

[0487] Following the same preparation method as in Synthesis Example 1, a-2, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of c-2, d-2, a-2, b-2, and g-505, respectively, to obtain compound 505 (16.63 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 977.3606 (theoretical value: 977.3617). Theoretical elemental content (%) C 70 H 47 N3O3: C, 85.95; H, 4.84; N, 4.30. Measured elemental content (%): C, 85.91; H, 4.87; N, 4.28.

[0488] Synthesis Example 22: Synthesis of Compound 532

[0489] Following the same preparation method as in Synthesis Example 1, a-2, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of a-532, b-156, a-532, b-2, and g-329, respectively, to obtain compound 532 (15.14 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 840.3948 (theoretical value: 840.3933). Theoretical elemental content (%) C 58 H 24 D 15N3O3: C, 82.83; H, 6.47; N, 5.00. Measured elemental content (%): C, 82.80; H, 6.51; N, 5.03.

[0490] Synthesis Example 23: Synthesis of Compound 534

[0491] Following the same preparation method as in Synthesis Example 1, a-2, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of a-534, d-83, a-2, b-28, and g-505, respectively, to obtain compound 534 (17.05 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 973.5172 (theoretical value: 973.5182). Theoretical elemental content (%) C 68 H 67 N3O3: C, 83.83; H, 6.93; N, 4.31. Measured elemental content (%): C, 83.85; H, 6.89; N, 4.29.

[0492] Synthesis Example 24: Synthesis of Compound 548

[0493] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-548, c-548, b-28, and g-548, respectively, to obtain compound 548 (16.45 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 981.4820 (theoretical value: 981.4807). Theoretical elemental content (%) C 69 H 55 D4N3O3: C, 84.37; H, 6.46; N, 4.28. Measured elemental content (%): C, 84.35; H, 6.50; N, 4.30.

[0494] Synthesis Example 25: Synthesis of Compound 555

[0495] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-156, a-2, d-555, and g-505, respectively, to obtain compound 555 (16.50 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 999.4408 (theoretical value: 999.4400). Theoretical elemental content (%) C 71 H 57N3O3: C, 85.26; H, 5.74; N, 4.20. Measured elemental content (%): C, 85.30; H, 5.71; N, 4.17.

[0496] Synthesis Example 26: Synthesis of Compound 561

[0497] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-561, a-2, d-561, and g-561, respectively, to obtain compound 561 (16.74 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 1029.3911 (theoretical value: 1029.3930). Theoretical elemental content (%) C 74 H 51 N3O3: C, 86.27; H, 4.99; N, 4.08. Measured elemental content (%): C, 86.23; H, 4.94; N, 4.11.

[0498] Synthesis Example 27: Synthesis of Compound 601

[0499] Following the same preparation method as in Synthesis Example 9, b-2 and g-151 were replaced with equimolar amounts of d-83 and g-601, respectively, to obtain compound 601 (15.23 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 845.3243 (theoretical value: 845.3254). Theoretical elemental content (%) C 58 H 43 N3O4: C, 82.35; H, 5.12; N, 4.97. Measured elemental content (%): C, 82.39; H, 5.08; N, 4.95.

[0500] Synthesis Example 28: Synthesis of Compound 711

[0501] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-83, c-711, d-711, and g-329, respectively, to obtain compound 711 (15.98 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 953.3455 (theoretical value: 953.3440). Theoretical elemental content (%) C 68 H 47N3OS: C, 85.59; H, 4.96; N, 4.40. Measured elemental content (%): C, 85.62; H, 4.91; N, 4.37.

[0502] Synthesis Example 29: Synthesis of Compound 744

[0503] Following the same preparation method as in Synthesis Example 1, b-2, c-2, and g-2 were replaced with equimolar amounts of b-744, a-2, and g-744, respectively, to obtain compound 744 (15.57 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 957.3762 (theoretical value: 957.3753). Theoretical elemental content (%) C 68 H 51 N3OS: C, 85.23; H, 5.36; N, 4.39. Measured elemental content (%): C, 85.19; H, 5.40; N, 4.41.

[0504] Synthesis Example 30: Synthesis of Compound 745

[0505] Following the same preparation method as in Synthesis Example 6, b-2, c-114, d-114, e-114, f-114, and g-114 were replaced with equimolar amounts of b-28, a-2, d-745, a-2, f-745, and g-745, respectively, to obtain compound 745 (15.22 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 965.3426 (theoretical value: 965.3440). Theoretical elemental content (%) C 69 H 47 N3OS: C, 85.77; H, 4.90; N, 4.35. Measured elemental content (%): C, 85.80; H, 4.88; N, 4.39.

[0506] Synthesis Example 31: Synthesis of Compound 754

[0507] Following the same preparation method as in Synthesis Example 6, b-2, c-114, d-114, e-114, f-114, and g-114 were replaced with equimolar amounts of b-28, a-2, d-754, a-2, f-754, and g-754, respectively, to obtain compound 754 (14.13 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 882.3881 (theoretical value: 882.3872). Theoretical elemental content (%) C62 H 42 D4N4O2: C, 84.33; H, 5.71; N, 6.34. Measured elemental content (%): C, 84.36; H, 5.69; N, 6.38.

[0508] Synthesis Example 32: Synthesis of Compound 782

[0509] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-782, a-532, b-28, and g-782, respectively, to obtain compound 782 (14.77 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 922.3372 (theoretical value: 922.3390). Theoretical elemental content (%) C 64 H 38 D5N3O2S: C, 83.27; H, 5.24; N, 4.55. Measured elemental content (%): C, 83.30; H, 5.20; N, 4.53.

[0510] Synthesis Example 33: Synthesis of Compound 811

[0511] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of d-2, a-2, d-811, and g-329, respectively, to obtain compound 811 (15.64 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 947.2652 (theoretical value: 947.2640). Theoretical elemental content (%) C 64 H 41 N3O2S2: C, 81.07; H, 4.36; N, 4.43. Measured elemental content (%): C, 81.11; H, 4.31; N, 4.46.

[0512] Synthesis Example 34: Synthesis of Compound 840

[0513] Following the same preparation method as in Synthesis Example 9, a-2, b-2, and g-151 were replaced with equimolar amounts of a-840, d-2, and g-840, respectively, to obtain compound 840 (16.81 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 1033.3324 (theoretical value: 1033.3338). Theoretical elemental content (%) C 72 H47 N3O3S: C, 83.62; H, 4.58; N, 4.06. Measured elemental content (%): C, 83.59; H, 4.60; N, 4.11.

[0514] Synthesis Example 35: Synthesis of Compound 884

[0515] Following the same preparation method as in Synthesis Example 6, a-2, b-2, c-114, d-114, e-114, f-114, and g-114 were replaced with equimolar amounts of a-884, f-745, a-2, d-884, a-2, b-28, and g-884, respectively, to obtain compound 884 (14.13 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 882.3967 (theoretical value: 882.3951). Theoretical elemental content (%) C 63 H 38 D7N3O2: C, 85.68; H, 5.93; N, 4.76. Measured elemental content (%): C, 85.72; H, 5.89; N, 4.81.

[0516] Synthesis Example 36: Synthesis of Compound 897

[0517] Following the same preparation method as in Synthesis Example 1, b-2, c-2, and g-2 were replaced with equimolar amounts of b-28, c-897, and g-897, respectively, to obtain compound 897 (16.08 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 959.3866 (theoretical value: 959.3876). Theoretical elemental content (%) C 71 H 49 N3O: C, 88.81; H, 5.14; N, 4.38. Measured elemental content (%): C, 88.79; H, 5.17; N, 4.40.

[0518] Synthesis Example 37: Synthesis of Compound 914

[0519] Following the same preparation method as in Synthesis Example 9, b-2 and g-151 were replaced with equimolar amounts of b-914 and g-914, respectively, to obtain compound 914 (16.54 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 1001.2585 (theoretical value: 1001.2568). Theoretical elemental content (%) C 67 H43 N3OS3: C, 80.29; H, 4.32; N, 4.19. Measured elemental content (%): C, 80.31; H, 4.27; N, 4.22.

[0520] Synthesis Example 38: Synthesis of Compound 921

[0521] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-28, c-921, d-921, and g-921, respectively, to obtain compound 921 (14.82 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 911.3636 (theoretical value: 911.3624). Theoretical elemental content (%) C 65 H 45 N5O: C, 85.59; H, 4.97; N, 7.68. Measured elemental content (%): C, 85.62; H, 4.93; N, 7.72.

[0522] Synthesis Example 39: Synthesis of Compound 968

[0523] Following the same preparation method as in Synthesis Example 6, b-2, c-114, d-114, e-114, f-114, and g-114 were replaced with equimolar amounts of b-968, a-2, d-968, a-2, b-28, and g-968, respectively, to obtain compound 968 (16.00 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 999.3631 (theoretical value: 999.3647). Theoretical elemental content (%) C 73 H 49 N3S: C, 87.66; H, 4.94; N, 4.20. Measured elemental content (%): C, 87.62; H, 4.97; N, 4.17.

[0524] Synthesis Example 40: Synthesis of Compound 995

[0525] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-995, a-2, d-995, and g-995, respectively, to obtain compound 995 (15.28 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 898.2558 (theoretical value: 898.2549). Theoretical elemental content (%) C58 H 38 N6OS2: C, 77.48; H, 4.26; N, 9.35. Measured elemental content (%): C, 77.46; H, 4.30; N, 9.31.

[0526] Synthesis Example 41: Synthesis of Compound 1039

[0527] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-1039, a-2, d-1039, and g-329, respectively, to obtain compound 1039 (15.84 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 879.4242 (theoretical value: 879.4222). Theoretical elemental content (%) C 61 H 57 N3OS: C, 83.24; H, 6.53; N, 4.77. Measured elemental content (%): C, 83.28; H, 6.49; N, 4.80.

[0528] Synthesis Example 42: Synthesis of Compound 1050

[0529] Following the same preparation method as in Synthesis Example 7, a-137, d-83, and g-137 were replaced with equimolar amounts of a-1050, b-1050, and g-1050, respectively, to obtain compound 1050 (15.65 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 947.3922 (theoretical value: 947.3909). Theoretical elemental content (%) C 67 H 53 N3OS: C, 84.87; H, 5.63; N, 4.43. Measured elemental content (%): C, 84.90; H, 5.58; N, 4.45.

[0530] Synthesis Example 43: Synthesis of Compound 1080

[0531] Following the same preparation method as in Synthesis Example 1, b-2, c-2, d-2, and g-2 were replaced with equimolar amounts of b-1080, a-2, d-1080, and g-329, respectively, to obtain compound 1080 (16.36 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 947.3013 (theoretical value: 947.3004). Theoretical elemental content (%) C65 H 45 N3OS2: C, 82.34; H, 4.78; N, 4.43. Measured elemental content (%): C, 82.29; H, 4.81; N, 4.46.

[0532] Device Examples

[0533] In this invention, the ITO glass substrate and the ITO / Ag / ITO glass substrate are ultrasonically cleaned twice with a 5% glass cleaning solution for 20 minutes each time, followed by ultrasonic cleaning twice with deionized water for 10 minutes each time. They are then ultrasonically cleaned sequentially with acetone and isoacetone for 20 minutes each, and dried at 120°C. All organic materials are sublimated and have a purity of over 99.99%.

[0534] A combined IVL testing system was constructed, consisting of testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectrophotometer, to test the driving voltage, luminous efficiency, and CIE color coordinates of organic electroluminescent devices. Lifetime testing was performed using a McScience M6000 OLED lifetime testing system. The testing environment was ambient air at room temperature.

[0535] Example 1: Fabrication of Organic Electroluminescent Device 1

[0536] A hole injection layer with a thickness of 11 nm was vacuum-deposited on the ITO anode using a HI-1:HI-2 ratio of 5:95 (wt%). Compound 2 of this invention was vacuum-deposited on the hole injection layer as a hole transport layer with a thickness of 125 nm. On the hole transport layer, the host material CBP and the dopant material Ir(ppy)2(acac) were vacuum-deposited in a CBP:Ir(ppy)2(acac) ratio of 92:8 (wt%) to form a light-emitting layer with a thickness of 22 nm. On the light-emitting layer, a BCP:Liq ratio of 1:1 (wt%) was vacuum-deposited as an electron transport layer with a thickness of 31 nm. On the electron transport layer, LiF was vacuum-deposited as an electron injection layer with a thickness of 1.1 nm. On the electron injection layer, Al was vacuum-deposited as a cathode with a thickness of 110 nm.

[0537] Examples 2-43: Fabrication of Organic Electroluminescent Devices 2-43

[0538] Replacing compound 2 in the hole transport layer of Example 1 with compounds 18, 28, 40, 83, 114, 137, 149, 151, 156, 210, 233, 248, 292, 329, 368, 384, 389, 393, 445, 505, 532, 534, 548, 555, 561, 601, 711, 744, 745, 754, 782, 811, 840, 884, 897, 914, 921, 968, 995, 1039, 1050, and 1080 respectively, while keeping all other steps the same, organic electroluminescent devices 2-43 are obtained.

[0539] Comparative Examples 1-2: Fabrication of Comparative Organic Electroluminescent Devices 1-2

[0540] By replacing compound 2 in the hole transport layer of Example 1 with R-1 and R-2 respectively, and keeping the other steps the same, comparative organic electroluminescent devices 1-2 were obtained.

[0541]

[0542]

[0543] The luminescence characteristics test results of the organic electroluminescent devices prepared in Examples 1 to 43 and Comparative Examples 1 to 2 of this invention are shown in Table 1.

[0544] Table 1. Test data on the luminescence characteristics of organic electroluminescent devices

[0545]

[0546] As can be seen from Table 1, the organic electroluminescent device containing the aromatic amine derivative of Formula 1 of the present invention in the hole transport layer has a lower driving voltage, higher luminous efficiency and longer lifespan compared with the comparative device.

[0547] Example 44: Fabrication of organic electroluminescent device 44

[0548] 2-TNATA was vacuum-deposited on the ITO anode as a hole injection layer with a thickness of 60 nm; HT-1 was vacuum-deposited on the hole injection layer as a first hole transport layer with a thickness of 85 nm; Compound 2 of the present invention was vacuum-deposited on the first hole transport layer as a second hole transport layer with a thickness of 40 nm; GH-1, the host material, and Ir(ppy)2(acac), the dopant material, were vacuum-deposited on the second hole transport layer in a ratio of GH-1:Ir(ppy)2(acac)=92:8 (wt%) to form a light-emitting layer with a thickness of 18 nm; BTB:Liq=1:1 (wt%) was vacuum-deposited on the light-emitting layer as an electron transport layer with a thickness of 27 nm; LiF was vacuum-deposited on the electron transport layer as an electron injection layer with a thickness of 1.0 nm; and Al was vacuum-deposited on the electron injection layer as a cathode with a thickness of 110 nm.

[0549] Examples 45-86: Fabrication of Organic Electroluminescent Devices 45-86

[0550] Replace compound 2 in the second hole transport layer of Example 44 with compounds 18, 28, 40, 83, 114, 137, 149, 151, 156, 210, 233, 248, 292, 329, 368, 384, 389, 393, 445, 505, 532, 534, 548, 555, 561, 601, 711, 744, 745, 754, 782, 811, 840, 884, 897, 914, 921, 968, 995, 1039, 1050, and 1080 respectively, and follow the same steps to obtain organic electroluminescent devices 45-86.

[0551] Comparative Examples 3-4: Fabrication of Comparative Organic Electroluminescent Devices 3-4

[0552] By replacing compound 2 in the second hole transport layer of Example 44 with R-3 and R-4 respectively, and keeping the other steps the same, comparative organic electroluminescent devices 3-4 were obtained.

[0553]

[0554]

[0555] The luminescence characteristics test results of the organic electroluminescent devices prepared in Examples 44-86 and Comparative Examples 3-4 of this invention are shown in Table 2.

[0556] Table 2. Test data on the luminescence characteristics of organic electroluminescent devices

[0557]

[0558] As can be seen from Table 2, the organic electroluminescent device containing the aromatic amine derivative of Formula 1 of the present invention in the second hole transport layer has a lower driving voltage, higher luminous efficiency and longer lifespan compared with the comparative device.

[0559] Example 87: Fabrication of Organic Electroluminescent Device 87

[0560] HAT-CN was vacuum-deposited as a hole injection layer with a thickness of 9 nm on the ITO / Ag / ITO anode; HT-1 was vacuum-deposited as a hole transport layer with a thickness of 120 nm on the hole injection layer; CBP, the host material, and RH-1, the dopant material, were vacuum-deposited on the hole transport layer in a ratio of CBP:RH-1 = 98:2 (wt%) to form a light-emitting layer with a thickness of 21 nm; BCP:Liq = 1:1 (wt%) was vacuum-deposited on the light-emitting layer as an electron transport layer with a thickness of 26 nm; LiF was vacuum-deposited on the electron transport layer as an electron injection layer with a thickness of 1.2 nm; Mg:Ag = 1:9 was vacuum-deposited on the electron injection layer as a cathode with a thickness of 11 nm; and then compound 2 of the present invention was vacuum-deposited on the cathode as a capping layer with a thickness of 70 nm.

[0561] Examples 88-102: Fabrication of Organic Electroluminescent Devices 88-102

[0562] By replacing compound 2 in the capping layer of Example 87 with compounds 28, 114, 151, 156, 233, 292, 329, 384, 445, 505, 754, 840, 897, 968, and 995 respectively, and following the same other steps, organic electroluminescent devices 88-102 were obtained.

[0563] Comparative Example 5: Fabrication of Comparative Organic Electroluminescent Device 5

[0564] By replacing compound 2 in the capping layer of Example 87 with R-5, and keeping the other steps the same, a comparative organic electroluminescent device 5 was obtained.

[0565]

[0566]

[0567] The luminescence characteristics test results of the organic electroluminescent devices prepared in Examples 87-102 and Comparative Example 5 of this invention are shown in Table 3.

[0568] Table 3. Test data on the luminescence characteristics of organic electroluminescent devices

[0569] As can be seen from Table 3, compared with the comparative device 5, the organic electroluminescent device containing the aromatic amine derivative of Formula 1 of the present invention in the capping layer has higher luminous efficiency and longer service life, and the device performance is superior.

[0570] It should be noted that the present invention has been specifically described with reference to individual embodiments, but those skilled in the art can make various forms or details of improvements to the present invention without departing from the principles of the present invention, and these improvements also fall within the protection scope of the present invention.

Claims

1. An aromatic amine derivative, characterized in that, It is represented by the following equation 1, Wherein, Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 are the same or different and are selected from one of the following: substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C2-C60 heteroaryl groups, fused cycloalkanes of substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic groups, and fused cycloalkanes of substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroaromatic groups. At least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is selected from the groups shown in Formula 1-c below. The x that are the same or different are selected from CH or N; The Y is selected from O or S; The R d The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R d They bond with each other to form substituted or unsubstituted rings; The s1 is selected from 0, 1, 2, 3, 4 or 5; The L is selected from one of the groups shown in formula 1-a or 1-b. The " "Indicates L" 10 L 20 L 30 Connection sites; X is selected from O, S, CR1R2 or NR3; The same or different R1 and R2 are selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R1 and R2 are bonded to each other to form a substituted or unsubstituted ring; The R3 is selected from one of the following: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl. The z that are the same or different are selected from CH or N; The R a R b The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R a Two adjacent R b They bond with each other to form substituted or unsubstituted rings; The n1 is selected from 0, 1, 2, 3 or 4; the n2 is selected from 0, 1 or 2; The same or different v is selected from CH or N; The R c The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R c They bond with each other to form substituted or unsubstituted rings; The m1 is selected from 0, 1, 2, 3, 4 or 5; The L 10 L 20 L 30 The same or different is selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic ring fused cycloyl group, substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroarylene ring fused cycloyl group; The L1, L2, L3, L4, L5, and L6 are the same or different from one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, substituted or unsubstituted C3-C25 alicyclic and C6-C30 aromatic rings in a fused cycloalcoholic group, or substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroarylene rings in a fused cycloalcoholic group.

2. The aromatic amine derivative according to claim 1, characterized in that, Formula 1-c is selected from one of the following groups. The Y is selected from O or S; The s1 is selected from 0, 1, 2, 3, 4 or 5; the s2 is selected from 0, 1, 2, 3 or 4; the s3 is selected from 0, 1, 2 or 3; the s4 is selected from 0, 1 or 2; the s5 is selected from 0 or 1; the s6 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the s7 is selected from 0, 1, 2, 3, 4, 5 or 6; the s8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; and the s9 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

3. The aromatic amine derivative according to claim 1, characterized in that, Formula 1-a is selected from one of the following groups. The n1 is selected from 0, 1, 2, 3 or 4; the n2 is selected from 0, 1 or 2; the n3 is selected from 0, 1, 2, 3, 4, 5 or 6; the n4 is selected from 0, 1, 2 or 3; the n5 is selected from 0, 1, 2, 3, 4 or 5; the n6 is selected from 0 or 1; and the n7 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

4. The aromatic amine derivative according to claim 1, characterized in that, Formula 1-b is selected from one of the following groups. The m1 is selected from 0, 1, 2, 3, 4 or 5; the m2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m3 is selected from 0, 1, 2, 3 or 4; the m4 is selected from 0, 1, 2 or 3; the m5 is selected from 0, 1, 2, 3, 4, 5 or 6; and the m6 is selected from 0, 1 or 2.

5. The aromatic amine derivative according to claim 1, characterized in that, At least one of Ar1, Ar2, Ar3, Ar4, Ar5, and Ar6 is selected from the groups shown in 1-c, and the remaining groups are independently selected from one or a combination of the groups shown below. The R i The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R i They bond with each other to form substituted or unsubstituted rings; The R t The same or different is selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; The R4 is selected from one of the following: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl. The R5 and R6 are the same or different and are selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R5 and R6 are bonded to each other to form a substituted or unsubstituted ring; r1 is selected from 0, 1, 2, 3, 4, or 5; r2 is selected from 0, 1, 2, 3, or 4; r3 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; r4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; r5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; r6 is selected from 0, 1, 2, or 3; r7 is selected from 0, 1, or 2; r8 is selected from 0, 1, 2, 3, 4, 5, or 6; r9 is selected from 0 or 1. t1 is selected from 0, 1, or 2; t2 is selected from 0, 1, 2, 3, or 4; t3 is selected from 0, 1, 2, 3, 4, 5, or 6; t4 is selected from 0, 1, 2, 3, 4, or 5; t5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; t6 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; t7 is selected from 0, 1, 2, or 3.

6. The aromatic amine derivative according to claim 1, characterized in that, The L 10 L 20 L 30 The same or different groups are selected from single bonds, or one or a combination of the groups shown below. The R s The same or different from one selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R s They bond with each other to form substituted or unsubstituted rings; The R k The same or different is selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl; The value of e1 is selected from 0, 1, 2, 3, or 4; the value of e2 is selected from 0, 1, 2, 3, 4, 5, or 6; the value of e3 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; the value of e4 is selected from 0, 1, 2, or 3; the value of e5 is selected from 0, 1, or 2; the value of e6 is selected from 0 or 1; the value of e7 is selected from 0, 1, 2, 3, 4, or 5; the value of e8 is selected from 0, 1, 2, 3, 4, 5, 6, or 7. The j1 is selected from 0, 1 or 2; the j2 is selected from 0, 1, 2, 3 or 4; the j3 is selected from 0, 1, 2, 3, 4, 5 or 6; the j4 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

7. The aromatic amine derivative according to claim 1, characterized in that, The L1, L2, L3, L4, L5, and L6 groups, whether identical or different, are selected from single bonds, or from one or a combination of the following groups. The s that are the same or different are selected from CR e Or N; The R e Selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent R e They bond with each other to form substituted or unsubstituted rings; Z is selected from O, S, CR7R8 or NR9; The R7 and R8 are the same or different and are selected from one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R7 and R8 are bonded to each other to form a substituted or unsubstituted ring; The R9 is selected from one of the following: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl.

8. The aromatic amine derivative according to claim 1, characterized in that, The aromatic amine derivative is selected from any one of the structures shown below. 。 9. An organic electroluminescent device, characterized in that, The organic electroluminescent device contains the aromatic amine derivative as described in any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic layer, wherein the organic layer is located between the cathode and the anode or outside one or more electrodes of the anode and the cathode, and the organic layer contains an aromatic amine derivative as described in any one of claims 1 to 8.

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