Starburst triarylamine derivatives and organic electroluminescent devices thereof

Abstract

This invention provides a star-shaped triarylamine derivative and its organic electroluminescent device, specifically relating to the field of organic electroluminescence technology. To address the issue of suboptimal performance in current organic electroluminescent devices, this invention provides a star-shaped triarylamine derivative. Using this derivative as a hole transport layer material in organic electroluminescent devices can effectively improve the device's luminous efficiency and lifespan. This is because the star-shaped triarylamine derivative possesses strong electron-donating ability, significantly increasing hole mobility and carrier recombination probability, as well as advantages such as a high glass transition temperature, resistance to crystallization, and good film-forming properties. Therefore, its application in organic electroluminescent devices can effectively improve the device's luminous efficiency and lifespan.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, specifically to a star-shaped triarylamine derivative and its organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are self-emissive devices with many excellent characteristics such as low voltage, fast response, high efficiency, and long lifespan. Therefore, they are widely used in the fields of lighting and display and have broad development prospects.

[0003] In an OLED, holes generated at the anode and electrons generated at the cathode are injected into the hole transport layer and electron transport layer, respectively, and transported to the light-emitting layer. When they meet, they generate excitons, which activate the light-emitting material in the light-emitting layer. Electrons in the light-emitting material molecules transition from the ground state to the excited state. Since the electrons in the excited state are extremely unstable, they return to the stable ground state. During the transition, energy is released in the form of light, thus enabling the device to emit light.

[0004] Organic electroluminescent devices are a type of sandwich structure, typically consisting of an anode, a cathode, and an organic layer. The organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a capping layer. The interaction between these functions can effectively improve the performance of the device.

[0005] The luminous efficiency and lifespan of organic electroluminescent devices are affected by the injection and transport of charge carriers within the device and the recombination probability of charge carriers in the light-emitting layer. Inside the device, there is a low energy level matching between the hole transport layer material and the adjacent functional layer. Holes need to overcome a high energy barrier during transport, which increases Joule heating during device operation, reduces hole transport efficiency, and consequently reduces the luminous efficiency and lifespan of the device.

[0006] To obtain high-performance organic electroluminescent devices, it is crucial to develop organic functional layer materials (e.g., hole transport layers, light-emitting layers) with good performance and high energy level matching. Summary of the Invention

[0007] To address the problems affecting the performance of devices in the prior art, this invention provides a star-shaped triarylamine derivative and its organic electroluminescent device. When applied to organic electroluminescent devices, it can effectively improve the luminous efficiency and lifespan of the device.

[0008] This invention provides a star-shaped triarylamine derivative having the structure shown in Formula I.

[0009]

[0010] In Equation I, the R a The alkyl group is selected from substituted or unsubstituted C1-C12 alkyl groups; m is selected from 1 or 2;

[0011] Ar1 to Ar6 may be the same as or different from each other, and at least one of them is selected from... The indicated groups, the rest of which are the same as or different from each other, are selected from those of R. b The R is a substituted or unsubstituted aryl group of C6 to C30. b It is selected from any one of hydrogen, halogen atom, cyano, nitro, C1-C6 alkyl, and C6-C30 aryl;

[0012] X is selected from any one of CR0, R0, O, S, and NR;

[0013] The R0 and R are the same or different from each other, and are selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R0 and R can be directly bonded to any one of L1-L6, or R0 can be connected to each other to form substituted or unsubstituted rings.

[0014] The R1s may be the same as or different from each other, and are selected from any one of hydrogen, halogen atom, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0015] a is selected from 0, 1, 2 or 3; b is selected from 0, 1, 2, 3 or 4; when there are two or more R1s, the two or more R1s are the same or different from each other, or two adjacent R1s can be connected to each other to form substituted or unsubstituted rings;

[0016] L1 to L6 may be the same as or different from each other, and are selected from single bonds, bonds affected by R... c The following groups, substituted or unsubstituted, are: any one of C6-C30 arylene groups, C2-C30 heteroarylene groups, and combinations thereof, wherein the R c It is selected from any one of hydrogen, halogen atom, cyano, nitro, C1-C6 alkyl, and C6-C30 aryl.

[0017] The present invention also provides an organic electroluminescent device comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside either the anode or the cathode, and the organic layer comprises a hole transport region, a light-emitting layer, and an electron transport region, wherein the hole transport region and the light-emitting layer comprise any one or more of the aforementioned star-shaped triarylamine derivatives.

[0018] Beneficial effects: The star-shaped triarylamine derivative of Formula I provided by this invention has a strong electron-donating ability, which improves the hole transport capability. It has a suitable HOMO value, which reduces the energy barrier that needs to be overcome during hole transport. It also has good film-forming properties and is not prone to crystallization. When used as a hole transport layer material in organic electroluminescent devices, it can significantly improve the luminous efficiency and lifespan of the device. In addition, when this star-shaped triarylamine derivative is used as a hole transport layer material and the heterocyclic derivative of Formula II is used as an electron transport region material in organic electroluminescent devices, it can effectively improve the transport rate of holes and electrons, increase the transport balance between the two, and enable them to recombine effectively in the light-emitting layer, which greatly improves the performance of the device. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0020] In the compounds of this invention, any atom not specified as a particular isotope is included as any stable isotope of that atom, and comprises atoms at both their natural and non-natural isotopic abundances. Taking hydrogen as an example, each hydrogen atom in all naturally occurring compounds contains about 0.0156 atomic percent deuterium.

[0021] In this invention, the use of "H" and "hydrogen" refers to the presence of no more than the natural abundance of deuterium or tritium atoms in the chemical structure, for example, no more than 0.0156 atomic% of deuterium. "D" and "deuterium" refer to a deuterium abundance greater than the natural abundance, for example, any value exceeding 0.1 atomic%, 1 atomic%, or 10 atomic%, such as approximately 95 atomic% of deuterium. "T" and "tritium" refer to a tritium abundance greater than the natural abundance, for example, any value exceeding 0.1 atomic%, 1 atomic%, or 10 atomic%, such as approximately 95% of tritium. In this invention, the omission of undrawn hydrogen atoms signifies "H" or "hydrogen".

[0022] In this specification, "*" indicates a portion connected to another substituent.

[0023] In this specification, 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 And so on.

[0024] Examples of halogen atoms described in this invention may include fluorine, chlorine, bromine, or iodine.

[0025] The alkyl group described in this invention refers to a monovalent group obtained by removing one hydrogen atom from an alkane molecule. It can be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and particularly preferably having 1 to 6 carbon atoms. The alkyl group can be substituted or unsubstituted. Specific examples may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, etc., but are not limited thereto.

[0026] The alkenyl group described in this invention refers to a monovalent group obtained by removing one hydrogen atom from an olefin molecule. It can be a straight-chain alkenyl or a branched alkenyl, preferably having 2 to 15 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms. The alkenyl group can be substituted or unsubstituted. Specific examples may include vinyl, 1-propenyl, isopropenyl, butenyl, pentenyl, 3-methyl-1-butenyl, allyl, 1-phenylvinyl-1-yl, styryl, etc., but are not limited thereto.

[0027] The alkynyl group described in this invention refers to a monovalent group obtained by removing one hydrogen atom from an alkyne molecule. The alkynyl group includes mono-alkynyl, di-alkynyl, and poly-alkynyl groups. There is no particular limitation on the number of carbon atoms in the alkynyl group, but it is preferably C2–C15, more preferably C2–C12, even more preferably C2–C8, and most preferably C2–C6. The alkynyl group can be substituted or unsubstituted. Examples of the alkynyl group include, but are not limited to, the groups described below, such as ethynyl and butyrynyl.

[0028] The cycloalkyl group described in this invention refers to a hydrocarbon group formed by removing one hydrogen atom from a cycloalkane molecule, preferably with 3 to 12 carbon atoms, and particularly preferably with 3 to 6 carbon atoms. The cycloalkyl group can be substituted or unsubstituted. Examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, canyl, norbornyl, etc., but are not limited thereto.

[0029] The heterocyclic alkyl group described in this invention refers to a general term for groups obtained by replacing one or more carbon atoms in a cycloalkyl group with heteroatoms, including but not limited to O, S, N, Si, or P atoms. The heterocyclic alkyl group may be substituted or unsubstituted. Specific examples may include tetrahydropyrrolyl, piperidinyl, furanyl, thiophenyl, etc., but are not limited to these.

[0030] The aryl group described in this invention refers to a monovalent group obtained by removing a hydrogen atom from the aromatic carbon atom of an aromatic compound molecule. It can be a monocyclic aryl, polycyclic aryl, or fused-ring aryl, preferably having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 12 carbon atoms. The aryl group can be substituted or unsubstituted. The monocyclic aryl refers to an aryl group with only one aromatic ring in the molecule, such as phenyl, but not limited to this; the polycyclic aryl refers to an aryl group containing two or more independent aromatic rings in the molecule, such as biphenyl, terphenyl, tetraphenyl, etc., but not limited to this; the fused-ring aryl refers to an aryl group containing two or more aromatic rings fused together by sharing two adjacent carbon atoms, such as naphthyl, anthracene, phenanthryl, pyrene, perylene, etc. It includes, but is not limited to, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, benzo[a]fluorenyl, triphenylene, fluoranyl, 9,9'-spirodifluorenyl, etc.

[0031] The heteroaryl group described in this invention refers to a group obtained by replacing one or more aromatic carbon atoms in an aryl group with heteroatoms. The heteroatoms include, but are not limited to, O, S, N, Si, or P atoms, and preferably have 2 to 30 carbon atoms, more preferably 2 to 18 carbon atoms, and particularly preferably 2 to 12 carbon atoms. The linking site of the heteroaryl group can be located on a cyclic carbon atom or on a cyclic heteroatom. The heteroaryl group can be a monocyclic heteroaryl, polycyclic heteroaryl, or fused-ring heteroaryl. The heteroaryl group can be substituted or unsubstituted. The monocyclic heteroaryl groups include pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furanyl, thiopheneyl, pyrroleyl, oxazolyl, thiazolyl, imidazolyl, etc., but are not limited thereto; the polycyclic heteroaryl groups include bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, etc., but are not limited thereto; the fused-ring heteroaryl groups include quinolinyl, isoquinolinyl, benzo[a]quinolinyl, benzo[a]isoquinolinyl, quinazolinyl, quinoxalinyl, benzo[a]quinoxalinyl, benzo[a]quinoxalinyl, benzo[a]quinoxalinyl, etc. The following are examples of compounds, but not limited to: phenanthroline, naphthidyl, indolyl, benzothiophene, benzofuranyl, benzooxazolyl, benzoimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophene, benzodibenzothiophene, dibenzooxazolyl, dibenzoimidazolyl, dibenzothiazolyl, carbazole, 9-carbazole, benzocarbazole, acridineyl, phenoxazinyl, phenthiazinyl, phenoxthiayl, spirofluorenexanthracene, spirofluorenethixanthracene, etc.

[0032] The aliphatic ring described in this invention refers to a cyclic hydrocarbon with aliphatic properties, containing a closed carbon ring in the molecule, preferably with 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms, and even more preferably 3 to 7 carbon atoms. It can form monocyclic or polycyclic hydrocarbons, and can be completely unsaturated or partially unsaturated. The aliphatic ring can be substituted or unsubstituted. Specific examples may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, etc., but are not limited to these. Multiple monocyclic hydrocarbons can also be linked in various ways: two rings in the molecule can share a carbon atom to form a spiro ring; two carbon atoms on the ring can be connected by a carbon bridge to form a bridged ring; several rings can also be interconnected to form a cage-like structure.

[0033] The arylene group referred to in this invention refers to the general term for the divalent group remaining after removing two hydrogen atoms from the aromatic carbon atom of an aromatic hydrocarbon molecule. It can be a monocyclic arylene, a polycyclic arylene, or a fused-ring arylene, preferably having 6 to 30 carbon atoms, more preferably 6 to 22 carbon atoms, even more preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. Regarding the aforementioned arylene groups, monocyclic arylene groups can be phenylene, etc., but are not limited to these. The arylene group can be substituted or unsubstituted. Polycyclic arylene groups can be biphenylene, terphenylene, tetraphenylene, etc., but are not limited to these. Fused-ring arylene groups can be naphthylene, anthraceneene, phenanthrene, pyrene, fluorene, spirofluorene, triphenylene, perylene, fluorenyl, etc. It includes, but is not limited to, basic, and advanced technologies.

[0034] The heteroaryl group described in this invention refers to the general term for a divalent group formed by removing two hydrogen atoms from the nucleus carbon of an aromatic heterocycle composed of carbon and heteroatoms. The heteroatoms can be one or more of N, O, S, Si, and P, and can be monocyclic heteroaryl, polycyclic heteroaryl, or fused-ring heteroaryl. Preferably, it has 2 to 30 carbon atoms, more preferably 2 to 22 carbon atoms, even more preferably 2 to 20 carbon atoms, and most preferably 3 to 12 carbon atoms. The heteroaryl group can be substituted or unsubstituted. Examples may include, but are not limited to, pyridinyl, pyrazinyl, pyridazinyl, triazinyl, thiopheneyl, pyrroloyl, furanyl, pyranyl, oxazolyl, thiazolyl, imidazolyl, benzoxazolyl, benzothiazolyl, benzoimidazolyl, carbazolyl, benzocarbazolyl, acridineyl, imoxazanyl, thionazanyl, phenazinyl, phenthiazolyl, phenoxazinyl, indolyl, quinolinyl, isoquinolinyl, benzothiopheneyl, benzofuranyl, dibenzofuranyl, dibenzothiopheneyl, quinoxolinyl, quinoxolinyl, naphthinyl, purineyl, and phenanthrolineyl.

[0035] The fused ring of a divalent aromatic ring and an aliphatic ring described in this invention refers to the collective term for the divalent groups remaining after removing two hydrogen atoms from the fused ring of an aromatic ring and an aliphatic ring. The aromatic ring preferably has 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. The aliphatic ring preferably has 3 to 30 carbon atoms, more preferably C3 to C18 carbon atoms, more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. The fused ring of the divalent aromatic ring and the aliphatic ring can be substituted or unsubstituted. Examples include, but are not limited to, divalent groups such as benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptenyl, naphthocyclopropane, naphthocyclobutane, naphthocyclopentane, naphthocyclohexane, naphthocyclopentenyl, naphthocyclohexenyl, etc.

[0036] In this invention, "unsubstituted" in "substituted or unsubstituted" means that the hydrogen atom on the group is not substituted by any substituent; "substituted" means that at least one hydrogen atom on the group is substituted by a substituent, and the position of substitution is not limited. When multiple hydrogen atoms are substituted by multiple substituents, the multiple substituents may be the same or different.

[0037] The substituents described in the "substituted or unsubstituted" category of this invention can be independently selected from cyano, nitro, amino, halogen atom, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl. Preferably, cyano, halogen atom, amino, C1-C12 alkyl, C6-C30 aryl, and C2-C30 heteroaryl are used. Specific examples may include fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, biphenyl, terphenyl, tolyl, biphenyl, naphthyl, anthracene, phenanthrene, pyrene, and triphenylene. The following are some of the following groups: yl, peryl, fluoranyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, spirofluorenyl, carbazole, 9-phenylcarbazole, 9,9'-spirodifluorenyl, pyrroleyl, furanyl, thiopheneyl, benzofuranyl, benzothiopheneyl, dibenzofuranyl, dibenzothiopheneyl, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, benzooxazolyl, benzothiazolyl, benzotriazolyl, benzoimidazolyl, quinolinyl, isoquinolinyl, quinoxolinyl, quinazolinyl, phenothiazinyl, phenothiazinyl, acridineyl, etc., but not limited to these.

[0038] Unless otherwise stated, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 30 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, which may contain saturated or unsaturated rings.

[0039] The "linked ring formation" described in this invention refers to two groups being linked together by chemical bonds and optionally undergoing aromatization. Examples are shown below:

[0040]

[0041] In this invention, the ring formed by the connection can be an aromatic ring system, an aliphatic ring system, or a ring system formed by the fusion of the two. The ring formed by the connection can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or a fused ring, such as benzene, naphthalene, cyclopentene, cyclopentane, cyclopentanophenene, cyclohexene, cyclohexane, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene, or pyrene, but is not limited thereto.

[0042] This invention provides a star-shaped triarylamine derivative having the structure shown in Formula I:

[0043]

[0044] In Equation I, the R a The alkyl group is selected from substituted or unsubstituted C1-C12 alkyl groups; m is selected from 1 or 2;

[0045] Ar1 to Ar6 may be the same as or different from each other, and at least one of them is selected from... The indicated groups, the rest of which are the same as or different from each other, are selected from those of R. b The R is a substituted or unsubstituted aryl group of C6 to C30. b It is selected from any one of hydrogen, halogen atom, cyano, nitro, C1-C6 alkyl, and C6-C30 aryl;

[0046] X is selected from any one of CR0, R0, O, S, and NR;

[0047] The R0 and R are the same or different from each other, and are selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R0 and R can be directly bonded to any one of L1-L6, or R0 can be connected to each other to form substituted or unsubstituted rings.

[0048] The R1s may be the same as or different from each other, and are selected from any one of hydrogen, halogen atom, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0049] a is selected from 0, 1, 2 or 3; b is selected from 0, 1, 2, 3 or 4; when there are two or more R1s, the two or more R1s are the same or different from each other, or two adjacent R1s can be connected to each other to form substituted or unsubstituted rings;

[0050] L1 to L6 may be the same as or different from each other, and are selected from single bonds, bonds affected by R... c The following groups, substituted or unsubstituted, are: any one of C6-C30 arylene groups, C2-C30 heteroarylene groups, and combinations thereof, wherein the R c It is selected from any one of hydrogen, halogen atom, cyano, nitro, C1-C6 alkyl, and C6-C30 aryl.

[0051] Preferably, in Formula I, the three aromatic amine groups are linked to the benzene ring in a meta-position relative to each other.

[0052] Preferably, the star-shaped triarylamine derivative is selected from any one of the structures represented by formula I-1 and formula I-2.

[0053]

[0054] Preferably, the R a They may be the same as or different from each other, and are selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl.

[0055] Preferably, at least one of Ar1 to Ar6 is selected from The indicated groups include: one of Ar1 to Ar6 selected from the group, specifically, Ar1, Ar2, Ar3, Ar4, Ar5, or Ar6 selected from the group; two of Ar1 to Ar6 selected from the group, specifically, Ar1 and Ar2, Ar1 and Ar3, Ar1 and Ar5, Ar3 and Ar4, Ar3 and Ar5, and Ar5 and Ar6 selected from the group; and three of Ar1 to Ar6 selected from the group, specifically, Ar1, Ar2 and Ar3, Ar1, Ar2 and Ar5, Ar1, Ar3 and Ar4, Ar1, Ar3 and Ar5, Ar1, Ar5 and Ar6, Ar3, Ar4 and Ar5, and Ar3, Ar5, and Ar6 selected from the group. Group; four of Ar1 to Ar6 are selected from this group, specifically, Ar1, Ar2, Ar3 and Ar4, Ar1, Ar2, Ar3 and Ar5, Ar1, Ar2, Ar5 and Ar6, Ar1, Ar3, Ar4 and Ar5, Ar1, Ar3, Ar5 and Ar6, Ar3, Ar4, Ar5 and Ar6 are selected from this group; five of Ar1 to Ar6 are selected from this group, specifically, Ar1, Ar2, Ar3, Ar4 and Ar5, Ar1, Ar2, Ar3, Ar5 and Ar6 are selected from this group; six of Ar1 to Ar6 are selected from this group, specifically, Ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are selected from this group.

[0056] Preferably, the Selected from any one of the following groups,

[0057]

[0058] The R0 and R are the same or different from each other, and are selected from hydrogen, or substituted or unsubstituted by one or more C1 to C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, and triphenylene.

[0059] a is selected from 0, 1, 2 or 3; b is selected from 0, 1, 2, 3 or 4; when there are two or more R1s, the two or more R1s are the same or different from each other, or two adjacent R1s can be connected to each other to form substituted or unsubstituted: benzene ring, naphthalene ring;

[0060] The L a Selected from any one of single-bonded, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C2-C30 heteroaryl groups;

[0061] The ring A is selected from substituted or unsubstituted C3-C15 saturated or unsaturated aliphatic rings;

[0062] Preferably, ring A is selected from any one of the following groups:

[0063]

[0064] The R5s may be the same as or different from each other, and are selected from any one of hydrogen, halogen atom, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; when there are two or more R5s, the two or more R5s may be the same as or different from each other, or two adjacent R5s may be connected to each other to form a substituted or unsubstituted ring;

[0065] The number e1 is selected from 0, 1, 2, 3 or 4; the number e2 is selected from 0, 1, 2, 3, 4, 5 or 6; the number e3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; the number e4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the number e5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; and the number e6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0066] Preferably, the Selected from any one of the following groups,

[0067]

[0068]

[0069] The R x They may be the same as or different from each other, and are selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, and triphenylene.

[0070] The q1 is selected from 0, 1, 2, or 3; the q2 is selected from 0, 1, 2, 3, or 4; the q6 is selected from 0, 1, 2, 3, 4, or 5; the q7 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; the q8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; the q9 is selected from 0, 1, 2, 3, 4, 5, or 6; the q 10 The value q is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8. 11 Choose from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0071] Preferably, at least one of Ar1 to Ar6 is selected from... The indicated groups, and the remaining groups that are the same as or different from each other, are selected from any of the groups shown below.

[0072]

[0073] The R y They may be the same as or different from each other, and are selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, and triphenylene.

[0074] p1 is selected from 0, 1, 2, 3, 4 or 5; p2 is selected from 0, 1, 2, 3 or 4; p3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; p4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; and p5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

[0075] Preferably, at least one of Ar1 to Ar6 is selected from... The indicated groups, and the remaining groups that are the same as or different from each other, are selected from any of the groups shown below.

[0076]

[0077] Preferably, L1 to L6 may be the same as or different from each other, and are selected from single bonds or groups as shown below, and any combination thereof.

[0078]

[0079] The R c R d R z They may be the same as or different from each other, selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or R c R d They can connect with each other to form substituted or unsubstituted rings;

[0080] The R2s may be the same as or different from each other, and are selected from any one of hydrogen, C1-C12 alkyl, C6-C30 aryl, and C2-C30 heteroaryl.

[0081] a1 is selected from 0, 1, 2, 3 or 4, a2 is selected from 0, 1, 2, 3, 4 or 5, a3 is selected from 0, 1, 2 or 3, a4 is selected from 0, 1 or 2, and a5 is selected from 0, 1, 2, 3, 4, 5 or 6.

[0082] More preferably, L1 to L6 may be the same as or different from each other, and are selected from single bonds or groups as shown below, and any combination thereof.

[0083]

[0084] Most preferably, the star-shaped triarylamine derivative is selected from any one of the following structures.

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] The above lists some specific structural forms of the star-shaped triarylamine derivatives represented by chemical formula I according to the present invention. However, the present invention is not limited to these listed chemical structures. Any structure based on the structure shown in chemical formula I, with substituents as defined above, should be included.

[0103] The present invention also provides an organic electroluminescent device comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside either the anode or the cathode, and the organic layer comprises a hole transport region, a light-emitting layer, and an electron transport region, wherein the hole transport region and the light-emitting layer comprise any one or more of the aforementioned star-shaped triarylamine derivatives.

[0104] Preferably, the organic layer is located between the anode and the cathode, and includes at least one of a hole transport region, a light-emitting layer, and an electron transport region.

[0105] Preferably, the hole transport region of the present invention comprises at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.

[0106] More preferably, the hole transport region of the present invention includes at least one of a hole injection layer and a hole transport layer. More preferably, the hole transport region of the present invention includes a hole transport layer, and the hole transport layer includes any one or more of the star-shaped triarylamine derivatives of the present invention.

[0107] More preferably, the hole transport layer of the present invention comprises a first hole transport layer and a second hole transport layer, wherein at least one of the first hole transport layer and the second hole transport layer comprises any one or more of the star-shaped triarylamine derivatives of the present invention.

[0108] Preferably, the light-emitting layer of the present invention comprises a host material and a guest material; preferably, the host material comprises a single host material or dual host materials, and the host material comprises any one or more of the star-shaped triarylamine derivatives of the present invention.

[0109] Preferably, the electron transport region of the present invention comprises at least one of an electron injection layer, an electron transport layer, and a hole blocking layer; more preferably, the electron transport region of the present invention comprises at least one of an electron transport layer and a hole blocking layer; even more preferably, the electron transport region of the present invention comprises a hole blocking layer.

[0110] Preferably, the electron transport region includes any one or more of the derivatives shown in Formula II.

[0111]

[0112] In Formula II, Ar7 and Ar8 may be the same as or different from each other, and are selected from... The shown groups;

[0113] X1 is selected from any one of O, S, and N (R4); R4 is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0114] Z is selected from C(R5) or N; R5 is selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C30 heterocycloalkyl, substituted or unsubstituted C2-C15 alkenyl, substituted or unsubstituted C2-C15 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or adjacent groups can be connected to each other to form a substituted or unsubstituted ring;

[0115] The R 00 It is selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0116] The X0 is selected from any one of O, S, N(Ar), C(Ar)2, and Si(Ar)2; the Ars are the same or different from each other and are selected from any one of substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C3-C30 heteroaryl groups.

[0117] The R3s may be the same as or different from each other, and are selected from any one of hydrogen, deuterium, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C15 alkenyl, substituted or unsubstituted C2-C15 alkynyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0118] The c is selected from 0, 1, 2, 3 or 4. When there are two or more R3s, the two or more R3s are the same or different from each other, or two adjacent R3s can be connected to each other to form substituted or unsubstituted rings.

[0119] The L x L y L0 may be the same as or different from each other, and are selected from any combination thereof, including single-bonded, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, divalent substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring fused ring.

[0120] Preferably, the Ar7 and Ar8 are the same or different from each other, and are selected from any of the following groups.

[0121]

[0122]

[0123] X1 is selected from any one of O, S, and N(R4);

[0124] The R4 is selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl.

[0125] The n1 is selected from 1, 2, 3 or 4, and the n2 is selected from 1, 2, 3, 4 or 5.

[0126] Preferably, the L x L y L0 may be the same as or different from each other, and are selected from single bonds or groups as shown below, and any combination thereof.

[0127]

[0128] The T values ​​are either the same or different from each other, and are selected from N or C(R). m ), the R m It is selected from one of hydrogen, deuterium, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.

[0129] Q is selected from O, S, N(R) n ), C(R n Any one of )2, wherein R n It is selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups connected to form a substituted or unsubstituted cyclization.

[0130] More preferably, the L x L y L0 may be the same as or different from each other, and are selected from single bonds or groups as shown below, and any combination thereof.

[0131]

[0132]

[0133] b1 is selected from 1, 2, 3 or 4, b2 is selected from 1, 2, 3, 4 or 5, b3 is selected from 1, 2 or 3, and b4 is selected from 1, 2, 3, 4, 5 or 6.

[0134] Preferably, the derivative of formula II is selected from any one of the following structures.

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144] The above lists some specific structural forms of the derivatives represented by Formula II of the present invention. However, the present invention is not limited to these listed chemical structures. Any structure based on the structure shown in Formula II, with substituents as defined above, should be included.

[0145] The organic layer described in this invention can be a single-layer structure, a double-layer structure, or a multi-layer structure. Furthermore, each organic layer can contain a variety of compounds. However, the structure of the organic electroluminescent device is not limited to this.

[0146] The organic electroluminescent device of the present invention is typically formed on a substrate. The substrate need not change during the formation of electrodes and organic layers; for example, substrates made of glass, plastic, polymer films, silicon, etc.

[0147] The anode material described in this invention preferably uses a material with a high energy function, which improves hole injection efficiency. The anode material that can be used in this invention is selected from the following: indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO) or any combination thereof, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) or any combination thereof. The anode can have a single-layer structure or a multilayer structure including two or more layers. For example, the anode can have a single-layer structure of Al or a three-layer structure of ITO / Ag / ITO, but is not limited thereto.

[0148] The hole injection layer material described in this invention is preferably a material with good hole acceptance capability. It can be selected from any one or more of the following structures: metalloporphyrins, oligothiophenes, aryl amine derivatives, perylene derivatives, hexanitrile hexaazabenzophenanthrene compounds, phthalocyanine compounds, polycyano conjugated organic materials, quinacridone compounds, anthraquinone compounds, and conductive polymers based on polyaniline and polythiophene, etc., but not limited thereto.

[0149] The hole transport layer material described in this invention is preferably a material with high hole mobility. It can be selected from any one or more of the following structures: carbazole derivatives, triarylamine derivatives, biphenyl diamine derivatives, fluorene derivatives, stilbene derivatives, hexanitrile hexaazabenzophenanthrene compounds, quinacridone compounds, anthraquinone compounds, polyaniline, polythiophene, polyvinylcarbazole, etc. Examples of the hole transport layer material include, but are not limited to, the following materials: N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), 4-[1-[4-[di(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC), N,N,N',N'-tetra(3-methylphenyl)-3,3'-dimethylbiphenyldiamine (HMTPD), etc. Preferably, the star-shaped triarylamine derivatives of the present invention are preferred.

[0150] The light-emitting layer material of this invention includes a host material and a dopant material. The host material of the light-emitting layer can be selected from 4,4'-bis(9-carbazole)biphenyl (CBP), 9,10-bis(2-naphthyl)anthracene (ADN), 4,4-bis(9-carbazole)biphenyl (CPB), 9,9'-(1,3-phenyl)bis-9H-carbazole (mCP), 4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA), 9,10-bis(1-naphthyl)anthracene (α-AND), N,N'-bis-(1-naphthyl)-N,N' -Diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamino (4PNPB), 1,3,5-tris(9-carbazolyl)benzene (TCP), etc. Besides the above materials and combinations thereof, the host material of the luminescent layer may also include other known materials suitable for the luminescent layer, but is not limited thereto. Preferably, the star-shaped triarylamine derivative described in this invention is preferred. The luminescent layer doping materials of this invention are divided into blue luminescent materials, green luminescent materials, and red luminescent materials. The luminescent layer doping materials can be selected from (6-(4-( Diphenylamino(phenyl)-N,N-diphenylpyrene-1-amine (DPAP-DPPA), 2,5,8,11-tetra-tert-butylperylene (TBPe), 4,4'-bis[4-(diphenylamino)styryl]biphenyl (BDAVBi), 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (DPAVBi), bis(2-hydroxyphenylpyridine)beryllium (Bepp2), bis(4,6-difluorophenylpyridine-C2,N)pyridinecarboxyiridium (FIrpic), tris(2-phenylpyridine)iridium (Ir(ppy)3), bis(2-phenylpyridine)iridium acetylacetonate (Ir(ppy)2(acac)), 9,10-bis[N-(p-tolyl)aniline]anthracene (TPA), 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), tris[1-phenylisoquinoline-C2,N]iridium(III) (Ir(piq)3), bis(1-phenylisoquinoline)(acetylacetonate)iridium (Ir(piq)2(acac)), etc., but not limited to these.

[0151] The doping ratio of the host material and the guest material in the light-emitting layer of the present invention is determined according to the materials used. The amount of dopant material is preferably 0.1–70% by mass, more preferably 0.1–30% by mass, further preferably 1–30% by mass, even more preferably 1–20% by mass, and particularly preferably 1–10% by mass.

[0152] The hole-blocking layer material of this invention is preferably a material that can effectively block hole transport, causing excitons to recombine in the luminescent layer rather than the electron transport layer. Besides the nitrogen-containing heterocyclic derivatives provided by this invention, it can also be selected from any one or more of the following structures: phenanthroline derivatives, rare earth derivatives, imidazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, diazanphenanthrene derivatives, azirbenzene derivatives, anthrone derivatives, etc., but is not limited thereto. The derivative shown in Formula II of this invention is preferred.

[0153] The electron transport layer material of the present invention is preferably a material with high electron mobility. It can be selected from any one or more of the following structures: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tris(N-phenyl-2-benzimidazole)benzene (TPBi), tris(8-hydroxyquinoline)aluminum(III) (Alq3), 8-hydroxyquinoline-lithium (Liq), di(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum(III) (BAlq), and 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 4,7-diphenyl-1,10-phenanthroline (Bphen), etc., but is not limited thereto. The derivative shown in Formula II of the present invention is preferred.

[0154] The electron injection layer material described in this invention is preferably a material with a small barrier difference to the adjacent organic layer material. Specific examples may include: alkali metal compounds (such as lithium oxide, lithium fluoride, cesium carbonate, cesium fluoride, cesium 8-hydroxyquinoline, 8-hydroxyquinoline aluminum), organometallic salts (metal acetate, metal benzoate, or metal stearate), molybdenum trioxide, aluminum, etc., but are not limited to these.

[0155] The cathode material of the present invention preferably uses a material with a low work function that can promote electron injection into the organic layer, thereby reducing the electron injection barrier. It can be selected from any one or more of the following materials: Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, compounds thereof, or mixtures thereof (e.g., mixtures of Ag and Mg), but is not limited thereto.

[0156] The present invention does not impose any special restrictions on the thickness of each organic layer of the organic electroluminescent device; thicknesses commonly used in the field can be adopted.

[0157] The organic electroluminescent device of the present invention can be manufactured by sequentially stacking the above-described structures. The manufacturing method can utilize known methods such as wet film deposition and dry film deposition. Specific examples of wet film deposition methods include various coating methods such as spin coating, dip coating, casting, and inkjet coating. Specific examples of dry film deposition methods include vacuum evaporation, sputtering, plasma deposition, and ion plating, but are not limited to these.

[0158] The organic light-emitting device described in this invention can be widely used in panel displays, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photosensitive materials or organic thin-film transistors, signs, signal lights and other fields.

[0159] The invention is explained in more detail through the following examples, but is not intended to limit the invention. Based on this description, those skilled in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the entire scope disclosed without inventive effort.

[0160] This invention provides a method for preparing the compound represented by Formula I, but the preparation method of this invention is not limited thereto. The specific synthetic route is shown below:

[0161] [Synthetic Route of Formula I]

[0162] Preparation of intermediate A:

[0163]

[0164] Preparation of intermediate B:

[0165]

[0166] Preparation of intermediate C:

[0167]

[0168] Preparation of compound I:

[0169] 1. When intermediate A, intermediate B, and intermediate C are different from each other:

[0170]

[0171] 2. When intermediate A and intermediate B are the same:

[0172]

[0173] 3. When intermediates A, B, and C are identical:

[0174]

[0175] Among them, Xa They may be the same or different from each other, and are selected from any one of Cl, Br, and I; Ar1 ​​to Ar6, L1 to L6, R a R b The restrictions on m and n are the same as those mentioned above.

[0176] The above-mentioned substituents can be bonded by methods known in the art, and the type and position or number of substituents can be changed according to techniques known in the art.

[0177] Formula II indicates that the preparation of the compound can be referred to CN112442023A.

[0178] Description of raw materials, reagents, and characterization equipment:

[0179] The present invention does not impose any particular restrictions on the source of raw materials and reagents used in the following embodiments, which can be commercially available products or prepared using preparation methods well known to those skilled in the art.

[0180] Mass spectrometry was performed using a Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer, with chloroform as the solvent.

[0181] Elemental analysis was performed using a Vario EL cube organic elemental analyzer from Elementar GmbH, Germany, with sample masses ranging from 5 to 10 mg.

[0182] Synthetic Example 1: Preparation of Compounds 1-18

[0183]

[0184] Preparation of intermediate A-1-18:

[0185] Under nitrogen protection, a-1-18 (18.42 g, 70 mmol), b-1-18 (6.52 g, 70 mmol), and sodium tert-butoxide (10.09 g, 105 mmol) were added to 260 mL of toluene. Pd(OAc)₂ (0.17 g, 0.74 mmol) and P(t-Bu)₃ (2.96 mL of 0.5 M toluene solution, 1.48 mmol) were added with stirring. The mixture of the above reactants was heated under reflux for 4 h. After the reaction was complete, the mixture was cooled to room temperature, and distilled water was added. The mixture was extracted with dichloromethane, allowed to stand, and separated. The organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystallization was precipitated by cooling and filtration. The resulting solid was recrystallized from toluene / methanol (8:1 v / v) to give intermediate A-1-18 (16.96 g, yield 88%) with an HPLC purity ≥ 99.77%. Mass spectrometry m / z: 275.0781 (theoretical value: 275.0769).

[0186] Preparation of compounds 1-18:

[0187] Under nitrogen protection, intermediates A-1-18 (16.52 g, 60 mmol), g-1-18 (7.14 g, 20 mmol), and sodium tert-butoxide (3.84 g, 40 mmol) were added to 150 mL of toluene. Pd₂(dba)₃ (0.22 g, 0.24 mmol) and P(t-Bu)₃ (0.96 mL of 0.5 M toluene solution, 0.48 mmol) were added with stirring. The mixture was heated under reflux for 7 h. After the reaction was complete, the mixture was cooled to room temperature, and extracted with dichloromethane and distilled water. The mixture was allowed to stand and separated. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystallization was precipitated by cooling and filtered. The resulting solid was recrystallized from toluene to give compound 1-18 (12.79 g, 68%) with an HPLC purity ≥ 99.92%. Mass spectrometry m / z: 939.2765 (theoretical value: 939.2776). Theoretical elemental content (%) C 63 H 45 N3S3: C, 80.48; H, 4.82; N, 4.47. Measured elemental content (%): C, 80.45; H, 4.84; N, 4.48.

[0188] Synthetic Example 2: Preparation of Compounds 1-54

[0189]

[0190] Preparation of intermediate A-1-54:

[0191] Under nitrogen protection, a-1-54 (14.83 g, 60 mmol), b-1-18 (5.59 g, 60 mmol), sodium tert-butoxide (10.28 g, 107 mmol), and 320 mL of toluene were added to a reaction flask. Pd(OAc)₂ (0.16 g, 0.72 mmol) and P(t-Bu)₃ (2.88 mL of 0.5 M toluene solution, 1.44 mmol) were added with stirring. The mixture of the above reactants was heated under reflux for 4 h. After the reaction was complete, the mixture was cooled to room temperature, extracted with dichloromethane, allowed to stand, and separated. The organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystallization was carried out at a lower temperature, filtered, and the resulting solid was recrystallized from toluene / methanol (8:1 v / v) to give intermediate A-1-54 (13.07 g, 84%) with an HPLC purity ≥ 99.56%. Mass spectrometry m / z: 259.0986 (theoretical value: 259.0997).

[0192] Preparation of intermediate B-1-54:

[0193] Under nitrogen protection, c-1-54 (13.99 g, 60 mmol), b-1-18 (5.59 g, 60 mmol), and sodium tert-butoxide (10.28 g, 107 mmol) were added to 320 mL of toluene. Pd(dppf)Cl2 (0.53 g, 0.72 mmol) was added with stirring, and the mixture was heated under reflux for 5 h. After the reaction was complete, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The layers were allowed to stand and separated, the organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystals were then precipitated by cooling and filtered again. The resulting solid was recrystallized from ethyl acetate to give intermediate B-1-54 (12.95 g, 88%) with an HPLC purity ≥ 99.62%. Mass spectrometry m / z: 245.1214 (theoretical value: 245.1204).

[0194] Preparation of intermediate I-1-54:

[0195] Under nitrogen protection, intermediates A-1-54 (12.97 g, 50 mmol), g-1-54 (12.00 g, 50 mmol), and sodium tert-butoxide (8.41 g, 87.5 mmol) were added to 260 mL of toluene. Pd(OAc)2 (0.13 g, 0.57 mmol) and P(t-Bu)3 (2.28 mL of 0.5 M toluene solution, 1.14 mmol) were added with stirring. The mixture was heated under reflux for 5.5 h. After the reaction was complete, the mixture was cooled to room temperature, and extracted with dichloromethane and distilled water. The mixture was allowed to stand and separated, and the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was purified by silica gel column chromatography with n-hexane / dichloromethane (9:1 v / v) to obtain intermediate I-1-54 (16.52 g, 79%) with an HPLC purity ≥ 99.81%. Mass spectrometry m / z: 417.0676 (theoretical value: 417.0687).

[0196] Preparation of compounds 1-54:

[0197] Under nitrogen protection, intermediates I-1-54 (10.04 g, 24 mmol), B-1-54 (11.78 g, 48 mmol), and sodium tert-butoxide (4.61 g, 48 mmol) were added to 160 mL of toluene. Pd2(dba)3 (0.27 g, 0.29 mmol) and X-Phos (0.28 g, 0.58 mmol) were added with stirring. The mixture of the above reactants was heated under reflux for 5 h. After the reaction was complete, the mixture was cooled to room temperature, and distilled water was added. The mixture was extracted with dichloromethane, allowed to stand, and separated. The organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystallization was carried out at a lower temperature, filtered, and the resulting solid was recrystallized from toluene to give compound 1-54 (14.45 g, 72%) with an HPLC purity ≥99.91%. Mass spectrometry m / z: 835.3577 (theoretical value: 835.3563). Theoretical element content (%) C 61 H 45 N3O: C, 87.63; H, 5.43; N, 5.03. Measured elemental content (%): C, 87.66; H, 5.41; N, 5.01.

[0198] Synthetic Example 3: Preparation of Compounds 1-96

[0199]

[0200] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, c-1-54, and g-1-54 were replaced with equimolar amounts of a-1-96, c-1-96, and g-1-96, respectively, to obtain compound 1-96 (13.82 g) with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 885.4665 (theoretical value: 885.4658). Theoretical elemental content (%) C 64 H 59 N3O: C, 86.74; H, 6.71; N, 4.74. Measured elemental content (%): C, 86.72; H, 6.74; N, 4.72.

[0201] Synthetic Example 4: Preparation of Compounds 1-108

[0202]

[0203] Preparation of intermediate A-1-108:

[0204] Under nitrogen protection, a-1-108 (6.28 g, 40 mmol), b-1-18 (3.73 g, 40 mmol), and sodium tert-butoxide (6.92 g, 72 mmol) were added to 200 mL of toluene. Pd(dppf)Cl2 (0.35 g, 0.48 mmol) was added with stirring, and the mixture was heated under reflux for 4 h. After the reaction was complete, the reaction solution was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The layers were allowed to stand and separated, the organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystals were then precipitated by cooling and filtered again. The resulting solid was recrystallized from ethyl acetate to give intermediate A-1-108 (6.02 g, 89%), with an HPLC purity ≥ 99.34%. Mass spectrometry m / z: 169.0879 (theoretical value: 169.0891).

[0205] Preparation of intermediate B-1-108:

[0206] Under nitrogen protection, c-1-108 (11.89 g, 40 mmol), b-1-18 (3.73 g, 40 mmol), and sodium tert-butoxide (6.92 g, 72 mmol) were added to 200 mL of toluene. Pd(OAc)₂ (0.11 g, 0.48 mmol) and P(t-Bu)₃ (1.92 mL of 0.5 M toluene solution, 0.96 mmol) were added with stirring. The mixture of the above reactants was heated under reflux for 4.5 h. After the reaction was complete, the reaction solution was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. After standing and separation, the organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystallization was precipitated by cooling and filtered. The obtained solid was recrystallized from toluene / methanol (volume ratio 10:1) to obtain intermediate B-1-108 (10.77 g, 87%) with an HPLC purity ≥ 99.41%. Mass spectrometry m / z: 309.1166 (theoretical value: 309.1154).

[0207] Preparation of intermediate C-1-108:

[0208] Under nitrogen protection, e-1-108 (13.91 g, 45 mmol), b-1-18 (4.19 g, 45 mmol), and sodium tert-butoxide (7.78 g, 81 mmol) were dissolved in 250 mL of toluene. Pd(dppf)Cl2 (0.40 g, 0.54 mmol) was added with stirring, and the mixture was heated under reflux for 5 h. After the reaction was complete, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The layers were allowed to stand and separated, the organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystals were then precipitated by cooling and filtered again. The resulting solid was recrystallized from ethyl acetate to give intermediate C-1-108 (12.29 g, 85%) with an HPLC purity ≥99.56%. Mass spectrometry m / z: 321.1524 (theoretical value: 321.1517).

[0209] Preparation of intermediate I-1-108:

[0210] Under nitrogen protection, intermediates A-1-108 (5.92 g, 35 mmol), g-1-108 (11.60 g, 35 mmol), and sodium tert-butoxide (5.96 g, 62 mmol) were added to 200 mL of toluene. Pd(OAc)₂ (0.09 g, 0.38 mmol) and P(t-Bu)₃ (1.52 mL of 0.5 M toluene solution, 0.76 mmol) were added with stirring. The mixture was heated under reflux for 4.5 h. After the reaction was complete, the mixture was cooled to room temperature, and extracted with dichloromethane and distilled water. The mixture was allowed to stand and separated, and the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was purified by silica gel column chromatography with petroleum ether / dichloromethane (v / v 10:1) to obtain intermediate I-1-108 (10.57 g, 81%) with an HPLC purity ≥ 99.60%. Mass spectrometry m / z: 371.0065 (theoretical value: 371.0076).

[0211] Preparation of intermediate II-1-108:

[0212] Under nitrogen protection, intermediates I-1-108 (9.32 g, 25 mmol), B-1-108 (7.73 g, 25 mmol), and sodium tert-butoxide (4.13 g, 43 mmol) were added to 150 mL of toluene. While stirring, Pd2(dba)3 (0.26 g, 0.28 mmol) and P(t-Bu)3 (1.12 mL of 0.5 M toluene solution, 0.56 mmol) were added. The mixture was heated under reflux for 5 h. After the reaction was complete, the mixture was cooled to room temperature, and extracted with dichloromethane and distilled water. The mixture was allowed to stand and separated. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was purified by silica gel column chromatography with petroleum ether / ethyl acetate (v / v 10:1) to obtain intermediate II-108 (12.32 g, 82%) with an HPLC purity ≥ 99.83%. Mass spectrometry m / z: 600.1955 (theoretical value: 600.1968).

[0213] Preparation of compound 1-108:

[0214] Under nitrogen protection, intermediates II-1-108 (12.02 g, 20 mmol), C-1-108 (6.43 g, 20 mmol), and sodium tert-butoxide (2.88 g, 30 mmol) were added to 140 mL of toluene. Pd2(dba)3 (0.23 g, 0.25 mmol) and X-Phos (0.24 g, 0.5 mmol) were added with stirring. The mixture of the above reactants was heated under reflux for 6 h. After the reaction was complete, the mixture was cooled to room temperature, and distilled water was added. The mixture was extracted with dichloromethane, allowed to stand, and the layers were separated. The organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. Crystals were precipitated by cooling and filtered again. The resulting solid was recrystallized from toluene to give compound 1-108 (12.76 g, 72%) with an HPLC purity ≥99.96%. Mass spectrometry m / z: 885.3727 (theoretical value: 885.3719). Theoretical element content (%) C 65 H 47 N3O: C, 88.11; H, 5.35; N, 4.74. Measured elemental content (%): C, 88.14; H, 5.33; N, 4.72.

[0215] Synthetic Example 5: Preparation of Compounds 1-142

[0216]

[0217] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, c-1-54, and g-1-54 were replaced with equimolar amounts of a-1-142, c-1-142, and g-1-96, respectively, to obtain compound 1-142 (13.04 g) with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 875.4231 (theoretical value: 875.4239). Theoretical elemental content (%) C 65 H 53 N3: C, 89.11; H, 6.10; N, 4.80. Measured elemental content (%): C, 89.09; H, 6.13; N, 4.78.

[0218] Synthetic Example 6: Preparation of Compounds 1-148

[0219]

[0220] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, g-1-54, and B-1-54 were replaced with equimolar amounts of a-1-148, g-1-96, and A-1-108, respectively, to obtain compound 1-148 (12.82 g) with an HPLC purity ≥ 99.92%. Mass spectrometry m / z: 847.3938 (theoretical value: 847.3926). Theoretical elemental content (%) C 63 H 49 N3: C, 89.22; H, 5.82; N, 4.95. Measured elemental content (%): C, 89.25; H, 5.80; N, 4.94.

[0221] Synthesis Example 7: Preparation of Compound 1-203

[0222]

[0223] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, g-1-54, and B-1-54 were replaced with equimolar amounts of a-1-203, g-1-203, and A-1-108, respectively, to obtain compound 1-203 (12.12 g) with an HPLC purity ≥ 99.93%. Mass spectrometry m / z: 827.4248 (theoretical value: 827.4239). Theoretical elemental content (%) C 61 H 53 N3: C, 88.47; H, 6.45; N, 5.07. Measured elemental content (%): C, 88.45; H, 6.46; N, 5.05.

[0224] Synthesis Example 8: Preparation of Compounds 1-232

[0225]

[0226] Following the same preparation method as compound 1-108 in Synthesis Example 4, equimolar amounts of c-1-108, e-1-108, and A-1-108 were replaced with equimolar amounts of c-1-232, e-1-232, and A-1-18, respectively, to obtain compound 1-232 (12.57 g) with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 951.3633 (theoretical value: 951.3647). Theoretical elemental content (%) C 69 H 49 N3S: C, 87.03; H, 5.19; N, 4.41. Measured elemental content (%): C, 87.07; H, 5.16; N, 4.40.

[0227] Synthetic Example 9: Preparation of Compounds 1-259

[0228]

[0229] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54 and B-1-54 were replaced with equimolar amounts of a-1-259 and A-1-108, respectively, to obtain compound 1-259 (15.00 g) with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 946.4983 (theoretical value: 946.4974). Theoretical elemental content (%) C 69 H 62 N4: C, 87.49; H, 6.60; N, 5.91. Measured elemental composition (%): C, 87.46; H, 6.62; N, 5.93. Synthesis Example 10: Preparation of Compound 1-261

[0230]

[0231] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, b-1-18, g-1-54, and B-1-54 were replaced with equimolar amounts of a-1-261, b-1-261, g-1-96, and A-1-108, respectively, to obtain compound 1-261 (14.46 g) with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 898.4019 (theoretical value: 898.4035). Theoretical elemental content (%) C 66 H 50 N4: C, 88.16; H, 5.61; N, 6.23. Measured elemental content (%): C, 88.17; H, 5.59; N, 6.22.

[0232] Synthetic Example 11: Preparation of Compound 1-267

[0233]

[0234] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54 and g-1-54 were replaced with equimolar amounts of a-1-267 and g-1-267, respectively, to obtain compound 1-267 (14.43 g) with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 924.4178 (theoretical value: 924.4192). Theoretical elemental content (%) C 68 H 52 N4: C, 88.28; H, 5.67; N, 6.06. Measured elemental content (%): C, 88.24; H, 5.69; N, 6.08.

[0235] Synthesis Example 12: Preparation of Compound 1-302

[0236]

[0237] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54 and B-1-54 were replaced with equimolar amounts of a-1-302 and A-1-108, respectively, to obtain compound 1-302 (13.03 g) with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 834.3734 (theoretical value: 834.3722). Theoretical elemental content (%) C 61 H 46 N4: C, 87.74; H, 5.55; N, 6.71. Measured elemental content (%): C, 87.75; H, 5.53; N, 6.72.

[0238] Synthetic Example 13: Preparation of Compound 1-309

[0239]

[0240] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, b-1-18, c-1-54, and g-1-54 were replaced with equimolar amounts of a-1-259, b-1-309, c-1-309, and g-1-309, respectively, to obtain compound 1-309 (15.68 g) with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 974.5275 (theoretical value: 974.5287). Theoretical elemental content (%) C 71 H 66 N4: C, 87.43; H, 6.82; N, 5.74. Measured elemental content (%): C, 87.46; H, 6.80; N, 5.72.

[0241] Synthetic Example 14: Preparation of Compounds 1-323

[0242]

[0243] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54 and b-1-18 were replaced with equimolar amounts of a-1-323 and b-1-323, respectively, to obtain compound 1-323 (16.00 g) with an HPLC purity ≥ 99.92%. Mass spectrometry m / z: 925.3655 (theoretical value: 925.3668). Theoretical elemental content (%) C 67 H 47 N3O2: C, 86.89; H, 5.12; N, 4.54. Measured elemental content (%): C, 86.90; H, 5.09; N, 4.52.

[0244] Synthetic Example 15: Preparation of Compound 1-354

[0245]

[0246] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of g-1-54, A-1-54, and B-1-54 were replaced with equimolar amounts of g-1-354, B-1-54, and A-1-142, respectively, to obtain compound 1-354 (14.29 g) with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 915.4542 (theoretical value: 915.4552). Theoretical elemental content (%) C 68 H 57 N3: C, 89.14; H, 6.27; N, 4.59. Measured elemental content (%): C, 89.17; H, 6.25; N, 4.57.

[0247] Synthetic Example 16: Preparation of Compound 1-356

[0248]

[0249] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of c-1-54 and A-1-54 were replaced with equimolar amounts of c-1-356 and A-1-108, respectively, to obtain compound 1-356 (17.37 g) with an HPLC purity ≥ 99.92%. Mass spectrometry m / z: 1185.5942 (theoretical value: 1185.5961). Theoretical elemental content (%) C 89 H 75 N3: C, 90.09; H, 6.37; N, 3.54. Measured elemental content (%): C, 90.11; H, 6.36; N, 3.53.

[0250] Synthetic Example 17: Preparation of Compound 1-380

[0251]

[0252] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, b-1-18, and B-1-54 were replaced with equimolar amounts of a-1-323, b-1-380, and B-1-142, respectively, to obtain compound 1-380 (15.31 g) with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 951.4180 (theoretical value: 951.4189). Theoretical elemental content (%) C 70 H 53 N3O: C, 88.30; H, 5.61; N, 4.41. Measured elemental content (%): C, 88.27; H, 5.59; N, 4.43.

[0253] Synthetic Example 18: Preparation of Compound 1-388

[0254]

[0255] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of g-1-54, A-1-54, and B-1-54 were replaced with equimolar amounts of g-1-388, B-1-54, and A-1-18, respectively, to obtain compound 1-388 (13.36 g) with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 881.2879 (theoretical value: 881.2898). Theoretical elemental content (%) C 61 H 43 N3S2: C, 83.05; H, 4.91; N, 4.76. Measured elemental content (%): C, 83.07; H, 4.89; N, 4.77.

[0256] Synthetic Example 19: Preparation of Compound 1-445

[0257]

[0258] Following the same preparation method as compounds 1-54 in Synthesis Example 2, equimolar amounts of b-1-18 were replaced with equimolar amounts of d-1-445 to obtain compound 1-445 (16.37 g), with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 987.4196 (theoretical value: 987.4189). Theoretical elemental content (%) C 73 H 53 N3O: C, 88.72; H, 5.41; N, 4.25. Measured elemental content (%): C, 88.74; H, 5.39; N, 4.23.

[0259] Synthetic Example 20: Preparation of Compound 1-455

[0260]

[0261] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54 and c-1-54 were replaced with equimolar amounts of a-1-455 and c-1-455, respectively, to obtain compound 1-455 (13.61 g) with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 833.3422 (theoretical value: 833.3406). Theoretical elemental content (%) C 61 H 43 N3O: C, 87.85; H, 5.20; N, 5.04. Measured elemental content (%): C, 87.86; H, 5.19; N, 5.07.

[0262] Synthetic Example 21: Preparation of Compounds 1-459

[0263]

[0264] Following the same preparation method as compound 1-108 in Synthesis Example 4, equimolar amounts of c-1-108, b-1-18, and e-1-108 were replaced with equimolar amounts of c-1-459, d-1-445, and e-1-459, respectively, to obtain compound 1-459 (11.35 g) with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 859.3575 (theoretical value: 859.3563). Theoretical elemental content (%) C 63 H 45 N3O: C, 87.98; H, 5.27; N, 4.89. Measured elemental content (%): C, 87.95; H, 5.30; N, 4.91.

[0265] Synthesis Example 22: Preparation of Compounds 1-461

[0266]

[0267] Following the same preparation method as compound 1-108 in Synthesis Example 4, equimolar amounts of e-1-108 and B-1-108 were replaced with equimolar amounts of e-1-461 and A-1-54, respectively, to obtain compound 1-461 (10.84 g) with an HPLC purity ≥ 99.93%. Mass spectrometry m / z: 859.3554 (theoretical value: 859.3563). Theoretical elemental content (%) C 63 H 45N3O: C, 87.98; H, 5.27; N, 4.89. Measured elemental content (%): C, 87.97; H, 5.25; N, 4.88.

[0268] Synthetic Example 23: Preparation of Compound 1-487

[0269]

[0270] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, b-1-18, g-1-54, and B-1-54 were replaced with equimolar amounts of a-1-487, b-1-487, g-1-388, and A-1-108, respectively, to obtain compound 1-487 (13.95 g) with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 907.3915 (theoretical value: 907.3926). Theoretical elemental content (%) C 68 H 49 N3: C, 89.93; H, 5.44; N, 4.63. Measured elemental content (%): C, 89.91; H, 5.45; N, 4.64.

[0271] Synthetic Example 24: Preparation of Compounds 1-497

[0272]

[0273] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54, c-1-54, and g-1-54 were replaced with equimolar amounts of a-1-497, c-1-497, and g-1-388, respectively, to obtain compound 1-497 (14.48 g) with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 985.4388 (theoretical value: 985.4396). Theoretical elemental content (%) C 74 H 55 N3: C, 90.12; H, 5.62; N, 4.26. Measured elemental content (%): C, 90.13; H, 5.59; N, 4.25.

[0274] Synthetic Example 25: Preparation of Compounds 1-514

[0275]

[0276] Following the same preparation method as compound 1-108 in Synthesis Example 4, equimolar amounts of c-1-108, e-1-108, and A-1-108 were replaced with equimolar amounts of c-1-514, e-1-514, and B-1-54, respectively, to obtain compound 1-514 (10.86 g) with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 861.4095 (theoretical value: 861.4083). Theoretical elemental content (%) C 64 H 51 N3: C, 89.16; H, 5.96; N, 4.87. Measured elemental content (%): C, 89.17; H, 5.97; N, 4.84.

[0277] Synthetic Example 26: Preparation of Compounds 1-521

[0278]

[0279] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54 were replaced with equimolar amounts of a-1-521 to obtain compound 1-521 (13.35 g), with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 911.4259 (theoretical value: 911.4239). Theoretical elemental content (%) C 68 H 53 N3: C, 89.54; H, 5.86; N, 4.61. Measured elemental content (%): C, 89.55; H, 5.87; N, 4.59.

[0280] Synthetic Example 27: Preparation of Compound 1-537

[0281]

[0282] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54 and g-1-54 were replaced with equimolar amounts of a-1-537 and g-1-388, respectively, to obtain compound 1-537 (14.70 g) with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 927.3660 (theoretical value: 927.3647). Theoretical elemental content (%) C 67 H 49 N3S: C, 86.70; H, 5.32; N, 4.53. Measured elemental content (%): C, 86.69; H, 5.30; N, 4.55.

[0283] Synthetic Example 28: Preparation of Compounds 1-549

[0284]

[0285] Following the same preparation method as compound 1-108 in Synthesis Example 4, equimolar amounts of e-1-108, b-1-18, g-1-108, and B-1-108 were replaced with equimolar amounts of a-1-18, f-1-549, g-1-549, and B-1-445, respectively, to obtain compound 1-549 (13.46 g) with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 1003.3969 (theoretical value: 1003.3960). Theoretical elemental content (%) C 73 H 53 N3S: C, 87.30; H, 5.32; N, 4.18. Measured elemental content (%): C, 87.29; H, 5.34; N, 4.16.

[0286] Synthetic Example 29: Preparation of Compound 1-556

[0287]

[0288] Following the same preparation method as compound 1-108 in Synthesis Example 4, equimolar amounts of e-1-108, I-1-108, and B-1-108 were replaced with equimolar amounts of e-1-556, I-1-549, and B-1-54, respectively, to obtain compound 1-556 (11.40 g) with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 825.3189 (theoretical value: 825.3178). Theoretical elemental content (%) C 59 H 43 N3S: C, 85.79; H, 5.25; N, 5.09. Measured elemental content (%): C, 85.80; H, 5.22; N, 5.11.

[0289] Synthetic Example 30: Preparation of Compounds 1-569

[0290]

[0291] Following the same preparation method as compound 1-54 in Synthesis Example 2, equimolar amounts of a-1-54 and B-1-54 were replaced with equimolar amounts of a-1-259 and B-1-142, respectively, to obtain compound 1-569 (14.21 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 910.4050 (theoretical value: 910.4035). Theoretical elemental content (%) C 67 H 50 N4: C, 88.32; H, 5.53; N, 6.15. Measured elemental content (%): C, 88.33; H, 5.52; N, 6.14.

[0292] [Device Example 1]

[0293] First, the ITO substrate is washed three times in distilled water and ultrasonically cleaned for 15 minutes. After the distilled water cleaning is completed, isopropanol, acetone, methanol and other solvents are ultrasonically cleaned in sequence, and then dried at 120°C.

[0294] An organic electroluminescent device was fabricated by vacuum evaporation on a cleaned ITO substrate. A 35 nm thick HAT-CN layer was deposited as the hole injection layer. A 70 nm thick compound 1-18 layer was then deposited as the hole transport layer on the hole injection layer. A 40 nm thick light-emitting layer was formed by depositing a mixture of CBP:Ir(piq)2(acac) = 98:2 (mass ratio) on the hole transport layer. A 30 nm thick electron transport layer was formed by depositing TPBi and Liq (doping ratio 1:1) on the light-emitting layer. A 1.0 nm thick LiF layer was then deposited as the electron injection layer. Finally, Al was deposited as the cathode on the electron injection layer, with a thickness of 130 nm.

[0295]

[0296] [Device Examples 2-30]

[0297] Compounds 1-54, 1-96, 1-108, 1-142, 1-148, 1-203, 1-232, 1-259, 1-261, 1-267, 1-302, 1-309, 1-323, 1-354, 1-356, 1-380, 1-388, 1-445, 1-455, 1-459, 1-461, 1-487, 1-497, 1-514, 1-521, 1-537, 1-549, 1-556, and 1-569 of the present invention were used to replace compound 1-18 in device example 1 as the hole transport layer. Otherwise, an organic electroluminescent device was prepared using the same preparation method as in device example 1.

[0298] [Comparative Device Examples 1-2]

[0299] Comparative compound 1 and comparative compound 2 were used to replace compounds 1-18 in device example 1 as hole transport layers, and organic electroluminescent devices were prepared using the same preparation method as in device example 1.

[0300] A combined IVL testing system was used to test the luminous efficiency of organic electroluminescent devices (OLEDs), comprising testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectral scanning luminance meter. Lifetime testing was performed using a McScience M6000 OLED lifetime testing system. The testing environment was atmospheric, at room temperature.

[0301] The luminescence characteristics test results of the organic electroluminescent devices obtained in Examples 1 to 30 of the present invention and Comparative Examples 1 to 2 are shown in Table 1 below.

[0302]

[0303] As can be seen from the data results in Table 1, when the star-shaped triarylamine derivative of the present invention is used as a hole transport layer material in organic electroluminescent devices, compared with comparative examples 1 and 2, the luminous efficiency and lifespan of the device can be significantly improved. This is because the compound of the present invention has a high hole transport capability and increases the recombination probability of excitons, thereby optimizing the performance of the device.

[0304] [Device Example 31]

[0305] First, the ITO substrate is washed three times in distilled water and ultrasonically cleaned for 15 minutes. After the distilled water cleaning is completed, isopropanol, acetone, methanol and other solvents are ultrasonically cleaned in sequence, and then dried at 120°C.

[0306] An organic electroluminescent device was fabricated by vacuum evaporation on a cleaned ITO substrate. A 30 nm thick HAT-CN layer was deposited as the hole injection layer. A 70 nm thick compound 1-18 layer was deposited as the hole transport layer on the hole injection layer. A 35 nm thick CBP:Ir(ppy)3 (mass ratio 92:8) light-emitting layer was deposited on the hole transport layer. A 30 nm thick compound 2-71 layer was deposited as the hole blocking layer on the light-emitting layer. A 25 nm thick electron transport layer was deposited on the hole blocking layer using a TPBi and Liq (doping ratio 1:1). A 1.0 nm thick LiF layer was then deposited as the electron injection layer on the electron injection layer. Finally, a 120 nm thick Al layer was deposited as the cathode on the electron injection layer.

[0307] [Device Examples 32-60]

[0308] Compounds 1-54, 1-96, 1-108, 1-142, 1-148, 1-203, 1-232, 1-259, 1-261, 1-267, 1-302, 1-309, 1-323, 1-354, 1-356, 1-380, 1-388, 1-445, 1-455, 1-459, 1-461, 1-487, 1-497, 1-514, 1-521, 1-537, 1-549, 1-556, and 1-569 of the present invention are used to replace compound 1-18 in device example 31 as the hole transport layer; compounds 2-7 of the present invention are used. 3. Compounds 2-59, 2-202, 2-262, 2-21, 2-234, 2-306, 2-41, 2-201, 2-41, 2-169, 2-234, 2-54, 2-262, 2-47, 2-35, 2-54, 2-96, 2-59, 2-202, 2-82, 2-12, 2-269, 2-82, 2-42, 2-47, 2-211, 2-304, and 2-201 are used to replace compound 2-71 in device example 31 as a hole blocking layer. Otherwise, an organic electroluminescent device is prepared using the same preparation method as in device example 31.

[0309] [Comparative Device Examples [3-10]]

[0310] Organic electroluminescent devices were prepared by replacing compounds 1-18 and 2-71 in Device Example 31 with comparative compounds 1 and 2-211, 2-269, 2-96, 2-304, 54 and 3, 380 and 4, 259 and 4, and 521 and 4, respectively, using the same preparation method as in Device Example 31.

[0311] [Comparative Device Example 11]

[0312] First, the ITO substrate is washed three times in distilled water and ultrasonically cleaned for 15 minutes. After the distilled water cleaning is completed, isopropanol, acetone, methanol and other solvents are ultrasonically cleaned in sequence, and then dried at 120°C.

[0313] An organic electroluminescent device was fabricated by vacuum evaporation on a cleaned ITO substrate. A 30 nm thick HAT-CN layer was deposited as the hole injection layer. A 70 nm thick compound 1-54 layer was then deposited as the hole transport layer on the hole injection layer. A 35 nm thick CBP:Ir(ppy)3 (mass ratio 92:8) light-emitting layer was deposited on the hole transport layer. A 25 nm thick electron transport layer was then deposited on the light-emitting layer using a TPBi and Liq (doping ratio 1:1). A 1.0 nm thick LiF layer was then deposited as the electron injection layer on the electron transport layer. Finally, Al was deposited as the cathode on the electron injection layer, with a thickness of 120 nm.

[0314] [Comparative Device Examples 12-15]

[0315] Using the same preparation method as Comparative Device Example 11, compounds 1-54, which serve as the hole transport layer, were replaced with compounds 1-455, 1-259, 1-380, and 1-521, respectively, to obtain Comparative Device Examples 12-15.

[0316] The luminescence characteristics test results of the organic electroluminescent devices obtained in Examples 31-60 and Comparative Examples 3-15 of the present invention are shown in Table 2 below.

[0317]

[0318] As can be seen from the data structure in Table 2, when the star-shaped triarylamine derivative of the present invention is used as a hole transport layer material in conjunction with a specific hole blocking layer material in an organic light-emitting device, the luminous efficiency and lifespan of the device are significantly improved compared to the comparative devices 3-15. This indicates that there is a synergistic effect between the specific hole transport layer material and the specific hole blocking layer material of the present invention, which helps to significantly improve the luminous efficiency and extend the lifespan of the organic light-emitting device of the present invention, thereby breaking through the limitations of conventional organic light-emitting devices.

[0319] 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. A star-shaped triarylamine compound, characterized in that, The star-shaped triarylamine compound has the structure shown in Formula I. In Equation I, the R a The radical is selected from methyl, ethyl, isopropyl, and tert-butyl; m is selected from 1 or 2; Ar1 to Ar6 may be the same as or different from each other, and at least one of them is selected from... The shown group, the Selected from any one of the following groups, ； The remaining Ar1 to Ar6 groups, whether identical or different from each other, are selected from any of the following groups. ； The R is selected from any one of unsubstituted phenyl or naphthyl groups; The R1s may be the same or different from each other, and are selected from hydrogen and unsubstituted phenyl groups. a is selected from 0, 1, 2 or 3; b is selected from 0, 1, 2, 3 or 4; when there are two or more R1s, the two or more R1s are the same as or different from each other, or two adjacent R1s are connected to each other to form an unsubstituted benzene ring; The R x Selected from hydrogen; The q2 is selected from 4; The R y They may be the same as or different from each other, and are selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl. p1 is selected from 0, 1, 2, 3, 4 or 5; p2 is selected from 0, 1, 2, 3 or 4; p3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; and p4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9. The L1 to L6 may be the same as or different from each other, and are selected from single bonds or groups as shown below, and any combination thereof. ； The R2 is selected from hydrogen; a1 is selected from 3 or 4, and a3 is selected from 3.

2. The star-shaped triarylamine compound according to claim 1, characterized in that, The star-shaped triarylamine compound is selected from any one of the structures represented by formula I-1 and formula I-2. 。 3. The star-shaped triarylamine compound according to claim 1, characterized in that, The Selected from any one of the following groups, ; The R x Selected from hydrogen; The R x1 Selected from hydrogen; q1 is selected from 3, q2 is selected from 4, q6 is selected from 5, q7 is selected from 7, and q9 is selected from 6.

4. The star-shaped triarylamine compound according to claim 1, characterized in that, At least one of Ar1 to Ar6 is selected from The indicated groups, and the remaining groups that are the same as or different from each other, are selected from any of the groups shown below. 。 5. The star-shaped triarylamine compound according to claim 1, characterized in that, The L1 to L6 may be the same as or different from each other, and are selected from single bonds or any of the groups shown below. 。 6. A star-shaped triarylamine compound, characterized in that, The star-shaped triarylamine compound is selected from any of the following structures. 。 7. An organic electroluminescent device, comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside either the anode or the cathode, and the organic layer comprises a hole transport region, a light-emitting layer, and an electron transport region, characterized in that, The hole transport region and the light-emitting layer comprise any one or more of the star-shaped triarylamine compounds described in any one of claims 1 to 6.

8. An organic electroluminescent device, comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside either the anode or the cathode, and the organic layer comprises a hole transport region, a light-emitting layer, and an electron transport region, characterized in that, The hole transport region includes a hole transport layer, which includes one or more of the star-shaped triarylamine compounds shown in Formula I; the electron transport region includes a hole blocking layer, which includes one or more of the compounds shown in Formula II. In Equation I, the R a The radical is selected from methyl, ethyl, isopropyl, and tert-butyl; m is selected from 1 or 2; Ar1 to Ar6 may be the same as or different from each other, and at least one of them is selected from... The shown group, the Selected from any one of the following groups, The remaining Ar1 to Ar6 groups, whether identical or different from each other, are selected from any of the following groups. ； The R is selected from any one of unsubstituted phenyl or naphthyl groups; The R1s may be the same or different from each other, and are selected from any one of hydrogen, unsubstituted C1-C6 alkyl groups, and unsubstituted phenyl groups; a is selected from 0, 1, 2 or 3; b is selected from 0, 1, 2, 3 or 4; when there are two or more R1s, the two or more R1s are the same as or different from each other, or two adjacent R1s are connected to each other to form an unsubstituted benzene ring; The R x They may be the same as or different from each other, and are selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl. The q2 is selected from 0, 1, 2, 3 or 4; The R y They may be the same as or different from each other, and are selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl. p1 is selected from 0, 1, 2, 3, 4 or 5; p2 is selected from 0, 1, 2, 3 or 4; p3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; and p4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9. The L1 to L6 may be the same as or different from each other, and are selected from single bonds or groups as shown below, and any combination thereof. ； The R2 is selected from hydrogen; a1 is selected from 3 or 4, and a3 is selected from 3; In Formula II, Ar7 and Ar8 may be the same as or different from each other, and are selected from any of the following groups. ； X1 is selected from any one of O, S, and N(R4); The R4 is selected from any one of the unsubstituted C6 to C12 aryl groups; The n1 is selected from 1, 2, 3 or 4; X0 is selected from any one of O, S, N(Ara), and C(Arb)2; Ara is selected from unsubstituted C6-C12 aryl groups; Arb may be the same or different from each other and is selected from unsubstituted C1-C6 alkyl groups. The R3s may be the same or different from each other, and are selected from any one of hydrogen, deuterium, and unsubstituted C1 to C6 alkyl groups; The c is selected from 0, 1, 2, 3 or 4. When there are two or more R3s, the two or more R3s are the same or different from each other, or two adjacent R3s are connected to each other to form an unsubstituted benzene ring. The L x L y They may be the same as or different from each other, and are selected from single bonds or any of the groups shown below. ； The L0 group is selected from single bonds or any combination thereof, as shown below. ； b1 is selected from 1, 2, 3 or 4; b2 is selected from 1, 2, 3, 4 or 5; b3 is selected from 1, 2 or 3; and b4 is selected from 1, 2, 3, 4, 5 or 6. The T values ​​are identical to each other and are selected from C(R). m ), the R m Selected from hydrogen; Q is selected from either O or S.

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