A triamine derivative and an organic light emitting device thereof

Abstract

The application provides a triamine derivative and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The application mainly solves the problems of low light-emitting efficiency and short service life of most current organic light-emitting devices. The derivative of the application takes benzene as a center, and at least one or two alkyl groups are connected to the center benzene. The derivative has good film-forming property and thermal stability on one hand, and has good hole mobility, appropriate HOMO energy level and T1 value on the other hand. When the derivative is applied to an organic light-emitting device as a hole transport layer material, the light-emitting efficiency of the device can be effectively improved, and the service life of the device can be prolonged. The derivative of the application is combined with a heterocyclic compound represented by formula II and applied to the device, so that the maximum recombination of carriers is realized, thereby improving the light-emitting efficiency and service life of the device. The application can be widely applied to the fields of panel display, lighting source, organic solar cell, organic photoreceptor or organic thin film transistor and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of organic photoelectric materials, in particular to a triamine derivative and an organic light-emitting device thereof. Background Art

[0002] With the development of electronic technology and advancements in materials science, the application of electronic components used to achieve electroluminescence or photoelectric conversion is becoming increasingly widespread. Organic electroluminescent devices (OLEDs), as a next-generation display technology, are gradually gaining attention due to their self-luminescence, wide viewing angle, fast response time, high luminous efficiency, and wide color gamut.

[0003] An organic light-emitting device (OLED) consists of an anode on a substrate, organic layers that sequentially form a hole transport region, an emissive layer, and an electron transport region on the anode, a cathode, and a capping layer on the cathode. OLEDs operate by applying a voltage across the electrodes. Driven by the electric field, positive and negative charges in the organic layer recombine in the emissive layer, generating light. Therefore, enhancing the recombination of electrons and holes in OLED devices is crucial.

[0004] At present, the types of hole transport and electron transport materials used in organic light-emitting devices are relatively limited, resulting in many problems that need to be solved in organic light-emitting devices. The materials commonly used in the hole transport layer have problems such as low hole mobility and low glass transition temperature. The electron and hole transport cannot reach a balance, and the excitons cannot effectively recombine. At the same time, the triplet energy level is low, which cannot effectively prevent the escape of excitons to the hole transport layer, resulting in low device luminescence efficiency and decreased device stability.

[0005] In response to the above problems, the research on hole transport materials with higher hole mobility, high glass transition temperature, high triplet energy level and good moldability has become an urgent issue to be solved. Summary of the Invention

[0006] The purpose of the present invention is to provide a triamine derivative and an organic light-emitting device thereof based on the existing technology and with the goal of industrialization. The present invention provides a triamine derivative, the general molecular structure of which is shown in Formula I:

[0007]

[0008] wherein at least one of R1 and R2 is selected from a substituted or unsubstituted C1-C10 alkyl group, R3 is selected from hydrogen, cyano or halogen, and the substituent in the above “substituted or unsubstituted” is selected from one or more of methyl, ethyl, isopropyl and tert-butyl;

[0009] The Ar1 is selected from substituted or unsubstituted C10-C25 aryl groups, wherein the substituent in "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, and tert-butyl;

[0010] Ar2, Ar3, Ar4, Ar5, and Ar6 are independently selected from the group shown in formula a:

[0011]

[0012] The R m The same or different R is selected from one of hydrogen, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, or two adjacent R m The groups may be bonded together to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring, wherein the substituent in "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, and tert-butyl;

[0013] The m1 is selected from 0, 1, 2, 3, 4 or 5;

[0014] The L1, L2, L3, L4, L5, and L6 are independently selected from a single bond, a substituted or unsubstituted C6-C25 arylene group, wherein the substituent in "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, and tert-butyl.

[0015] The present invention also provides an organic light-emitting device, comprising an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0016] Beneficial effects of the present invention:

[0017] The present invention provides a triamine derivative and an organic light-emitting device thereof. The present invention uses benzene as the center, connected to three triarylamines, and at least one or two alkyl groups (straight or branched) are connected to the central benzene. On the one hand, the derivative contains an alkyl group, which enhances solubility, facilitates film formation, and is less likely to crystallize in the thin film state. In addition, one or two alkyl groups provide less steric hindrance than three alkyl groups, thereby enabling orderly molecular stacking during vapor deposition, increasing the compound's glass transition temperature, and enhancing device stability. On the other hand, the derivative has good hole mobility, an appropriate HOMO energy level, and a T1 value. Application in organic light-emitting devices, particularly as hole transport layer materials, can effectively improve the device's luminous efficiency and extend its service life.

[0018] The triamine derivative represented by formula I is applied to the hole transport layer, and the heterocyclic compound represented by formula II is applied to the electron transport region. The combination of the two materials is applied to an organic light-emitting device to improve the transmission efficiency of holes and electrons in the device, and effectively block the holes and electrons in the light-emitting layer to achieve maximum carrier recombination, thereby improving the luminous efficiency and service life of the organic light-emitting device. DETAILED DESCRIPTION

[0019] The following is a clear and complete description of the technical solutions of the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts shall fall within the scope of protection of the present invention.

[0020] In the compounds of the present invention, any atom not designated as a specific isotope is included as any stable isotope of that atom, and includes atoms at both their natural isotopic abundance and unnatural abundance. Taking hydrogen as an example, all naturally occurring compounds contain approximately 0.0156 atomic % deuterium per hydrogen atom.

[0021] As used herein, the use of "H" and "hydrogen" means that the hydrogen atoms in a chemical structure contain no more than natural abundance of deuterium atoms or tritium atoms, for example, no more than 0.0156 atomic % of deuterium. "D" and "deuterium" mean that the abundance of deuterium content is above natural abundance, for example, any value exceeding 0.1 atomic %, exceeding 1 atomic %, or exceeding 10 atomic %, for example, wherein about 95 atomic % is deuterium. "T" and "tritium" mean that the abundance of tritium content is above natural abundance, for example, any value exceeding 0.1 atomic %, exceeding 1 atomic %, or exceeding 10 atomic %, for example, wherein about 95 atomic % is tritium. As used herein, "H" or "hydrogen" is represented by omitting unillustrated hydrogen atoms.

[0022] In this specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example, Can represent And so on.

[0023] The halogen mentioned in the present invention refers to fluorine, chlorine, bromine and iodine.

[0024] The alkyl group described in the present invention refers to a hydrocarbon group formed by missing 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 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight-chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, etc., but is not limited thereto; the branched-chain alkyl group includes isopropyl, isobutyl, sec-butyl, tert-butyl, isomeric groups of n-pentyl, isomeric groups of n-hexyl, isomeric groups of n-heptyl, isomeric groups of n-octyl, isomeric groups of n-nonyl, isomeric groups of n-decyl, etc., but is not limited thereto. The above-mentioned alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.

[0025] The chain alkyl group having more than three carbon atoms described in the present invention includes its isomers. For example, propyl includes n-propyl and isopropyl, butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl, and so on.

[0026] The cycloalkyl group herein refers to a hydrocarbon group formed by removing one hydrogen atom from a cycloalkane molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, bornyl, and norbornyl. Preferred cycloalkyl groups include cyclobutyl, cyclopentyl, and cyclohexyl.

[0027] The heterocycloalkyl group of the present invention refers to a monovalent group in which at least one parent carbon atom in a cycloalkyl group is replaced by a heteroatom. The heteroatom includes, but is not limited to, atoms such as N, O, S, Si, B, and P. Preferably, it has 3 to 30 carbon atoms, more preferably 3 to 15 carbon atoms, and even more preferably 3 to 10 carbon atoms. Examples of the heterocycloalkyl group include, but are not limited to, groups such as aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, homopiperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, oxazolidinyl, thiazolidinyl, and imidazolidinyl.

[0028] The aryl group described in the present invention refers to a monovalent group remaining after removing a hydrogen atom from the aromatic carbon nucleus of an aromatic compound molecule. It can be a monocyclic aryl group, a polycyclic aryl group, or a condensed aryl group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl group refers to an aryl group with only one aromatic ring in the molecule, such as, but not limited to, phenyl; the polycyclic aryl group refers to an aryl group containing two or more independent aromatic rings in the molecule, such as, but not limited to, biphenyl and terphenyl; the condensed aryl group refers to an aryl group containing two or more aromatic rings in the molecule that are fused together by sharing two adjacent carbon atoms, such as, but not limited to, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, etc. The aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthracenyl group (preferably a 2-anthryl group), a phenanthrenyl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylene group, or a spirobifluorenyl group.

[0029] The heteroaryl group described in the present invention refers to a general term for a group in which one or more aromatic carbon atoms in an aromatic group are replaced by a heteroatom, wherein the heteroatom includes but is not limited to oxygen, sulfur, nitrogen or phosphorus atoms, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms. The attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a condensed-ring heteroaryl group. The monocyclic heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, triazine, furyl, thienyl, pyrrolyl, imidazolyl, etc.; the polycyclic heteroaryl groups include, but are not limited to, bipyridyl, bipyrimidinyl, phenylpyridyl, etc.; the fused-ring heteroaryl groups include, but are not limited to, quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothienyl, benzodibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9,10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl, etc., but are not limited to. The above-mentioned heteroaryl group is preferably pyridyl, pyrimidinyl, thienyl, furyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, benzodibenzothienyl, benzodibenzofuranyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, or phenoxathiyl.

[0030] The arylene group described in the present invention refers to the general term for a divalent group remaining after removing two hydrogen atoms from the aromatic carbon nucleus of an aromatic compound molecule. It can be a monocyclic arylene group, a polycyclic arylene group, or a condensed-ring arylene group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene group includes, but is not limited to, phenylene groups; the polycyclic arylene group includes, but is not limited to, biphenylene groups and terphenylene groups; the condensed-ring arylene group includes, but is not limited to, naphthylene groups, anthrylene groups, phenanthrenyl groups, fluorenyl groups, pyrenyl groups, triphenylene groups, fluoranthenyl groups, and phenylenefluorenyl groups. The above-mentioned arylene groups are preferably phenylene groups, biphenylene groups, terphenylene groups, naphthylene groups, fluorenyl groups, and phenylenefluorenyl groups.

[0031] The heteroarylene group of the present invention is a general term for a group in which one or more aromatic carbon atoms in an arylene group are replaced by a heteroatom, including but not limited to oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably, the group has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms. The attachment point of the heteroarylene group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom. The heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a condensed-ring heteroarylene group. The monocyclic heteroarylene group includes, but is not limited to, pyridylene, pyrimidylene, triazinylene, furylene, thienylene, etc.; the polycyclic heteroarylene group includes, but is not limited to, bipyridylene, bipyrimidylene, phenylpyridylene, etc.; the condensed-ring heteroarylene group includes, but is not limited to, quinolylene, isoquinolylene, indolylene, benzothiophenylene, benzofuranylene, benzoxazolylene, benzimidazolylene, benzothiazolylene, dibenzofuranylene, benzodibenzofuranylene, dibenzothiophenylene, benzodibenzothiophenylene, carbazolylene, benzocarbazolylene, acridinylene, 9,10-dihydroacridinylene, phenoxazinylene, phenothiazinylene, phenoxathiylene, etc., but is not limited to. The above-mentioned heteroaryl group is preferably a pyridylene group, a pyrimidylene group, a thienylene group, a furylene group, a benzothienylene group, a benzofurylene group, a benzoxazolylene group, a benzimidazolylene group, a benzothiazolylene group, a dibenzofurylene group, a dibenzothienylene group, a benzodibenzothienylene group, a benzodibenzofurylene group, a carbazolylene group, an acridinylene group, a phenoxazinylene group, a phenothiazinylene group, or a phenoxathiylene group.

[0032] The fused cyclic group of an alicyclic ring and an aromatic ring as described herein refers to a general term for a divalent group formed by condensing an alicyclic ring and an aromatic ring together and removing two hydrogen atoms. Preferably, the group has 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 13 carbon atoms. Examples thereof may include, but are not limited to, benzocyclopropylene, benzocyclobutylene, benzocyclopentylene, benzocyclohexylene, benzocycloheptylene, benzocyclopentenylene, benzocyclohexenylene, benzocycloheptenylene, naphthocyclopropylene, naphthocyclobutylene, naphthocyclopentylene, and naphthocyclohexylene.

[0033] The fused ring of an aromatic ring and an aliphatic ring described in the present invention refers to a ring containing one or more aromatic rings and one or more aliphatic rings fused to each other by sharing two adjacent carbon atoms in the molecule. 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. Examples include benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexanyl, benzocycloheptanyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptenyl, naphthocyclopropanyl, naphthocyclobutanyl, naphthocyclopentanyl, naphthocyclohexanyl, naphthocyclopentenyl, naphthocyclohexenyl, etc., but are not limited thereto.

[0034] The aliphatic ring described in the present invention refers to a cyclic hydrocarbon with aliphatic properties, containing a closed carbon ring in the molecule, preferably having 3 to 60 carbon atoms, more preferably 3 to 30 carbon atoms, further preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. It can form a monocyclic hydrocarbon or a polycyclic hydrocarbon, which can be completely unsaturated or partially unsaturated. Specific examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, etc., but are not limited to these. Multiple monocyclic hydrocarbons can also be connected in various ways: two rings in the molecule can share a carbon atom to form a spirocycle; two carbon atoms on the ring can be connected by a carbon bridge to form a bridged ring; and several rings can also be connected to form a cage-like structure.

[0035] The “unsubstituted…” mentioned in the present invention, such as unsubstituted alkyl, unsubstituted cycloalkyl, unsubstituted heterocycloalkyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted arylene, unsubstituted heteroarylene, etc., means that the “hydrogen” (H) in the group is not replaced by other groups including deuterium and tritium.

[0036] The "substituted..." in the present invention, such as substituted alkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, etc., refers to a group independently selected from, but not limited to, deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amino, etc., which is monosubstituted or polysubstituted, preferably selected from, deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, etc. The present invention also includes but is not limited to substituted or polysubstituted groups selected from the group consisting of cyclohexyl, adamantyl, norbornyl, bornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, peryl, pyrenyl, benzyl, tolyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, diphenylamino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, phenothiazinyl, phenoxazinyl, and indolyl. In addition, the above substituents may be substituted by one or more substituents selected from the group consisting of deuterium, halogen, cyano, alkyl, cycloalkyl, and aryl.

[0037] The two adjacent substituents described in the present invention can combine with each other to form a substituted or unsubstituted C3-C8 aliphatic ring, which can be the following substituted or unsubstituted aliphatic ring:

[0038]

[0039] Wherein, “*” represents the connection site of the loop.

[0040] The connection to form a substituted or unsubstituted ring in the present invention refers to two groups connected to each other by a chemical bond and optionally aromatized. For example:

[0041]

[0042] In the present invention, the ring formed by connection can be a five-membered ring, a six-membered ring or a condensed ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclohexene, cyclopentane, cyclohexane, cyclohexanedone, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.

[0043] The present invention provides a triamine derivative, the general molecular structure of which is shown in Formula I:

[0044]

[0045] wherein at least one of R1 and R2 is selected from a substituted or unsubstituted C1-C10 alkyl group, R3 is selected from hydrogen, cyano or halogen, and the substituent in the above “substituted or unsubstituted” is selected from one or more of methyl, ethyl, isopropyl and tert-butyl;

[0046] The Ar1 is selected from substituted or unsubstituted C10-C25 aryl groups, wherein the substituent in "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, and tert-butyl;

[0047] Ar2, Ar3, Ar4, Ar5, and Ar6 are independently selected from the group shown in formula a:

[0048]

[0049] The R m The same or different R is selected from one of hydrogen, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, or two adjacent R m The groups may be bonded together to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring, wherein the substituent in "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, and tert-butyl;

[0050] The m1 is selected from 0, 1, 2, 3, 4 or 5;

[0051] The L1, L2, L3, L4, L5, and L6 are independently selected from a single bond, a substituted or unsubstituted C6-C25 arylene group, wherein the substituent in "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, and tert-butyl.

[0052] Preferably, the three aromatic amine groups in Formula I are connected to the benzene ring in a meta-position.

[0053] Preferably, at least one of R1 and R2 is selected from the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, wherein the substituent in "substituted or unsubstituted" is selected from methyl, ethyl, isopropyl, tert-butyl.

[0054] Preferably, Ar1 is selected from any one of the following groups:

[0055]

[0056] The R rThe same or different R is selected from one of hydrogen, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, or two adjacent R r The groups may be bonded together to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, wherein the substituent in "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, and tert-butyl;

[0057] The r1 is selected from 0, 1, 2, 3, 4 or 5; the r2 is selected from 0, 1, 2, 3 or 4; and the r4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

[0058] Further preferably, the Ar1 is selected from any one of the following groups:

[0059]

[0060] The Rr are the same as or different from each other and are selected from hydrogen or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, terphenyl, naphthyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, and in the case of being substituted by multiple substituents, the multiple substituents are the same as or different from each other;

[0061] Said r1 is selected from 0, 1, 2, 3, 4 or 5; said r2 is selected from 0, 1, 2, 3 or 4; said r3 is selected from 0, 1, 2 or 3; said r4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; said r5 is selected from 0, 1 or 2; said r6 is selected from 0, 1, 2, 3, 4, 5 or 6; said r7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

[0062] Preferably, Ar2, Ar3, Ar4, Ar5, and Ar6 are independently selected from any one of the following groups:

[0063]

[0064] The R m is selected from one of hydrogen, cyano, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, or two adjacent R m The groups can be bonded together to form substituted or unsubstituted benzene rings;

[0065] wherein R m Can also be R mm Replaced by Rmm One or more selected from hydrogen, cyano, halogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl, and triphenylene; when substituted with multiple substituents, the multiple substituents may be the same or different;

[0066] The m1 is selected from 0, 1, 2, 3, 4 or 5; the m2 is selected from 0, 1, 2, 3 or 4; the m3 is selected from 0, 1, 2 or 3; the m4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

[0067] Further preferably, Ar2, Ar3, Ar4, Ar5, and Ar6 are independently selected from any one of the following groups:

[0068]

[0069]

[0070] The R m The same as or different from each other, and are selected from hydrogen or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, terphenyl, naphthyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, and when substituted by multiple substituents, the multiple substituents are the same as or different from each other;

[0071] The m1 is selected from 0, 1, 2, 3, 4 or 5; the m2 is selected from 0, 1, 2, 3 or 4; the m3 is selected from 0, 1, 2 or 3; the m4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m5 is selected from 0, 1 or 2; the m6 is selected from 0, 1, 2, 3, 4, 5 or 6; the m7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

[0072] More preferably, Ar2, Ar3, Ar4, Ar5, and Ar6 are independently selected from any one of the following groups:

[0073]

[0074] Preferably, L1, L2, L3, L4, L5, and L6 are independently selected from a single bond or one of the following groups:

[0075]

[0076] The R nAny one selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C25 aryl; n1 is selected from 0, 1, 2, 3 or 4; n2 is selected from 0, 1, 2, 3, 4, 5 or 6.

[0077] Further preferably, the R n A group selected from hydrogen, a substituted or unsubstituted group: one of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, and triphenylene, wherein the substituent is one or more of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, and naphthyl, and when substituted by multiple substituents, the multiple substituents are the same or different from each other.

[0078] More preferably, L1, L2, L3, L4, L5, and L6 are independently selected from a single bond or one of the following groups:

[0079]

[0080] Most preferably, L1, L2, L3, L4, L5, and L6 are independently selected from a single bond or one of the following groups:

[0081]

[0082] Most preferably, the triamine derivative is selected from any one of the following chemical structures:

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] The preparation method of the triamine derivative of formula I of the present invention can be prepared by conventional coupling reactions in the art, for example, by the following synthetic route, but the present invention is not limited thereto:

[0099]

[0100] The triamine derivative is subjected to a Buchwald-Hartwig coupling reaction to obtain intermediates A1, A2, and A3; the raw material e is subjected to a Buchwald-Hartwig coupling reaction with intermediate A1 to obtain intermediate B; intermediate B and intermediate A2 are subjected to a Buchwald-Hartwig coupling reaction to obtain intermediate C; intermediate C and intermediate A3 are subjected to a Buchwald-Hartwig coupling reaction to finally obtain a compound of formula I, wherein X1, X2, X3, X4, X5, and X6 independently represent Cl, Br, or I.

[0101] The present invention has no particular limitation on the sources of the raw materials used in the above-mentioned reactions. The present invention has no particular limitation on the above-mentioned reactions, and conventional reactions well known to those skilled in the art can be used.

[0102] The present invention also provides an organic light-emitting device, comprising an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0103] Preferably, the organic layer comprises a hole transport region, a light emitting layer, an electron transport region and a covering layer, and at least one of the hole transport region, the light emitting layer and the covering layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0104] Preferably, the organic layer comprises a hole transport region, which is located between the anode and the light-emitting layer. The hole transport region contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0105] Preferably, the hole transport region comprises a hole transport layer, which is located between the anode and the light-emitting layer. The hole transport layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0106] Preferably, the hole transport region comprises a hole transport layer and / or a luminescent auxiliary layer (second hole transport layer), the luminescent auxiliary layer is located between the hole transport layer and the luminescent layer, and the hole transport layer and / or the luminescent auxiliary layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0107] Preferably, the organic layer comprises a light-emitting layer, which is located between the hole transport region and the electron transport region, and the light-emitting layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0108] Preferably, the light-emitting layer comprises a host material and / or a dopant material, and the host material contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0109] Preferably, the organic layer comprises an electron transport region, which is located between the light-emitting layer and the cathode. The electron transport region contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0110] Preferably, the electron transport region comprises an electron transport layer, which is located between the light-emitting layer and the cathode. The electron transport layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0111] Preferably, the electron transport region comprises an electron transport layer and / or a hole blocking layer, the hole blocking layer is located between the light-emitting layer and the electron transport layer, and the electron transport layer and / or the hole blocking layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.

[0112] The light-emitting device of the present invention is typically formed on a substrate. This substrate can be any material, as long as it remains unchanged during the formation of the electrodes and organic layer. For example, it can be made of glass, plastic, polymer film, silicon, or the like. If the substrate is opaque, the opposing electrode is preferably transparent or translucent.

[0113] The anode material is generally selected from materials having a high work function to facilitate hole injection. The anode can be a reflective electrode or a transmissive electrode. The material used for the anode can be a transparent and highly conductive material, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2) and zinc oxide (ZnO), but the structure of the anode material is not limited thereto. When the anode is a semi-transmissive electrode or a reflective electrode, as far as the material used to form the anode is concerned, at least one selected from magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In) and magnesium-silver (Mg-Ag) can be used.

[0114] The anode may have a single-layer structure or a multilayer structure including two or more layers. For example, the anode may have a three-layer structure of ITO / Ag / ITO, but the structure of the anode is not limited thereto. Preferably, the anode of the present invention uses a transparent ITO substrate. The anode can be formed by depositing or spraying the material for forming the anode onto the substrate.

[0115] The hole transport zone may include a single-layer structure of multiple different materials, a hole injection layer / hole transport layer structure, a hole injection layer / hole transport layer / buffer layer structure, a hole injection layer / buffer layer structure, a hole transport layer / buffer layer structure, or a hole injection layer / hole transport layer / electron blocking layer structure, wherein the layers of each structure are stacked successively from the anode in the order described, but the structure of the hole transport zone is not limited thereto.

[0116] The hole injection material is a material having the function of promoting hole injection from the anode. The hole injection layer can be formed at a thickness in the range of 10 nm to 150 nm. The material of the hole injection layer may include triphenylamine-containing polyetherketone (TPAPEK), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (PPBI), N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine (DNTPD), copper phthalocyanine (II) (abbreviation: CuPc), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (abbreviation: HAT-CN), 4,4',4"-tri{N ,N-diphenylamino}triphenylamine (TDATA), 4,4',4"-tris(N,N-2-naphthylphenylamino)triphenylamine (2-TNATA), polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA) or polyaniline / poly(4-styrenesulfonate) (PANI / PSS), etc. It can be a single structure composed of a single substance or a single-layer or multi-layer structure composed of different substances. In addition to the above materials and their combinations, other known materials suitable for the hole injection layer can also be selected.

[0117] The hole transport material is a material having good hole transport properties, and the hole transport layer can be formed with a layer thickness of 10 nm to 150 nm (for example, the total layer thickness of the multilayer structure). The hole transport layer material can be selected from small molecule materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and polymer materials such as polyparaphenylene derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyvinylcarbazole and its derivatives, polysilane and its derivatives, but is not limited thereto. Examples of hole transport materials may include 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB), 2,2,7,7-tetrakis(diphenylamino)-9,9- Spirobifluorene (abbreviated as Spiro-TAD), etc. Preferably, the hole transport layer is selected from the triamine derivatives described in the present invention, which can be a single structure composed of a single substance, or a single-layer structure or a multi-layer structure formed by different substances. The hole transport layer may include a single layer, or may include a first hole transport layer and a second hole transport layer or more layers. One or more layers of the hole transport layer contain the triamine derivative provided by the present invention, the first hole transport layer is located between the hole injection layer and the light-emitting layer, and the second hole transport layer is located between the first hole transport layer and the light-emitting layer.

[0118] A light-emitting layer is a layer that emits light. It includes a host material and a dopant material and emits light through fluorescence or phosphorescence. The light-emitting layer can have a thickness ranging from 10 nm to 60 nm. The light-emitting layer can be formed to emit light of a specific color. For example, the light-emitting layer can be formed as a red light-emitting layer, a green light-emitting layer, or a blue light-emitting layer.

[0119] The host material is selected from 4,4'-di(9-carbazole)biphenyl (CBP), 9,10-di(2-naphthyl)anthracene (ADN), 4,4-di(9-carbazolyl)biphenyl (CPB), 9,9'-(1,3-phenyl)di-9H-carbazole (mCP), 4,4',4"-tri(carbazol-9-yl)triphenylamine (TCTA), 9,10-di(1-naphthyl)anthracene (α-AND), N,N'-di-(1-naphthyl)-N,N'-diphenyl-[1,1':4',1":4",1"'-tetraphenyl]-4,4"'-diamine (4PNPB), 1,3,5-tri(9-carbazolyl)benzene (TCP), etc. In addition to the above materials and combinations thereof, the host material of the light-emitting layer can be selected from the triamine derivatives provided by the present invention, and other known materials suitable for the light-emitting layer can also be selected.

[0120] When the light-emitting layer is a blue light-emitting layer, a suitable blue dopant can be used. For example, perylene and its derivatives, iridium (Ir) complexes such as bis[2-(4,6-difluorophenyl)pyridinium (pyridinate)] picolinate iridium (III) (FIrpic) can be used as blue dopants. When the light-emitting layer is a red light-emitting layer, a suitable red dopant can be used. For example, rubrene and its derivatives, 4-dicyanomethyl-2-(p-dimethylaminophenyl)-6-methyl-4H-pyran (DCM) and its derivatives, iridium complexes such as bis(1-phenylisoquinoline)(acetylacetonate)iridium (III) (Ir(piq)2(acac), osmium (Os) complexes, platinum complexes, etc. can be used as red dopants. When the light-emitting layer is a green light-emitting layer, a suitable green dopant can be used. For example, coumarin and its derivatives, iridium complexes such as tris(2-phenylpyridine)iridium (III) (Ir(ppy)3) and the like can be used.

[0121] The optimal doping ratio of the main material and the guest material of the light-emitting layer may vary depending on the materials used. Usually, the doping mass percentage of the guest material of the light-emitting layer is 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

[0122] The electron transport region may include at least one of an electron injection layer, an electron transport layer, a buffer layer, and a hole blocking layer. It may be a single structure composed of a single substance, or a single-layer structure or a multi-layer structure formed by different substances. The electron transport layer may include a single layer, or may include a first electron transport layer and a second electron transport layer or more layers. The type of the electron transport region may be a structure of electron injection layer / electron transport layer, a structure of electron injection layer / electron transport layer / buffer layer, a structure of electron injection layer / buffer layer, a structure of electron transport layer / buffer layer, or a structure of electron injection layer / electron transport layer / hole blocking layer, wherein the layers of each structure are stacked successively from the cathode in the order described, but the structure of the electron transport region is not limited thereto.

[0123] The hole-blocking layer can effectively prevent the escape of excitons to the hole-transporting layer. Preferably, the hole-blocking layer comprises a material having a high triplet energy level and a suitable HOMO energy level. The hole-blocking layer can be formed to a layer thickness in the range of 15 nm to 50 nm. Examples of the hole-blocking layer may include, but are not limited to, oxadiazole derivatives, triazole derivatives, quinoline derivatives, phenanthroline derivatives, anthraquinone derivatives, anthrone derivatives, azobenzene derivatives, and imidazole derivatives. Preferably, the hole-blocking material is selected from the heterocyclic compounds provided by the present invention.

[0124] The electron transport layer is a layer having an electron transport function and can be formed to have a thickness in the range of 15 nm to 50 nm. The electron transport layer material can be selected from quinoline derivatives such as tris(8-hydroxyquinolinolato)aluminum (Alq3), 1,2,4-triazole derivatives (TAZ), bis(2-methyl-8-hydroxyquinolinolato)-(p-phenylphenolato)-aluminum (BAlq), bis(10-hydroxybenzoquinolinolato)beryllium (BeBq2), Li complexes such as 8-hydroxyquinolinolato lithium (LiQ), nitrogen-containing aromatic rings, etc. Examples of nitrogen-containing aromatic rings may include pyridine ring-containing materials such as 1,3,5-tris[(3-pyridyl)-phenyl-3-yl]benzene, triazine ring-containing materials such as 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine, imidazole derivative-containing materials such as 2-(4-(N-phenylbenzimidazolyl-1-ylphenyl)-9,10-dinaphthylanthracene), etc. It can be a single structure composed of a single substance, or a single-layer structure or a multi-layer structure formed by different substances. In addition to the above materials, the electron transport layer can be selected from the heterocyclic compound provided by the present invention, and other known materials suitable for the electron transport layer can also be selected.

[0125] The electron injection layer is a layer having the function of promoting electron injection from the cathode. The electron injection layer can be formed with a layer thickness in the range of 0.3nm to 9nm. The electron injection layer material can be selected from lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li2O), barium oxide (BaO), 8-hydroxyquinoline lithium (LiQ), etc. In addition to the above materials, the electron injection layer can be selected from the heterocyclic compound provided by the present invention, and other known materials suitable for the electron injection layer can also be selected.

[0126] Preferably, the electron transport region contains a heterocyclic compound represented by formula II:

[0127]

[0128] The Arb and Arc are the same or different and are selected from the structure shown in formula b,

[0129] The Z is selected from any one of O, S or N(Ry); the Ry is selected from any one of hydrogen, deuterium, 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;

[0130] The Ys are the same or different and are selected from C(Rx) or N; the Rxs are the same or different and are 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, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rxs are connected to form a substituted or unsubstituted ring;

[0131] The R b 、R c are independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted fused ring of a C6-C30 aromatic ring and a C3-C30 aliphatic ring, and a substituted or unsubstituted C2-C30 heteroaryl, or R b 、R c They can combine with each other to form a substituted or unsubstituted spiro ring; R b 、R c Any one of them can be directly bonded to the bridging La;

[0132] The R0 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, substituted or unsubstituted C2-C30 heteroaryl; the a is selected from 0, 1, 2 or 3;

[0133] The R a 、R t Any one independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or two adjacent R a They can be connected to form a substituted or unsubstituted aromatic ring or aliphatic ring; or two adjacent R t They can be connected to form substituted or unsubstituted aromatic rings or aliphatic rings;

[0134] The a1 is selected from 0, 1, 2, 3 or 4; the a2 is selected from 0, 1, 2, 3 or 4; the t is selected from 0, 1, 2, 3 or 4;

[0135] The L a , L b , L cThe same or different one is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted C3-C10 alicyclic ring and a C6-C25 aromatic ring.

[0136] Preferably, the R t are the same as or different from each other and are selected from hydrogen, deuterium or a substituted or unsubstituted group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, canyl, norbornyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, cyano, fluoro, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzocyclopentanyl, benzocyclohexanyl, benzocyclopentenyl, benzocyclohexenyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, oxazolidinyl, thiazolidinyl and imidazolidinyl; or two adjacent R t They can be connected to form a benzene ring, a naphthalene ring or a three- to eight-membered aliphatic ring; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, canyl, norbornyl, phenyl, biphenyl and naphthyl. When substituted by multiple substituents, the multiple substituents are the same or different from each other.

[0137] More preferably, the formula b is selected from one of the structural groups shown:

[0138]

[0139]

[0140]

[0141] Preferably, the R b 、R c independently selected from hydrogen, deuterium, or any one of the following substituted or unsubstituted groups: C1-C6 alkyl, C3-C7 cycloalkyl, adamantyl, norbornyl, C6-C12 aryl, C2-C12 heteroaryl, benzocyclopentanyl, benzocyclohexanyl, benzocyclopentenyl, benzocyclohexenyl, naphthocyclopentanyl, naphthocyclohexanyl, naphthocyclopentenyl, and naphthocyclohexenyl; the “substituted or unsubstituted” substituent group is selected from any one or more of deuterium, C1-C12 alkyl, and C3-C12 cycloalkyl;

[0142] Or the R b 、R cAny of the following spirocyclic structures can be formed:

[0143]

[0144] The R p Selected from hydrogen, deuterium or substituted or unsubstituted groups: methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl, triphenylene, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, substituted groups are deuterium, methyl, ethyl, One or more of n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl, or adjacent R p can bond together to form benzene or naphthalene rings;

[0145] wherein p1 is selected from 0, 1 or 2; p2 is selected from 0, 1, 2, 3 or 4; p3 is selected from 0, 1, 2, 3, 4, 5 or 6; p4 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; p5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; p6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; and p7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0146] Preferably, the Any one selected from the following groups:

[0147]

[0148]

[0149]

[0150] wherein a is selected from 0, 1, 2 or 3; b is selected from 0, 1, 2, 3 or 4; c is selected from 0, 1, 2, 3, 4 or 5; e is selected from 0, 1, 2, 3, 4, 5 or 6; d is selected from 0, 1, 2, 3, 4, 5, 6 or 7; f is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; g is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; h is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; i is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

[0151] Preferably, the R a selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, oxazolidinyl, thiazole The above groups may also be substituted by one or more of deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphthyl, and deuterated biphenyl.

[0152] Preferably, the R a is selected from hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, or one of the following groups:

[0153]

[0154]

[0155] Preferably, the L a , L b , L c The same or different ones are selected from a single bond or any one of the structures shown below,

[0156]

[0157] Wherein, the R9 are the same or different and are selected from any one of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, and indenyl. The above groups may also be substituted by one or more of deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphthyl, and deuterated biphenyl;

[0158] The R4 are the same or different and are selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, diphenyl Any one of hydronaphthyl, indanyl, and indenyl, and the above groups may be further substituted by one or more of deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl, norbornyl, phenyl, naphthyl, biphenyl, terphenyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated phenyl, deuterated naphthyl, and deuterated biphenyl;

[0159] The k1 is selected from 0, 1, 2, 3 or 4, k2 is selected from 0, 1, 2, 3, 4, 5 or 6, k3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, k4 is selected from 0, 1, 2 or 3, k5 is selected from 0, 1 or 2, k6 is selected from 0, 1, 2, 3, 4 or 5; when k1, k2, k3, k4, k5, k6 is greater than 1, two or more R9 are the same or different.

[0160] Most preferably, the heterocyclic compound is selected from any one of the following chemical structures:

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175] The preparation method of the heterocyclic compound described in Formula II of the present invention can be prepared by conventional coupling reactions in the art, for example, by the following synthetic route, but the present invention is not limited thereto:

[0176]

[0177] The heterocyclic compound is subjected to Suzuki coupling reaction to finally obtain a compound of formula II, wherein Xa, Xb, Xc, Xd, Xe, Xf, and Xg independently represent Cl, Br, or I.

[0178] The present invention has no particular limitation on the sources of the raw materials used in the above-mentioned reactions. The present invention has no particular limitation on the above-mentioned reactions, and conventional reactions well known to those skilled in the art can be used.

[0179] The cathode is used to inject electrons into the electron injection / transport layer or the light-emitting layer, and can be formed as a reflective electrode using metals, alloys, conductive compounds, etc. with a low work function. The cathode can be formed using, for example, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The cathode can be formed as a thin film of a material having a thickness of about 20 nm or less, and can be formed as a transmissive electrode using ITO, IZO, etc. It can be prepared by forming a thin film by a method such as evaporation or sputtering, and the film thickness is generally 10 nm to 1 μm, preferably 50 to 200 nm.

[0180] The purpose of the cover layer material is to reduce total emission loss and waveguide loss in the OLED device, thereby improving light extraction efficiency. The cover layer material of the present invention can be selected from materials such as Alq3, TPBi, or other known materials suitable for the cover layer, or the triamine derivatives described in the present invention.

[0181] There is no particular limitation on the method for preparing and forming each layer in the organic light-emitting device. Any of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray coating, slit coating, and dip coating can be used. In the present invention, vacuum evaporation is preferably used.

[0182] The organic light-emitting device of the present invention can be widely used in the fields of panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal light, etc.

[0183] The present invention is explained in more detail by the following examples, but it is not intended that the present invention be limited thereby. Based on this description, those of ordinary skill in the art will be able to implement the present invention and prepare other compounds and devices according to the present invention within the disclosed entire range without inventive effort.

[0184] Preparation and characterization of compounds

[0185] Description of raw materials, reagents and characterization equipment:

[0186] The present invention has no particular limitation on the sources of the raw materials used in the following examples. The raw materials may be commercially available products or prepared using methods well known to those skilled in the art.

[0187] Mass spectrometry was performed using a British Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer, with chloroform as the solvent;

[0188] The elemental analysis was performed using a Vario EL cube organic element analyzer from Elementar, Germany, with a sample mass of 5 to 10 mg.

[0189] [Synthesis Example 1] Synthesis of Compound 8

[0190]

[0191] Synthesis of A1-8:

[0192] Under nitrogen, a1-8 (130.00 mmol, 20.41 g), intermediate b1-8 (140 mmol, 13.04 g), 1,1'-bis(diphenylphosphinoferrocene)palladium dichloride (1.30 mmol, 0.95 g), and sodium tert-butoxide (195.00 mmol, 18.74 g) were added to a reaction flask. Then, 350 mL of toluene was added and the reaction was heated under reflux 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 concentrated by distillation under reduced pressure. The mixture was recrystallized from ethyl acetate to obtain intermediate A1-8 (17.60 g, 80% yield). The solid purity was ≥99.29% as determined by HPLC. Mass spectrum: m / z: 169.0880 (theoretical value: 169.0891).

[0193] Synthesis of A2-8:

[0194] Following the same preparation method as A1-8, a1-8 was replaced with an equal molar amount of a2-8 to obtain A2-8 (30.34 g, 79% yield). The solid purity was ≥99.48% as determined by HPLC. Mass spectrum m / z: 295.1374 (theoretical value: 295.1361).

[0195] Synthetic B-8:

[0196] Under nitrogen, e-8 (45.00 mmol, 12.69 g), A2-8 (50.00 mmol, 14.77 g), palladium acetate (0.45 mmol, 0.10 g), tri-tert-butylphosphine (1.80 mL of a 0.5 M toluene solution, 0.90 mmol), sodium tert-butoxide (90.00 mmol, 8.65 g), and 200 ml of toluene were added to a reaction flask, stirred, and heated under reflux 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 concentrated by distillation under reduced pressure. The mixture was purified by silica gel column chromatography (dichloromethane:n-hexane = 1:4) to obtain B-8 (17.43 g, 78% yield). The solid purity was ≥99.65% as determined by HPLC. Mass spectrum: m / z: 495.1533 (theoretical value: 495.1521).

[0197] Synthesis of compound 8:

[0198] Under nitrogen, a reaction flask was added with B-8 (30.00 mmol, 14.89 g), A2-8 (65.00 mmol, 19.20 g), trisdibenzylideneacetone dipalladium (0.30 mmol, 0.27 g), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.60 mmol, 0.29 g), sodium tert-butoxide (60.00 mmol, 5.77 g), and 300 mL of toluene. The mixture was stirred and heated under reflux 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 concentrated by distillation under reduced pressure. The mixture was recrystallized from toluene to obtain compound 8 (17.60 g, 77% yield). The solid purity was ≥99.98% as determined by HPLC. Mass spectrum: m / z: 761.3785 (theoretical value: 761.3770). Theoretical element content (%) C 56 H 47 N3: C, 88.27; H, 6.22; N, 5.51. Measured element content (%): C, 88.23; H, 6.25; N, 5.53.

[0199] [Synthesis Example 2] Synthesis of Compound 22

[0200]

[0201] Following the same preparation method as in Synthesis Example 1, compound 22 (19.94 g) was obtained by replacing a1-8 with an equal molar amount of a1-22, a2-8 with an equal molar amount of a2-22, b1-8 with an equal molar amount of b2-22, and e-8 with an equal molar amount of e-22. The purity of the solid was ≥99.95% as determined by HPLC. Mass spectrum m / z: 885.5033 (theoretical value: 885.5022). Theoretical element content (%): C 65 H 63 N3: C, 88.09; H, 7.17; N, 4.74. Measured element content (%): C, 88.05; H, 7.18; N, 4.77.

[0202] [Synthesis Example 3] Synthesis of Compound 49

[0203]

[0204] Synthesis of A1-49:

[0205] Following the same preparation method as for A1-8 in Example 1, replacing a1-8 with an equal molar amount of a1-49 and b1-8 with an equal molar amount of b1-49, A1-49 (26.29 g, 78% yield) was obtained. HPLC analysis of the solid revealed a purity of ≥99.46%. Mass spectrum: m / z: 259.1355 (theoretical value: 259.1364).

[0206] Synthesis of compound 49:

[0207] Under nitrogen, e-49 (30.00 mmol, 5.86 g), A1-49 (95.00 mmol, 24.64 g), trisdibenzylideneacetone dipalladium (0.40 mmol, 0.37 g), tri-tert-butylphosphine (1.40 mL of a 0.5 M toluene solution, 0.70 mmol), sodium tert-butoxide (70.00 mmol, 6.73 g), and 350 ml of toluene were added to a reaction flask, stirred, and heated under reflux 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 concentrated by vacuum distillation. The compound was recrystallized from toluene to obtain compound 49 (20.48 g, 79% yield). The solid purity was ≥99.96% as determined by HPLC. Mass spectrum m / z: 863.4248 (theoretical value: 863.4239). Theoretical element content (%) C 64 H 53 N3: C, 88.96; H, 6.18; N, 4.86. Measured element content (%): C, 88.99; H, 6.16; N, 4.85.

[0208] [Synthesis Example 4] Synthesis of Compound 66

[0209]

[0210] Following the same preparation method as in Synthesis Example 3, a1-49 was replaced with an equal molar amount of a1-66, and b1-49 was replaced with an equal molar amount of b1-8 to obtain compound 66 (19.73 g). The solid purity was ≥99.95% as determined by HPLC. Mass spectrum m / z: 821.3785 (theoretical value: 821.3770). Theoretical element content (%): C 61 H 47 N3: C, 89.13; H, 5.76; N, 5.11. Measured element content (%): C, 89.15; H, 5.73; N, 5.13.

[0211] [Synthesis Example 5] Synthesis of Compound 69

[0212]

[0213] Following the same preparation method as in Synthesis Example 3, a1-49 was replaced with an equal molar amount of a1-66, and b1-49 was replaced with an equal molar amount of b1-69 to obtain compound 69 (21.10 g). The solid purity was ≥99.97% as determined by HPLC. Mass spectrum m / z: 989.5661 (theoretical value: 989.5648). Theoretical element content (%): C 73 H 71 N3: C, 88.53; H, 7.23; N, 4.24. Measured element content (%): C, 88.55; H, 7.25; N, 4.20.

[0214] [Synthesis Example 6] Synthesis of Compound 85

[0215]

[0216] Following the same preparation method as in Synthesis Example 3, a1-49 was replaced with an equal molar amount of a2-22, and b1-49 was replaced with an equal molar amount of b1-85 to obtain compound 85 (21.43 g). The solid purity was ≥99.98% as determined by HPLC. Mass spectrum m / z: 1049.4718 (theoretical value: 1049.4709). Theoretical element content (%): C 79 H 59 N3: C, 90.34; H, 5.66; N, 4.00. Measured element content (%): C, 90.33; H, 5.65; N, 4.02.

[0217] [Synthesis Example 7] Synthesis of Compound 175

[0218]

[0219] Following the same preparation method as in Synthesis Example 3, compound 175 (19.12 g) was obtained by replacing a1-49 with an equal molar amount of a1-66, b1-49 with an equal molar amount of b1-8, and e-49 with an equal molar amount of e-175. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum m / z: 849.4097 (theoretical value: 849.4083). Theoretical element content (%): C 63 H 51 N3: C, 89.01; H, 6.05; N, 4.94. Equimolar measured element content (%): C, 89.04; H, 6.04; N, 4.92.

[0220] [Synthesis Example 8] Synthesis of Compound 232

[0221]

[0222] Compound 232 (19.03 g) was obtained by the same preparation method as in Synthesis Example 1, except that a1-8 was replaced with an equal molar amount of a1-69, a2-8 was replaced with an equal molar amount of a2-232, b1-8 was replaced with an equal molar amount of b1-49, and e-8 was replaced with an equal molar amount of e-232. The purity of the solid was ≥99.96% as determined by HPLC. Mass spectrum m / z: 905.4718 (theoretical value: 905.4709). Theoretical element content (%): C 67 H 59 N3: C, 88.80; H, 6.56; N, 4.64. Measured element content (%): C, 88.85; H, 6.51; N, 4.63.

[0223] [Synthesis Example 9] Synthesis of Compound 242

[0224]

[0225] Following the same preparation method as in Synthesis Example 1, compound 242 (19.05 g) was obtained by replacing a2-8 with an equal molar amount of a2-242, b1-8 with an equal molar amount of b1-49, and e-8 with an equal molar amount of e-232. The purity of the solid was ≥99.94% as determined by HPLC. Mass spectrum: m / z: 857.4720 (theoretical value: 857.4709). Theoretical element content (%): C 63 H 59 N3: C, 88.17; H, 6.93; N, 4.90. Measured element content (%): C, 88.15; H, 6.90; N, 4.95.

[0226] [Synthesis Example 10] Synthesis of Compound 246

[0227]

[0228] Following the same preparation method as in Synthesis Example 1, compound 246 (18.34 g) was obtained by replacing a1-8 with an equal molar amount of a1-66, a2-8 with an equal molar amount of a2-246, and e-8 with an equal molar amount of e-232. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum: m / z: 773.3785 (theoretical value: 773.3770). Theoretical element content (%): C 57 H 47 N3: C, 88.45; H, 6.12; N, 5.43. Measured element content (%): C, 88.42; H, 6.18; N, 5.40.

[0229] [Synthesis Example 11] Synthesis of Compound 259

[0230]

[0231] Compound 259 (18.86 g) was obtained by the same preparation method as in Synthesis Example 1, except that a1-8 was replaced with an equal molar amount of a1-66, b1-8 was replaced with an equal molar amount of b1-49, a2-8 was replaced with an equal molar amount of a1-8, and e-8 was replaced with an equal molar amount of e-232. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum m / z: 897.4072 (theoretical value: 897.4083). Theoretical element content (%): C 67 H 51 N3: C, 88.60; H, 5.72; N, 4.68. Measured element content (%): C, 88.65; H, 5.70; N, 4.65.

[0232] [Synthesis Example 12] Synthesis of Compound 269

[0233]

[0234] Following the same preparation method as in Synthesis Example 1, compound 269 (19.34 g) was obtained by replacing a1-8 with an equal molar amount of a1-66, a2-8 with an equal molar amount of a2-269, and e-8 with an equal molar amount of e-232. The purity of the solid was ≥99.98% as determined by HPLC. Mass spectrum: m / z: 795.3623 (theoretical value: 795.3613). Theoretical element content (%): C 59 H 45 N3: C, 89.02; H, 5.70; N, 5.28. Measured element content (%): C, 89.05; H, 5.74; N, 5.21.

[0235] [Synthesis Example 13] Synthesis of Compound 278

[0236]

[0237] Following the same preparation method as in Synthesis Example 1, compound 278 (22.65 g, 73%) was obtained by replacing a1-8 with an equal molar amount of a1-278, a2-8 with an equal molar amount of a2-278, and e-8 with an equal molar amount of e-232. The purity of the solid was ≥99.95% as determined by HPLC. Mass spectrum: m / z: 1033.5325 (theoretical value: 1033.5335). Theoretical element content (%): C 77 H 67 N3: C, 89.41; H, 6.53; N, 4.06. Measured element content (%): C, 89.47; H, 6.51; N, 4.03.

[0238] [Synthesis Example 14] Synthesis of Compound 306

[0239]

[0240] Following the same preparation method as in Synthesis Example 1, compound 306 (21.63 g) was obtained by replacing a1-8 with an equal molar amount of a1-306, a2-8 with an equal molar amount of a1-8, and e-8 with an equal molar amount of e-232. The purity of the solid was ≥99.94% as determined by HPLC. Mass spectrum m / z: 897.4094 (theoretical value: 897.4083). Theoretical element content (%): C 67 H 51 N3: C, 89.60; H, 5.72; N, 4.68. Measured element content (%): C, 89.63; H, 5.70; N, 4.66.

[0241] [Synthesis Example 15] Synthesis of Compound 317

[0242]

[0243] Following the same preparation method as in Synthesis Example 1, compound 317 (23.06 g) was obtained by replacing a1-8 with an equal molar amount of a1-317, a2-1 with an equal molar amount of a2-237, and e-8 with an equal molar amount of e-232. The purity of the solid was ≥99.98% as determined by HPLC. Mass spectrum: m / z: 997.4388 (theoretical value: 997.4396). Theoretical element content (%): C 75 H 55 N3: C, 90.24; H, 5.55; N, 4.21. Measured element content (%): C, 90.28; H, 5.51; N, 4.21.

[0244] [Synthesis Example 16] Synthesis of Compound 343

[0245]

[0246] Following the same preparation method as in Synthesis Example 1, compound 343 (19.24 g) was obtained by replacing a2-8 with an equal molar amount of a2-343 and e-8 with an equal molar amount of e-343. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum m / z: 821.3785 (theoretical value: 821.3770). Theoretical element content (%): C 61 H 47 N3: C, 89.13; H, 5.76; N, 5.11. Measured element content (%): C, 89.15; H, 5.77; N, 5.08.

[0247] [Synthesis Example 17] Synthesis of Compound 351

[0248]

[0249] Following the same preparation method as in Synthesis Example 1, compound 351 (19.67 g) was obtained by replacing a1-8 with an equal molar amount of a1-66, a2-8 with an equal molar amount of a2-351, and e-8 with an equal molar amount of e-343. The purity of the solid was ≥99.96% as determined by HPLC. Mass spectrum m / z: 897.4095 (theoretical value: 897.4083). Theoretical element content (%): C 67 H 51 N3: C, 89.60; H, 5.72; N, 4.68. Measured element content (%): C, 89.63; H, 5.74; N, 4.63.

[0250] [Synthesis Example 18] Synthesis of Compound 367

[0251]

[0252] Compound 367 (21.27 g) was obtained by the same preparation method as in Synthesis Example 1, except that a1-8 was replaced with an equal molar amount of a2-22, a2-8 was replaced with an equal molar amount of a2-367, and e-8 was replaced with an equal molar amount of e-367. The purity of the solid was ≥99.95% as determined by HPLC. Mass spectrum: m / z: 885.4071 (theoretical value: 885.4083). Theoretical element content (%): C 66 H 51 N3: C, 89.46; H, 5.80; N, 4.74. Measured element content (%): C, 89.43; H, 5.85; N, 4.72.

[0253] [Synthesis Example 19] Synthesis of Compound 413

[0254]

[0255] Following the same preparation method as in Synthesis Example 1, compound 413 (21.00 g) was obtained by replacing a1-8 with an equal molar amount of a1-66, a2-8 with an equal molar amount of a2-413, and e-8 with an equal molar amount of e-413. The purity of the solid was ≥99.98% as determined by HPLC. Mass spectrum: m / z: 885.4091 (theoretical value: 885.4083). Theoretical element content (%): C 66 H 51 N3: C, 89.46; H, 5.80; N, 4.74. Measured element content (%): C, 89.47; H, 5.85; N, 4.68.

[0256] [Synthesis Example 20] Synthesis of Compound 421

[0257]

[0258] Following the same preparation method as in Synthesis Example 1, compound 421 (22.24 g) was obtained by replacing b1-8 with an equal molar amount of b2-22, a2-8 with an equal molar amount of a2-421, and e-8 with an equal molar amount of e-413. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum m / z: 987.4541 (theoretical value: 987.4552). Theoretical element content (%): C 74 H 57 N3: C, 89.93; H, 5.81; N, 4.25. Measured element content (%): C, 89.95; H, 5.85; N, 4.20.

[0259] [Synthesis Example 21] Synthesis of Compound 502

[0260]

[0261] Following the same preparation method as in Synthesis Example 1, compound 502 (21.21 g) was obtained by replacing a1-8 with an equal molar amount of a1-66, a2-8 with an equal molar amount of a2-502, and e-8 with an equal molar amount of e-232. The purity of the solid was ≥99.96% as determined by HPLC. Mass spectrum m / z: 897.4096 (theoretical value: 897.4083). Theoretical element content (%): C 67 H 51 N3: C, 89.60; H, 5.72; N, 4.68. Measured element content (%): C, 89.58; H, 5.75; N, 4.67.

[0262] [Synthesis Example 22] Synthesis of Compound 504

[0263]

[0264] Following the same preparation method as in Synthesis Example 3, a1-49 was replaced with an equal molar amount of a2-269, and b1-49 was replaced with an equal molar amount of b1-504 to obtain Compound 504 (18.68 g). HPLC analysis of the solid showed a purity of ≥99.95%. Mass spectrum m / z: 893.3783 (theoretical value: 893.3770). Theoretical element content (%): C 67 H 47 N3: C, 90.00; H, 5.30; N, 4.70. Measured element content (%): C, 90.02; H, 5.26; N, 4.72.

[0265] [Synthesis Example 23] Synthesis of Compound 506

[0266]

[0267] Following the same preparation method as in Synthesis Example 1, compound 506 (19.21 g) was obtained by replacing a2-8 with an equal molar amount of a1-8, b1-8 with an equal molar amount of b2-506, and e-8 with an equal molar amount of e-232. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum: m / z: 743.3312 (theoretical value: 743.3300). Theoretical element content (%): C 55 H 41 N3: C, 88.80; H, 5.56; N, 5.65. Measured element content (%): C, 88.83; H, 5.55; N, 5.62.

[0268] [Synthesis Example 24] Synthesis of Compound 507

[0269]

[0270] Following the same preparation method as in Synthesis Example 1, compound 507 (16.40 g) was obtained by replacing a1-8 with an equal molar amount of a1-66, a2-8 with an equal molar amount of a1-8, and e-8 with an equal molar amount of e-507. The purity of the solid was ≥99.97% as determined by HPLC. Mass spectrum: m / z: 759.3624 (theoretical value: 759.3613). Theoretical element content (%): C 56 H 45 N3: C, 88.50; H, 5.97; N, 5.53. Measured element content (%): C, 88.53; H, 5.95; N, 5.52.

[0271] [Synthesis Example 25] Synthesis of Compound 511

[0272]

[0273] Intermediate A1-8, intermediate A1-66, and intermediate A3-511 were prepared by the same method as that for Intermediate A1-8 in Synthesis Example 1.

[0274] Synthetic B-511:

[0275] Under nitrogen protection, e-511 (80.00 mmol, 26.51 g), A1-66 (85.00 mmol, 20.85 g), palladium acetate (0.80 mmol, 0.18 g), tri-tert-butylphosphine (3.00 mL of a 0.5 M toluene solution, 1.50 mmol), sodium tert-butoxide (200.00 mmol, 19.22 g) and 300 mL of toluene were added to the reaction flask, stirred and mixed, and heated under reflux 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 concentrated by distillation under reduced pressure. The mixture was purified by silica gel column chromatography (dichloromethane: n-hexane = 1:4) to obtain B-511 (24.41 g, yield 68%). The solid purity was ≥99.68% as determined by HPLC. Mass spectrum m / z: 447.0398 (theoretical value: 447.0389).

[0276] Synthesis of C-511:

[0277] Under nitrogen, B-511 (50.00 mmol, 22.44 g), A1-8 (55.00 mmol, 9.31 g), palladium acetate (0.75 mmol, 0.17 g), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (1.50 mmol, 0.72 g), sodium tert-butoxide (100.00 mmol, 9.61 g) and 300 mL of toluene were added to the reaction flask, stirred, and heated under reflux 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 concentrated by distillation under reduced pressure. The mixture was purified by silica gel column chromatography (dichloromethane: petroleum ether = 3:8) to obtain C-511 (20.95 g, yield 78%). The solid purity was ≥99.77% as determined by HPLC. Mass spectrum m / z: 536.2044 (theoretical value: 536.2019).

[0278] Synthesis of compound 511:

[0279] Under nitrogen, a reaction flask was added with C-511 (30.00 mmol, 16.11 g), A3-511 (35.00 mmol, 11.25 g), trisdibenzylideneacetone dipalladium (0.30 mmol, 0.28 g), tri-tert-butylphosphine (1.20 mL of a 0.5 M toluene solution, 0.60 mmol), sodium tert-butoxide (60.00 mmol, 5.77 g), and 150 ml of toluene. The mixture was stirred and heated under reflux 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 concentrated by distillation under reduced pressure. The mixture was recrystallized from toluene to obtain compound 511 (19.72 g, 80% yield). The solid purity was ≥99.95% as determined by HPLC. Mass spectrum: m / z: 821.3754 (theoretical value: 821.3770). Theoretical element content (%) C 61 H 47 N3: C, 89.13; H, 5.76; N, 5.11. Measured element content (%): C, 89.17; H, 5.73; N, 5.10.

[0280] [Synthesis Example 26] Synthesis of Compound 517

[0281]

[0282] Following the same preparation method as in Synthesis Example 3, a1-49 was replaced with an equal molar amount of a2-269, and b1-49 was replaced with an equal molar amount of b1-8 to obtain compound 517 (16.29 g). HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum m / z: 743.3320 (theoretical value: 743.3300). Theoretical element content (%): C 55 H 41 N3: C, 88.80; H, 5.56; N, 5.65. Measured element content (%): C, 88.83; H, 5.55; N, 5.63.

[0283] [Synthesis Example 27] Synthesis of Compound 520

[0284]

[0285] Following the same preparation method as in Synthesis Example 3, a1-49 was replaced with an equal molar amount of a1-66, b1-49 was replaced with an equal molar amount of b1-8, and e-49 was replaced with an equal molar amount of e-520 to obtain Compound 520 (18.14 g). The purity of the solid was ≥99.92% as determined by HPLC. Mass spectrum m / z: 863.4248 (theoretical value: 863.4239). Theoretical element content (%): C 64 H 53N3: C, 88.96; H, 6.18; N, 4.86. Equimolar measured element content (%): C, 88.99; H, 6.16; N, 4.85.

[0286] [Synthesis Example 28] Synthesis of Compound 2-67

[0287]

[0288] Preparation of intermediate F-67:

[0289] Under nitrogen, to a reaction flask were added starting material f-67 (120.00 mmol, 38.79 g), starting material g-67 (125.00 mmol, 19.55 g), Pd(PPh3)4 (2.50 mmol, 2.89 g), K2CO3 (240.00 mmol, 33.17 g), 360 mL of toluene, 120 mL of ethanol, and 120 mL of water. The mixture was stirred and heated under reflux for 3 hours. After the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene / ethanol (4:1) to obtain intermediate F-67 (37.05 g, 87% yield). HPLC purity was ≥98.32%. Mass spectrum: m / z: 354.1162 (theoretical value: 354.1175).

[0290] Preparation of intermediate G-67:

[0291] Under nitrogen, intermediate F-67 (100.00 mmol, 35.49 g), starting material h-67 (105.00 mmol, 26.66 g), Pd(dppf)Cl2 (1.50 mmol, 1.10 g), KOAc (200.00 mmol, 19.63 g), and 1,4-dioxane (500 mL) were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 5.5 hours. After completion of the reaction, the mixture was cooled to room temperature, 700 mL of distilled water was added, and the mixture was extracted with ethyl acetate (350 mL x 3). The organic layer was dried over anhydrous MgSO4, the ethyl acetate was removed by rotary evaporation, and the mixture was recrystallized from toluene to obtain intermediate G-67 (35.71 g, 80% yield); HPLC purity ≥98.61%. Mass spectrum: m / z: 446.2428 (theoretical value: 446.2417).

[0292] Preparation of intermediate H-67:

[0293] Under nitrogen, intermediate G-67 (75.00 mmol, 33.48 g), starting material i-67 (80.00 mmol, 18.07 g), Pd(dppf)Cl2 (1.30 mmol, 0.95 g), Na2CO3 (150.00 mmol, 15.90 g), 240 mL of toluene, 80 mL of ethanol, and 80 mL of water were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 7.5 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene / ethanol (8:1) to obtain intermediate H-67 (27.23 g, 78% yield). HPLC purity was ≥98.84%. Mass spectrum: m / z: 464.1085 (theoretical value: 464.1099).

[0294] Preparation of intermediate I-67:

[0295] Under nitrogen, intermediate H-67 (55.00 mmol, 25.60 g), starting material H-67 (115.00 mmol, 29.20 g), Pd(dppf)Cl2 (1.00 mmol, 0.73 g), KOAc (110.00 mmol, 10.80 g), and 1,4-dioxane (600 mL) were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 8 hours. After the reaction, the mixture was cooled to room temperature and 900 mL of distilled water was added. The mixture was then extracted with ethyl acetate (350 mL x 3). The organic layer was dried over anhydrous MgSO4, the ethyl acetate was removed by rotary evaporation, and the mixture was recrystallized from toluene and dried to afford intermediate I-67 (28.53 g, 80% yield). HPLC purity was ≥99.56%. Mass spectrum: m / z: 648.3595 (theoretical value: 648.3582).

[0296] Preparation of compound 2-67:

[0297] Under nitrogen, intermediate I-67 (35.00 mmol, 22.70 g), starting material j-67 (75.00 mmol, 11.52 g), Pd2(dba)3 (0.60 mmol, 0.55 g), P(t-Bu)3 (1.20 mmol, 2.40 ml of a 0.5 M toluene solution), K2CO3 (70.00 mmol, 9.67 g), and 150 ml of tetrahydrofuran were added to a reaction flask in sequence. The mixture was stirred and heated under reflux for 9 hours. After the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene to obtain compound 2-67 (17.44 g, 79% yield); HPLC purity ≥99.95%. Mass spectrum m / z: 630.2320 (theoretical value: 630.2307). Theoretical element content (%) C 45 H 30 N2O2: C, 85.69; H, 4.79; N, 4.44. Measured element content (%): C, 85.71; H, 4.78; N, 4.47.

[0298] [Synthesis Example 29] Synthesis of Compound 2-85

[0299]

[0300] Following the preparation method of Synthesis Example 28, F-67 was replaced with an equal molar amount of F-85 to obtain compound 2-85 (17.82 g, 81% yield); HPLC purity ≥ 99.97%. Mass spectrum m / z: 628.2163 (theoretical value: 628.2151). Theoretical element content (%) C 45 H 28 N2O2: C, 85.97; H, 4.49; N, 4.46. Measured element content (%): C, 85.95; H, 4.47; N, 4.47.

[0301] [Synthesis Example 30] Synthesis of Compound 2-90

[0302]

[0303] According to the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-90 to obtain compound 2-90 (17.61 g); HPLC purity ≥ 99.98%. Mass spectrum m / z: 670.2283 (theoretical value: 670.2256). Theoretical element content (%) C 47 H 30 N2O3: C, 84.16; H, 4.51; N, 4.18. Measured element content (%): C, 84.17; H, 4.52; N, 4.15.

[0304] [Synthesis Example 31] Synthesis of Compound 2-95

[0305]

[0306] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-95 to obtain compound 2-95 (19.27 g, 77% yield); HPLC purity ≥ 99.97%. Mass spectrum m / z: 714.3233 (theoretical value: 714.3246). Theoretical element content (%) C 51 H 42 N2O2: C, 85.68; H, 5.92; N, 3.92. Measured element content (%): C, 85.67; H, 5.93; N, 3.91.

[0307] [Synthesis Example 32] Synthesis of Compound 2-102

[0308]

[0309] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-102, and j-67 was replaced with an equal molar amount of j-102 to obtain compound 2-102 (19.12 g); HPLC purity ≥ 99.96%. Mass spectrum m / z: 718.2918 (theoretical value: 718.2901). Theoretical element content (%) C 47 H 18 D 10 N6O2: C, 78.53; H, 5.33; N, 11.69. Measured element content (%): C, 78.55; H, 5.38; N, 11.63.

[0310] [Synthesis Example 33] Synthesis of Compound 2-136

[0311]

[0312] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-136, and j-67 was replaced with an equal molar amount of j-136 to obtain compound 2-136 (18.02 g); HPLC purity ≥ 99.96%. Mass spectrum m / z: 714.3133 (theoretical value: 714.3122). Theoretical element content (%) C 51 H 26 D8N2O2: C, 85.69; H, 5.92; N, 3.92. Measured element content (%): C, 85.66; H, 5.91; N, 3.95.

[0313] [Synthesis Example 34] Synthesis of Compound 2-164

[0314]

[0315] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-164, and j-67 was replaced with an equal molar amount of j-164 to obtain compound 2-164 (21.79 g); HPLC purity ≥ 99.98%. Mass spectrum m / z: 914.3885 (theoretical value: 914.3872). Theoretical element content (%) C 67 H 50 N2O2: C, 87.94; H, 5.51; N, 3.06. Measured element content (%): C, 87.91; H, 5.53; N, 3.08.

[0316] [Synthesis Example 35] Synthesis of Compound 2-180

[0317]

[0318]

[0319] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-180, and j-67 was replaced with an equal molar amount of j-180 to obtain compound 2-180 (18.73 g); HPLC purity ≥ 99.97%. Mass spectrum m / z: 732.2756 (theoretical value: 732.2777). Theoretical element content (%) C 53 H 36 N2O2: C, 86.86; H, 4.95; N, 3.82. Measured element content (%): C, 86.83; H, 4.96; N, 3.81.

[0320] [Synthesis Example 36] Synthesis of Compound 2-258

[0321]

[0322] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-180, and g-67 was replaced with an equal molar amount of g-258 to obtain compound 2-258 (15.68 g); HPLC purity ≥ 99.95%. Mass spectrum m / z: 581.2123 (theoretical value: 581.2103). Theoretical element content (%) C 40 H 27 N3O2: C, 82.60; H, 4.68; N, 7.22. Measured element content (%): C, 82.63; H, 4.66; N, 7.23.

[0323] [Synthesis Example 37] Synthesis of Compound 2-269

[0324]

[0325] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-269, and g-67 was replaced with an equal molar amount of g-269 to obtain compound 2-269 (20.90 g); HPLC purity ≥ 99.97%. Mass spectrum m / z: 755.2585 (theoretical value: 755.2573). Theoretical element content (%) C 54 H 33 N3O2: C, 85.81; H, 4.40; N, 5.56. Measured element content (%): C, 85.85; H, 4.41; N, 5.53.

[0326] [Synthesis Example 38] Synthesis of Compound 2-297

[0327]

[0328] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-297, and g-67 was replaced with an equal molar amount of g-297 to obtain compound 2-297 (19.76 g, 75% yield); HPLC purity ≥ 99.96%. Mass spectrum m / z: 752.2473 (theoretical value: 752.2464). Theoretical element content (%): C 55 H 32 N2O2: C, 87.74; H, 4.28; N, 3.72. Measured element content (%): C, 87.77; H, 4.23; N, 3.71.

[0329] [Synthesis Example 39] Synthesis of Compound 2-308

[0330]

[0331] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-180, and g-67 was replaced with an equal molar amount of g-308 to obtain compound 2-308 (17.01 g); HPLC purity ≥ 99.97%. Mass spectrum m / z: 656.2423 (theoretical value: 656.2464). Theoretical element content (%) C 47 H 32 N2O2: C, 85.95; H, 4.91; N, 4.27. Measured element content (%): C, 85.92; H, 4.92; N, 4.29.

[0332] [Synthesis Example 40] Synthesis of Compound 2-345

[0333]

[0334] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-180, and g-67 was replaced with an equal molar amount of g-345 to obtain compound 2-345 (19.02 g); HPLC purity ≥ 99.98%. Mass spectrum m / z: 696.2788 (theoretical value: 696.2777). Theoretical element content (%) C 50 H 36 N2O2: C, 86.18; H, 5.21; N, 4.02. Measured element content (%): C, 86.23; H, 5.23; N, 4.00.

[0335] [Synthesis Example 41] Synthesis of Compound 2-355

[0336]

[0337] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-180, and g-67 was replaced with an equal molar amount of g-355 to obtain compound 2-355 (16.90 g); HPLC purity ≥ 99.97%. Mass spectrum m / z: 670.2244 (theoretical value: 670.2256). Theoretical element content (%) C 47 H 30 N2O3: C, 84.16; H, 4.51; N, 4.18. Measured element content (%): C, 84.18; H, 4.53; N, 4.16.

[0338] [Synthesis Example 42] Synthesis of Compound 2-360

[0339]

[0340] Preparation of intermediate F-360:

[0341] Under nitrogen, a reaction flask was charged with starting material f-360 (260.00 mmol, 94.98 g), starting material g-67 (270.00 mmol, 42.22 g), Pd(PPh3)4 (5.00 mmol, 5.78 g), K2CO3 (520.00 mmol, 71.87 g), 720 mL of toluene, 240 mL of ethanol, and 240 mL of water. The mixture was stirred and heated under reflux for 4 hours. After the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene / ethanol (5:1) to obtain intermediate F-360 (90.82 g, 88% yield). HPLC purity was ≥98.14%. Mass spectrum: m / z: 396.1658 (theoretical value: 396.1645).

[0342] Preparation of intermediate G-360:

[0343] Under nitrogen, intermediate F-360 (210.00 mmol, 83.36 g), starting material h-67 (215.00 mmol, 54.60 g), Pd(dppf)Cl2 (4.00 mmol, 2.93 g), KOAc (420.00 mmol, 41.22 g), and 1,4-dioxane (800 mL) were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, 900 mL of distilled water was added, and then extracted with ethyl acetate (500 mL x 3). The organic layer was dried over anhydrous MgSO4, the ethyl acetate was removed by rotary evaporation, and then recrystallized from toluene to obtain intermediate G-360 (84.12 g, 82% yield); HPLC purity ≥98.46%. Mass spectrum: m / z: 488.2878 (theoretical value: 488.2887).

[0344] Preparation of intermediate H-360:

[0345] Under nitrogen, intermediate G-360 (160.00 mmol, 78.16 g), starting material i-360 (165.00 mmol, 52.36 g), Pd(dppf)Cl2 (3.50 mmol, 2.56 g), Na2CO3 (320.00 mmol, 33.92 g), 480 mL of toluene, 160 mL of ethanol, and 160 mL of water were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 8 hours. After the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene / ethanol (8:1) to obtain intermediate H-360 (69.77 g, 79% yield). HPLC purity was ≥98.78%. Mass spectrum: m / z: 550.1074 (theoretical value: 550.1063).

[0346] Preparation of intermediate I-360:

[0347] Under nitrogen, intermediate H-360 (120.00 mmol, 66.23 g), starting material h-67 (250.00 mmol, 63.49 g), Pd(dppf)Cl2 (2.00 mmol, 1.46 g), KOAc (240.00 mmol, 23.55 g), and 1,4-dioxane (800 mL) were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 9 hours. After the reaction, the mixture was cooled to room temperature and 1000 mL of distilled water was added. The mixture was then extracted with ethyl acetate (350 mL x 3). The organic layer was dried over anhydrous MgSO4, the ethyl acetate was removed by rotary evaporation, and the mixture was recrystallized from toluene and dried to afford intermediate I-360 (57.51 g, 80% yield). HPLC purity was ≥99.13%. Mass spectrum: m / z: 598.2823 (theoretical value: 598.2810).

[0348] Preparation of intermediate J-360:

[0349] Under nitrogen, intermediate I-360 (80.00 mmol, 47.93 g), starting material J-67 (85.00 mmol, 13.05 g), Pd(dba) (1.60 mmol, 1.47 g), P(t-Bu) (3.20 mmol, 6.40 ml of a 0.5 M solution in toluene), KCO (160.00 mmol, 22.11 g), and 300 ml of tetrahydrofuran were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 9 hours. After the reaction, the mixture was cooled to room temperature and filtered to obtain a filter cake, which was rinsed with ethanol and recrystallized from toluene to obtain intermediate J-360 (36.35 g, 77% yield). HPLC purity was ≥99.47%. Mass spectrum: m / z: 589.2185 (theoretical value: 589.2172).

[0350] Preparation of intermediate K-360:

[0351] Under nitrogen, intermediate J-360 (60.00 mmol, 35.41 g), starting material h-67 (65.00 mmol, 16.51 g), Pd(dppf)Cl2 (1.00 mmol, 0.73 g), KOAc (120.00 mmol, 11.78 g), and 1,4-dioxane (600 mL) were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 5.5 hours. After completion of the reaction, the mixture was cooled to room temperature, 700 mL of distilled water was added, and the mixture was extracted with ethyl acetate (350 mL x 3). The organic layer was dried over anhydrous MgSO4, the ethyl acetate was removed by rotary evaporation, and the mixture was recrystallized from toluene to obtain intermediate K-360 (30.27 g, 74% yield); HPLC purity ≥99.78%. Mass spectrum: m / z: 681.3423 (theoretical value: 681.3414).

[0352] Preparation of compound 2-360:

[0353] Following the preparation method of Synthesis Example 28, I-67 was replaced with an equal molar amount of K-360, and j-67 was replaced with an equal molar amount of j-360 to obtain compound 2-360 (19.69 g, 75% yield); HPLC purity ≥ 99.97%. Mass spectrum m / z: 749.3051 (theoretical value: 749.3042). Theoretical element content (%) C 53 H 39 N3O2: C, 84.89; H, 5.24; N, 5.60. Measured element content (%): C, 84.91; H, 5.23; N, 5.61.

[0354] [Synthesis Example 43] Synthesis of Compound 2-362

[0355]

[0356] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-269, g-67 was replaced with an equal molar amount of g-632, and j-67 was replaced with an equal molar amount of j-362 to obtain compound 2-362 (21.40 g); HPLC purity ≥ 99.98%. Mass spectrum m / z: 860.3351 (theoretical value: 860.3341). Theoretical element content (%) C 63 H 36 D4N2O2: C, 87.88; H, 5.15; N, 3.25. Measured element content (%): C, 87.85; H, 5.18; N, 3.23. [Synthesis Example 44] Synthesis of Compound 2-409

[0357]

[0358] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-409, g-67 was replaced with an equal molar amount of g-409, and j-67 was replaced with an equal molar amount of j-409 to obtain compound 2-409 (20.82 g); HPLC purity ≥ 99.96%. Mass spectrum m / z: 792.2388 (theoretical value: 792.2381). Theoretical element content (%): C 53 H 36 N4S2: C, 80.27; H, 4.58; N, 7.07. Measured element content (%): C, 80.28; H, 4.59; N, 7.03.

[0359] [Synthesis Example 45] Synthesis of Compound 2-486

[0360]

[0361] Following the preparation method of Synthesis Example 28, f-67 was replaced with an equal molar amount of f-486, g-67 was replaced with an equal molar amount of g-486, and j-67 was replaced with an equal molar amount of j-486 to obtain compound 2-486 (21.97 g, 68% yield); HPLC purity ≥ 99.97%. Mass spectrum m / z: 922.4043 (theoretical value: 922.4035). Theoretical element content (%) C 68 H 50 N4: C, 88.47; H, 5.46; N, 6.07. Measured element content (%): C, 88.45; H, 5.47; N, 6.08.

[0362] Red organic light-emitting device (hole transport layer)

[0363] [Comparative Example 1-2] Device Preparation Example:

[0364] Comparative Example 1: Preparation of an organic light-emitting device using vacuum thermal evaporation. The experimental steps were as follows: The ITO substrate was rinsed three times in distilled water, ultrasonically cleaned for 15 minutes, and then ultrasonically cleaned with isopropyl alcohol, acetone, and methanol, sequentially. The substrate was then dried at 120°C and placed in a vapor deposition machine.

[0365] On the prepared ITO transparent electrode, a hole injection layer HI / 60nm, a hole transport layer HT-1 / 80nm, a main body H-1:H-2: doped Ir(piq)2acac (mass ratio 49%:49%:2% mixed) / 30nm, and then an electron transport layer Alq3 and Liq (doping ratio is 1:1 by mass) / 28nm, an electron injection layer LiF / 1nm, and a cathode Al / 120nm were evaporated by vacuum evaporation layer by layer. The device was sealed in a glove box to prepare an organic light-emitting device. After completing the production of the organic light-emitting device according to the above steps, the photoelectric performance of the device was measured. The molecular structure formula of the relevant materials is shown below:

[0366]

[0367] Comparative Example 2: The hole transport layer material HT-1 in Comparative Example 1 was replaced with HT-2, and the organic light-emitting device of Comparative Example 2 was manufactured in the same manner as Comparative Example 1.

[0368] [Application Examples 1-27]

[0369] Application Examples 1-27: The hole transport layer material HT-1 of the organic light-emitting device is replaced with compounds 8, 22, 49, 66, 69, 85, 175, 232, 242, 246, 259, 269, 278, 306, 317, 343, 351, 367, 413, 421, 502, 504, 506, 507, 511, 517, and 520 of the present invention in turn, and the other steps are the same as those in Comparative Example 1.

[0370] A combined IVL testing system, comprised of test software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectral scanning luminance meter, was used to test the luminous efficiency of organic light-emitting devices. Lifespan testing was performed using a McScience M6000 OLED Lifespan Test System. The test was conducted in an ambient atmosphere at room temperature. The luminescence characteristics of the resulting organic light-emitting devices are shown in Table 1. Table 1 shows the luminescence characteristics of light-emitting devices prepared using the compounds of the present invention and comparative materials.

[0371] [Table 1] Luminous characteristics test of light-emitting devices

[0372]

[0373]

[0374] Note: T97 refers to the current density of 10mA / cm 2 Under the condition of , the time taken for the device brightness to decay to 97%;

[0375] As can be seen from the results in Table 1, the triamine derivatives of the present invention are applied to organic light-emitting devices as hole transport layer materials. Compared with Comparative Examples 1-2, it can be seen that the performance of the devices is improved, showing the advantages of high luminous efficiency and long service life. In particular, the glass transition temperature of the compounds of the present invention is high, and the service life of the devices is extended.

[0376] [Comparative Example 3-17] Device Preparation Example:

[0377] Comparative Example 3: Fabrication of an organic light-emitting device using vacuum thermal evaporation. The experimental steps were as follows: The ITO substrate was rinsed three times in distilled water, ultrasonically cleaned for 15 minutes, and then ultrasonically cleaned with isopropyl alcohol, acetone, and methanol, sequentially. The substrate was then dried at 120°C and placed in a vapor deposition machine.

[0378] On the prepared ITO transparent electrode, a hole injection layer HI / 55nm, a hole transport layer HT-1 / 80nm, a main body H-1:H-2: doped Ir(ppy)2acac (mass ratio 46%:46%:8% mixed) / 30nm, and then a hole blocking layer compound 2-67 was evaporated, and an electron transport layer Alq3 and Liq (doping ratio is 1:1 by mass ratio) / 28nm, an electron injection layer LiF / 1nm, and a cathode Al / 125nm were evaporated. The device was sealed in a glove box to prepare an organic light-emitting device. After the organic light-emitting device was completed according to the above steps, the photoelectric performance of the device was measured. The molecular structure of the relevant materials is shown below:

[0379]

[0380] Comparative Example 4-6: The hole blocking layer compound 2-67 in Comparative Example 3 was replaced with 2-85, 2-258, or 2-308, and the organic light-emitting device of Comparative Example 4-6 was manufactured in the same manner as Comparative Example 3.

[0381] Comparative Examples 7-9: The hole transport layer HT-1 in Comparative Example 3 was replaced with compounds 49, 66, and 242 of the present invention, and the hole blocking layer compounds 2-67 were replaced with HB-1, HB-2, and HB-3. The organic light-emitting devices of Comparative Examples 7-9 were manufactured in the same manner as in Comparative Example 3.

[0382] Comparative Examples 10-18: The hole transport layer HT-1 in Comparative Example 3 was replaced with the compounds 242, 66, 259, 269, 517, 49, 69, 232, and 413 of the present invention, and the hole blocking layer compound HB-1 was replaced with none. The organic light-emitting devices of Comparative Examples 10-18 were manufactured in the same manner as in Comparative Example 3.

[0383] Application Examples 28-53: The hole transport layer material HT-1 of the organic light-emitting device is replaced with compounds 8, 22, 49, 66, 69, 85, 175, 232, 242, 246, 259, 269, 278, 306, 317, 343, 351, 367, 413, 421, 502, 504, 506, 507, 511, and 517 of the present invention, and the hole blocking layer compound HB-1 is replaced with compounds 2-67, 2-85, and 2-9 of the present invention. 0, 2-95, 2-102, 2-136, 2-164, 2-180, 2-258, 2-269, 2-297, 2-308, 2-345, 2-355, 2-360, 2-362, 2-409, 2-486, 2-67, 2-85, 2-95, 2-164, 2-180, 2-258, 2-297, 2-308, 2-345, 2-362, 2-409, 2-486, and other steps are the same as those in Comparative Example 3.

[0384] [Table 2] Luminous characteristics test of light-emitting devices

[0385]

[0386]

[0387] The results in Table 2 demonstrate that the organic light-emitting devices of the present invention exhibit high luminous efficiency and a long service life compared to Comparative Examples 3-18, demonstrating excellent performance. This is due to the combination of the specific hole-transporting material and the specific hole-blocking material of the present invention, which demonstrates the synergistic effect of the hole-transporting layer and the hole-blocking layer. The combined effect of these two materials enables the performance of the organic light-emitting devices of the present invention to surpass the limitations of conventional organic light-emitting devices, demonstrating the advantages of high luminous efficiency and long service life.

[0388] It should be noted that the present invention is particularly described using individual embodiments. However, without departing from the principles of the present invention, a person skilled in the art may make various improvements in form or detail to the present invention, and these improvements also fall within the scope of protection of the present invention.

Claims

1. A triamine derivative, characterized in that The molecular structure is shown in Formula I: wherein at least one of R1 and R2 is selected from unsubstituted methyl, ethyl, propyl, or butyl, and the others are selected from hydrogen, and R3 is selected from hydrogen; The Ar1 is selected from any one of the following groups: The Rr are the same or different and are selected from hydrogen or one of the following unsubstituted groups: methyl, ethyl, propyl, butyl; The R1 is selected from 0, 1, 2, 3, 4 or 5; the R2 is selected from 0, 1, 2, 3 or 4; the R3 is selected from 0, 1, 2 or 3; the R4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the R6 is selected from 0, 1, 2, 3, 4, 5 or 6; the R7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; and the Ar2, Ar3, Ar4, Ar5 and Ar6 are independently selected from any one of the following groups: The L1, L2, L3, L4, L5, and L6 are independently selected from single bonds.

2. The triamine derivative according to claim 1, characterized in that The Ar1 is selected from any one of the following groups:

3. The triamine derivative according to claim 1, characterized in that Ar2, Ar3, Ar4, Ar5, and Ar6 are independently selected from any one of the following groups:

4. A triamine derivative, characterized in that The triamine derivative is selected from any one of the following chemical structures:

5. An organic light-emitting device comprising an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more of the anode and the cathode, wherein: The organic layer contains any one or a combination of at least two of the triamine derivatives according to any one of claims 1 to 4.

6. The organic light-emitting device according to claim 5, wherein the organic layer comprises a hole transport region, a light-emitting layer, an electron transport region and a covering layer, wherein: At least one of the hole transport region, the light emitting layer, and the covering layer contains any one or a combination of at least two of the triamine derivatives according to any one of claims 1 to 4.

7. The organic light emitting device according to claim 6, characterized in that: The hole transport region comprises a hole transport layer, which is located between the anode and the light-emitting layer, and the hole transport layer contains any one or a combination of at least two of the triamine derivatives according to any one of claims 1 to 4; the electron transport region comprises an electron transport layer and a hole blocking layer, which is located between the light-emitting layer and the electron transport layer, and the hole blocking layer contains a heterocyclic compound represented by formula II: The Arb and Arc are the same or different and are selected from the structure shown in formula b, The formula b is selected from one of the structural groups shown: The Z is selected from any one of O, S or N(Ry); the Ry is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl; the "substituted..." refers to mono- or poly-substituted deuterium; described Any one selected from the following groups: a is selected from 0, 1, 2 or 3; b is selected from 0, 1, 2, 3 or 4; c is selected from 0, 1, 2, 3, 4 or 5; e is selected from 0, 1, 2, 3, 4, 5 or 6; d is selected from 0, 1, 2, 3, 4, 5, 6 or 7; The R a Selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, naphthyl, and the above groups may be further substituted by deuterium; The R a1 Selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, and the above groups may be substituted by deuterium; The R0 is selected from hydrogen and deuterium; the a is selected from 0, 1, 2 or 3; The L a Selected from a single bond or any one of the structures shown below, The L b , L c The same or different ones are selected from a single bond or any one of the structures shown below, Wherein, the R9 are the same or different and are selected from any one of hydrogen and deuterium; The R4 are the same or different and are selected from methyl groups, and the above groups may also be substituted by deuterium; The k1 is selected from 0, 1, 2, 3 or 4, k2 is selected from 0, 1, 2, 3, 4, 5 or 6, k3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, k4 is selected from 0, 1, 2 or 3, k5 is selected from 0, 1 or 2, k6 is selected from 0, 1, 2, 3, 4 or 5; when k1, k2, k3, k4, k5, k6 is greater than 1, two or more R9 are the same or different.

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