CN116589496A

CN116589496A - Star-shaped triamine compound and organic light-emitting device thereof

Info

Publication number: CN116589496A
Application number: CN202310558857.4A
Authority: CN
Inventors: 韩春雪; 周雯庭; 刘喜庆
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2023-05-17
Filing date: 2023-05-17
Publication date: 2023-08-15

Abstract

The invention provides a star-shaped triamine compound and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The compound takes benzene as a center, is connected with three triarylamines, and at least one dibenzo five-membered ring is connected to the triarylamines, and meanwhile, the structure of the formula I at least contains one substituted or unsubstituted silyl group, so that the solubility is enhanced, the film formation is facilitated, and the film formation property and the thermal stability are good; on the other hand, the compound has good hole mobility and proper HOMO energy level and T1 value, is applied to an organic light-emitting device, and particularly can effectively improve the light-emitting efficiency of the device and prolong the service life of the device when being used as a hole transport layer material and a cover layer material. The light source can be widely applied to the fields of panel display, illumination light sources, flexible OLED, organic solar cells, organic photoreceptors, signs, signal lamps and the like.

Description

Star-shaped triamine compound and organic light-emitting device thereof

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to a star-shaped triamine compound and an organic light-emitting device thereof.

Background

Materials used as the organic layer in the organic light emitting device can be largely classified into a light emitting material, a hole injecting material, a hole transporting material, an electron injecting material, a capping layer material, and the like according to their functions. Luminescent materials can be classified into fluorescent materials and phosphorescent materials according to a luminescence mechanism, and can be classified into blue, green, and red luminescent materials according to a luminescence color. The light emission principle of the organic light emitting device is that when a voltage is applied between an anode and a cathode, holes injected from the anode will move to the light emitting layer via the hole transporting layer, while electrons injected from the cathode will move to the light emitting layer via the electron transporting layer, and the holes and electrons will recombine at the light emitting layer and generate excitons. Light will be generated during the transition of the exciton from the excited state to the ground state.

The efficiency of an organic light emitting device can be generally classified into internal light emitting efficiency and external light emitting efficiency. The internal light emission efficiency is related to the efficiency of generating excitons in an organic layer such as a hole transport layer, a light emitting layer, and an electron transport layer between a cathode and an anode and realizing light conversion, and theoretically, the internal light emission efficiency of fluorescence is 25%, and phosphorescence is 100%. In addition, the external light emission efficiency refers to the efficiency with which light generated in the organic layer is extracted to the outside of the organic light emitting device, and in order to prevent loss of light irradiated to the outside due to total reflection, an organic compound is generally used as a coating layer.

In the present stage, the types of hole transport and electron transport materials applied to the organic light emitting device are limited, so that the organic light emitting device still has a plurality of problems to be solved, the materials commonly used for the hole transport layer at present have the problems of low hole mobility, low glass transition temperature and the like, electrons and hole transport cannot reach balance, excitons cannot be effectively combined, and at the same time, triplet energy level is low, so that the loss of excitons to the hole transport layer cannot be effectively avoided, and the light emitting efficiency of the device is low and the stability of the device is reduced. On the other hand, the organic light-emitting device can generate total reflection phenomenon at the interface when emitting light, so that the light-emitting efficiency of the OLED device is only about 20%, the improvement of the performance of the organic light-emitting device is seriously restricted, however, the refractive index and the glass transition temperature of the existing coating material are lower, the effect of improving the light-emitting efficiency is not obvious, and the light-emitting efficiency of the organic light-emitting device is low.

In order to solve the above problems, it is currently necessary to study a hole transport material having a high hole mobility, a high glass transition temperature, and a high triplet energy level, and a capping material having a high refractive index and a high glass transition temperature.

Disclosure of Invention

The invention aims to provide a star-shaped triamine compound and an organic light-emitting device thereof based on the prior art, and the star-shaped triamine compound is applied to a hole transmission layer, a light-emitting auxiliary layer (a second hole transmission layer) or a covering layer in the organic light-emitting device to develop a light-emitting device with high efficiency and long service life, wherein the molecular structural general formula of the star-shaped triamine compound is shown as the formula I:

wherein the Ar is ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ At least one of which is selected from the group represented by formula a below, and the remainder is independently selected from the group represented by formula b:

the formula a is fused to one of formula a-1, formula a-2, formula a-3, formula a-4, wherein "]" represents a fused attachment site of formula a to formula a-1, formula a-2, formula a-3, or formula a-4;

the R is _a Identically or differently selected from one of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, substituted or unsubstituted C6-C25 aromatic ring and C3-C25 aliphatic ring condensed ring group, or any adjacent two R _a The radicals being bonded togetherForming a substituted or unsubstituted cyclic structure;

the a is selected from 1, 2 or 3; said b is selected from 1, 2, 3 or 4;

the R is ₄ 、R ₅ Independently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted one of the following groups: silyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, or R ₄ 、R ₅ The groups may be bonded together to form a substituted or unsubstituted cyclic structure; or R is ₄ Or R is ₅ Corresponding to carbon atoms bridged with L ₁ ～L ₆ A site of ligation;

the R is ₆ One selected from the group consisting of substituted or unsubstituted: one of substituted or unsubstituted silyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl; or R is ₆ The nitrogen atom corresponding to the bridging L ₁ ～L ₆ A site of ligation;

the x are the same or different and are selected from CR _c Or N and L ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ The attached x is selected from the group consisting of C atoms;

R _c the same or different radicals are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C25 heterocycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, and substituted or unsubstitutedOne of the substituted C2-C25 heteroaryl groups, or optionally two adjacent R groups _c The groups may be bonded together to form a substituted or unsubstituted cyclic structure;

the R is ₁ 、R ₂ 、R ₃ Independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl;

the L is ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ Independently selected from one of a single bond, a substituted or unsubstituted C6-C25 arylene group, a substituted or unsubstituted C2-C25 heteroarylene group, a substituted or unsubstituted C3-C12 alicyclic ring, and a C6-C25 aromatic ring, a fused ring group;

The conditions are as follows: the Ar is as follows ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ 、L ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ 、R ₁ 、R ₂ 、R ₃ Containing one or more substituted or unsubstituted silyl groups.

The invention also provides an organic light-emitting device, which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or outside one or more than one of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the star-shaped triamine compounds.

The invention has the beneficial effects that:

the invention provides a star-shaped triamine compound and an organic light-emitting device thereof, wherein the compound takes benzene as a center, is connected with three triarylamines, and the triarylamines are at least connected with one dibenzo five-membered ring; on the other hand, the compound has good hole mobility and proper HOMO energy level and T1 value, is applied to an organic light-emitting device, and particularly can effectively improve the light-emitting efficiency of the device and prolong the service life of the device when being used as a hole transport layer material and a cover layer material.

Detailed Description

The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.

In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance.

In this specification, when a substituent is not fixed in position on a ring, it is meant that it can be attached to any of the corresponding selectable positions of the ring.

For example, the number of the cells to be processed,can indicate-> Can indicate-> Can indicate-> And so on. In this specification, when a substituent or linkage site is located across two or more rings, it is meant that it may be attached to either of the two or two rings, in particular to either of the respective selectable sites of the rings. For example, a->Can indicate-> Can indicate->And so on.

Halogen in the present invention means fluorine, chlorine, bromine and iodine.

The alkyl group according to the present invention is a hydrocarbon group having at least one hydrogen atom in the alkane molecule, and may be a straight chain alkyl group or a branched chain alkyl group, and preferably has 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, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, an isomeric group of n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, and the like. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

Cycloalkyl as used herein refers to a hydrocarbon group having at least one hydrogen atom in the cycloparaffin molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 3 to 6 carbon atoms, and examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, camphene, norbornyl, etc., but are not limited thereto. The cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, or a norbornyl group.

The silyl group in the present invention is preferably a silyl group, and the silyl group is preferably a silyl group in which one hydrogen atom is not contained in the silane molecule. The "substituted or unsubstituted silyl group" having-Si (R) ₃ The structure shown, R is selected from any one of H, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 alicyclic and C6-C30 aromatic ring condensed ring, substituted or unsubstituted C2-C30 heteroaryl, but not limited thereto; preferably, R. The substituted silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, phenyldimethylsilyl group and the like, and preferably trimethylsilyl group, triethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group and phenyldimethylsilyl group.

Aryl in the present invention refers to the generic term for monovalent radicals remaining after removal of one hydrogen atom from the aromatic nucleus carbon of an aromatic compound molecule, which may be a monocyclic aryl, polycyclic aryl or fused ring aryl, preferably having from 6 to 25 carbon atoms, more preferably from 6 to 20 carbon atoms, particularly preferably from 6 to 14 carbon atoms, and most preferably from 6 to 12 carbon atoms. The monocyclic aryl refers to aryl having only one aromatic ring in the molecule, for example, phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, etc., but is not limited thereto; the condensed ring aryl group refers to an aryl group having two or more aromatic rings in the molecule and condensed by sharing two adjacent carbon atoms with each other, for example, but not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylenyl, fluoranthryl, spirobifluorenyl, and the like. The aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthryl group (preferably a 2-anthryl group), a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylenyl group, or a spirobifluorenyl group.

Heteroaryl according to the present invention refers to the generic term for groups in which one or more aromatic nucleus carbon atoms in the aryl group are replaced by heteroatoms, including but 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, most preferably 3 to 12 carbon atoms, the attachment site of the heteroaryl group may be located on a ring-forming carbon atom, or on a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl, polycyclic heteroaryl or fused ring heteroaryl. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroaryl group includes, but is not limited to, quinolinyl, isoquinolinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiazinyl, and the like. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a benzodibenzothienyl group, a benzodibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, or a phenoxathiazide group.

The arylene group according to the present invention means a generic term for divalent groups remaining after removal of two hydrogen atoms from the aromatic nucleus carbon of an aromatic compound molecule, which may 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 phenylene and the like, but is not limited thereto; the polycyclic arylene group includes biphenylene, terphenylene, etc., but is not limited thereto; the condensed ring arylene includes, but is not limited to, naphthylene, anthrylene, phenanthrylene, fluorenylene, pyreylene, triphenylene, fluoranthenylene, phenylenedenyl, and the like. The arylene group is preferably phenylene, biphenylene, terphenylene, naphthylene, fluorenylene, or phenylenediyl.

Heteroaryl, as used herein, refers to the generic term for groups in which one or more of the aromatic nucleus carbons in the arylene group is replaced with a heteroatom, including but not limited to oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 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 heteroarylene group may be attached at a ring-forming carbon atom or at a ring-forming nitrogen atom, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group. The monocyclic heteroarylene group includes, but is not limited to, a pyridylene group, a pyrimidinylene group, a triazinylene group, a furanylene group, a thienyl group, and the like; the polycyclic heteroarylene group includes bipyridylene group, bipyrimidiylene group, phenylpyridylene group, etc., but is not limited thereto; the condensed ring heteroarylene group includes quinolinylene, isoquinolylene, indolylene, benzothienyl, benzofuranylene, benzoxazolylene, benzimidazolylene, benzothiazolylene, dibenzofuranylene, benzodibenzofuranylene, dibenzothiophenylene, benzodithiorenylene, carbazolylene, benzocarbazolylene, acridinylene, 9, 10-dihydroacridinylene, phenoxazinylene, phenothiazinylene, phenoxazinylene, and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidylene group, a thienyl group, a furanylene group, a benzothienyl group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzodibenzothiophenyl group, a benzodibenzofuranyl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, or a phenoxathiazide group.

The fused ring group of the aliphatic ring and the aromatic ring refers to the general term that two hydrogen atoms are removed after the aliphatic ring and the aromatic ring are fused together, and a bivalent group is remained. Preferably having 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 12 carbon atoms, examples may include, but are not limited to, benzobicyclopropyl, benzobicyclobutyl, benzocyclopentylene, benzocyclohexylene, benzocycloheptylene, benzocyclopentylene, benzocyclohexenylene, benzocycloheptylene, naphthocyclopropyl, naphthocyclobutylene, naphthocyclopentyl, naphthocyclohexyl, and the like.

The fused ring of an aromatic ring and an aliphatic ring according to the present invention means a ring having one or more aromatic rings and having 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 has 6 to 18 carbon atoms, most preferably has 6 to 12 carbon atoms, the aliphatic ring preferably has 3 to 30 carbon atoms, more preferably has 3 to 18 carbon atoms, more preferably has 3 to 12 carbon atoms, most preferably has 3 to 7 carbon atoms, and examples include benzocyclopropane group, benzocyclobutane group, benzocyclopentene group, benzocyclohexenyl group, benzocycloheptyl group, naphthocyclopropane group, naphthocyclobutane group, naphthocyclopentane group, naphthocyclohexenyl group, naphthocyclopentenyl group, naphthocyclohexenyl group, and the like, but are not limited thereto.

The alicyclic ring according to the present invention means a cyclic hydrocarbon having an aliphatic nature, and having a closed carbocyclic ring in the molecule, preferably having 3 to 60 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. Which may form a mono-or polycyclic hydrocarbon, may be fully unsaturated or partially unsaturated, and specific examples may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and the like, but are not limited thereto. The plurality of monocyclic hydrocarbons may also be linked in a variety of ways: two rings in the molecule can share one carbon atom to form a spiro ring; the two carbon atoms on the ring can be connected by a carbon bridge to form a bridge ring; several rings may also be interconnected to form a cage-like structure.

"substituted …" as used herein, such as a substituted silyl group, a substituted alkyl group, a substituted cycloalkyl group, a substituted aryl group, a condensed ring group of a substituted aromatic ring and an aliphatic ring, a substituted arylene group, a substituted aliphatic ring, a condensed ring group of an aromatic ring, etc., means that the groups independently selected from deuterium, tritium, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C2-C15 heteroaryl group, a substituted or unsubstituted amine group, etc., are mono-or poly-substituted, preferably mono-or polysubstituted with groups selected from deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, camphene, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylene, pyrenyl, benzyl, tolyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, diphenylamino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothiophenyl, phenothiazinyl, phenoxazinyl, indolyl. In addition, the substituent may be substituted with one or more substituents selected from deuterium, halogen atom, cyano, alkyl, cycloalkyl and aryl.

The term "ring" as used herein, unless otherwise specified, refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a heterocyclic ring having 2 to 60 carbon atoms or a combination thereof, which comprises a saturated or unsaturated ring.

In the present invention, the "at least one" means one, two, three, four, five, six or more.

In the present invention, the "one or more" means one, two, three, four, five, six or more.

The term "bonded to form a cyclic structure" as used herein means that two groups are attached to each other by a chemical bond and optionally aromatized. As exemplified below:

in the present specification, the ring formed by the connection may be an aromatic ring or a non-aromatic ring, and may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring, a condensed ring, or the like, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, adamantane, norbornane, benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, quinoline, isoquinoline, quinazoline, quinoxaline, fluorene, dibenzofuran, dibenzothiophene, carbazole, or the like, but is not limited thereto.

The invention provides a star-shaped triamine compound, the molecular structural general formula of which is shown as formula I:

the R is _a Identically or differently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C25 arylOne of a group, a substituted or unsubstituted C2-C25 heteroaryl group, a substituted or unsubstituted C6-C25 aromatic ring and a C3-C25 aliphatic ring condensed ring group, or any adjacent two R _a The groups are bonded together to form a substituted or unsubstituted cyclic structure;

the a is selected from 1, 2 or 3; said b is selected from 1, 2, 3 or 4;

R _c the same or different alkyl radicals selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkylOne of a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C3-C25 heterocycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted C2-C25 heteroaryl group, or optionally two adjacent R' s _c The groups may be bonded together to form a substituted or unsubstituted cyclic structure;

the R is ₁ 、R ₂ 、R ₃ Independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted C1-C25 silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl;

the conditions are as follows: the Ar is as follows ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ 、L ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ 、R ₁ 、R ₂ 、R ₃ Containing one or more silane groups.

Preferably, the formula I is selected from one of the following formulas I-1 to I-3:

preferably, the Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ One, two, three, four, five or six of the groups of formula a, and the remainder are independently selected from the groups of formula b.

PreferablyAr of (Ar) ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ At least one selected from the group consisting of groups of formula a, comprising: ar (Ar) ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ One of them is selected from the group represented by formula a, specifically Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ Or Ar ₆ Selected from the group represented by formula a; ar (Ar) ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ Two of them are selected from the group represented by formula a, specifically Ar ₁ And Ar is a group ₂ ，Ar ₁ And Ar is a group ₃ ，Ar ₁ And Ar is a group ₅ ，Ar ₃ And Ar is a group ₄ ，Ar ₃ And Ar is a group ₅ Or Ar ₅ And Ar is a group ₆ Selected from the group represented by formula a; ar (Ar) ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ Three of the groups represented by formula a, specifically Ar ₁ 、Ar ₂ And Ar is a group ₃ ，Ar ₁ 、Ar ₂ And Ar is a group ₅ ，Ar ₁ 、Ar ₃ And Ar is a group ₄ ，Ar ₁ 、Ar ₃ And Ar is a group ₅ ，Ar ₁ 、Ar ₅ And Ar is a group ₆ ，Ar ₃ 、Ar ₄ And Ar is a group ₅ Or Ar ₃ 、Ar ₅ And Ar is a group ₆ Selected from the group represented by formula a; ar (Ar) ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ Four of the groups represented by formula a, specifically Ar ₁ 、Ar ₂ 、Ar ₃ And Ar is a group ₄ ，Ar ₁ 、Ar ₂ 、Ar ₃ And Ar is a group ₅ ，Ar ₁ 、Ar ₂ 、Ar ₅ And Ar is a group ₆ ，Ar ₁ 、Ar ₃ 、Ar ₄ And Ar is a group ₅ Or Ar ₃ 、Ar ₄ 、Ar ₅ And Ar is a group ₆ Selected from the group represented by formula a; ar (Ar) ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ Wherein five are selected from the group represented by formula a, specifically Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ And Ar is a group ₅ Or Ar ₁ 、Ar ₃ 、Ar ₄ 、Ar ₅ And Ar is a group ₆ Selected from the group represented by formula a; ar (Ar) ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ Six of them are selected from the group represented by formula a, specifically Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ And Ar is a group ₆ Selected from the group represented by formula a.

Preferably, at least one of the groups of formula a contains one or more substituted or unsubstituted silyl groups.

More preferably, one, two or three of the groups of formula a contain one or more substituted or unsubstituted silyl groups.

Preferably, at least one of the groups of formula b contains one or more substituted or unsubstituted silyl groups.

More preferably, one, two or three of the groups of formula b contain one or more substituted or unsubstituted silyl groups.

Preferably, said R _c Is a substituted or unsubstituted silyl group.

More preferably, said R _c One, two or three of which are substituted or unsubstituted silyl groups.

Preferably, the formula a is selected from one of the following groups:

the R is _a Identically or differently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, one of the following substituted or unsubstituted groups: trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, and triphenylsilyl groupsOne of silyl, diphenylmethylsilyl, phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, one of the "substituted or unsubstituted" substituents being selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, camphene, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, or one or more of any two adjacent R _a The groups are bonded together to form a substituted or unsubstituted benzene or naphthalene ring;

the R is _m Identically or differently selected from one of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl, tert-butyldimethylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, tridecylphenylsilyl, dideuterophenylmethylsilyl, deuterated phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, or any two adjacent R _m The groups are bonded together to form a substituted or unsubstituted benzene or naphthalene ring; the R is _m Can also be R _mm Substituted, R _mm Selected from the group consisting of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, silyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl,One or more of norbornyl, camphene, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, where substituted with multiple substituents, the multiple substituents may be the same or different from each other;

The m is ₂ Selected from 1, 2, 3 or 4; m is m ₃ Selected from 1, 2, 3, 4, 5 or 6; m is m ₄ Selected from 1, 2, 3, 4, 5, 6, 7 or 8; m is m ₅ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; m is m ₆ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; m is m ₇ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

Further preferably, the formula a is selected from one of the following groups:

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the R is _b Identically or differently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, one of the following substituted or unsubstituted groups: one of trimethylsilyl, triethylsilyl, triphenylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, wherein the "substituted or unsubstituted" substituent is selected from one or more of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, and where substituted with multiple substituents, the multiple substituents may be the same or different from one another, or any two adjacent R _b The groups are bonded together to form a substituted or unsubstituted benzene ring;

the a is selected from 1, 2 or 3; said b is selected from 1, 2, 3 or 4; said c is selected from 1, 2, 3, 4 or 5; said d is selected from 1, 2, 3, 4, 5 or 6; said e is selected from 1, 2, 3, 4, 5, 6 or 7; said f is selected from 1, 2, 3, 4, 5, 6, 7 or 8; said g is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; the h is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the i is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

Preferably, said R _a Identically or differently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, one of the following substituted or unsubstituted groups: one of trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, wherein the "substituted or unsubstituted" substituents are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triethylsilyl, triphenylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, where substituted with multiple substituents are the same or different from each other, or any two adjacent R _a The groups are bonded together to form a substituted or unsubstituted benzene ring.

Preferably, R of formula I _a One or more silyl groups selected from substituted or unsubstituted silyl groups.

More preferably, R of formula I _a One, two or three of which are selected from substituted or unsubstituted silyl groups.

Preferably, said R ₆ One selected from the group consisting of substituted or unsubstituted: trimethylsilyl, triethylsilylOne of triisopropylsilyl, tri-tert-butylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl; the substituent of the "substituted or unsubstituted" is selected from one or more of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, camphene, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other; or R is ₆ The nitrogen atom corresponding to the bridging L ₁ ～L ₆ The site of ligation.

Preferably, the formula b is selected from one of the following groups:

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the R is _e The same or different radicals are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triphenylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, campheneOne of phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl; wherein said R is _e Can also be R _ee Substituted, R _ee One or more selected from hydrogen, deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl;

the c ₁ Selected from 1, 2, 3, 4 or 5; the c ₂ Selected from 1, 2, 3 or 4; the c ₃ Selected from 1, 2 or 3; the c ₄ Selected from 1, 2, 3, 4, 5, 6 or 7; the c ₅ Selected from 1 or 2; the c ₆ Selected from 1, 2, 3, 4, 5 or 6; the c ₇ Selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; the c ₈ Selected from 1, 2, 3, 4, 5, 6, 7 or 8; the c ₉ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the c ₁₀ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

Preferably, said R _c The same or different one selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl, tert-butyldimethylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, tridecylphenylsilyl, dideuterophenylmethylsilyl, deuterated phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, camphene, phenyl, naphthyl, tolyl, biphenyl, terphenyl, anthracenyl, phenanthryl, triphenylene, spirofluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl, or two R's optionally adjacent _c The groups may be bonded together to form a benzene ring; wherein said R is _c Can also be R _cc Substituted, R _cc Selected from the group consisting ofHydrogen, deuterium, tritium, trimethylsilyl, triphenylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, anthracenyl, phenanthryl, where substituted with multiple substituents, the multiple substituents may be the same or different from one another.

Preferably, R of formula I _c One or more silyl groups selected from substituted or unsubstituted silyl groups.

More preferably, R of formula I _c One, two or three of which are selected from substituted or unsubstituted silyl groups.

Preferably, the L ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ Independently selected from single bond, substituted or unsubstituted such groups: phenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, phenyl-naphthyl, naphthyl-naphthyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, and combinations thereof, wherein the substituents are one or more of deuterium, tritium, cyano, halogen, trifluoromethyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, and where substituted with multiple substituents, the multiple substituents are the same or different from each other.

Preferably, the L ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ Independently selected from a single bond or one of the following groups:

the R is _d Are the same or different from each other, and are selected from any one of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted C1-C25 silane groups, substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups and substituted or unsubstituted C6-C25 aryl groups;

said d ₀ Selected from 0, 1 or 2; said d ₁ Selected from 0, 1, 2, 3 or 4; said d ₂ Selected from 0, 1, 2, 3, 4, 5 or 6; said d ₃ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

the R is _x 、R _y Independently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl or substituted or unsubstituted groups of: one of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthryl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl;

the R is _z Selected from the group consisting of substituted or unsubstituted: one of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthryl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl.

Most preferably, the L ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ Independently selected from a single bond or one of the following groups:

preferably, formula I contains one or more of said substituted or unsubstituted silyl groups.

More preferably, one, two, three, four, five, six or more of said substituted or unsubstituted silyl groups are comprised in formula I.

Preferably, the substituted or unsubstituted silyl group is selected from trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl.

Most preferably, the star-shaped triamine compound is selected from any one of the chemical structures shown as follows:

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the preparation method of the star-shaped triamine compound shown in the formula I can be prepared through a coupling reaction conventional in the art, for example, the star-shaped triamine compound can be prepared through the following synthetic route, but the invention is not limited to the following steps:

the star-shaped triamine compound is subjected to Buchwald-Hartwig coupling reaction to obtain an intermediate A, B, C; the raw material g and the intermediate A are subjected to Buchwald-Hartwig coupling reaction to obtain an intermediate I; intermediate I and intermediate B are subjected to Buchwald-Hartwig coupling reaction to obtain intermediate II, and intermediate II and intermediate C are subjected to Buchwald-Hartwig coupling reaction to finally obtain a compound of formula I, wherein halogen compound X ₁ 、X ₂ 、X ₃ 、X ₄ 、X ₅ 、X ₆ Independently selected from Cl, br or I.

The sources of the raw materials used in the above-mentioned various reactions are not particularly limited in the present invention, and the star-shaped triamine compound represented by the formula I of the present invention can be obtained using commercially available raw materials or using a preparation method well known to those skilled in the art. The present invention is not particularly limited to the above reaction, and conventional reactions well known to those skilled in the art may be employed.

Preferably, the organic layer comprises a hole transport region, a light emitting layer, an electron transport region or a cover layer, and at least one of the hole transport region and the cover layer contains any one or a combination of at least two of the star-shaped triamine compounds of the present invention.

Preferably, the organic layer comprises a hole transport region, and the hole transport region contains any one or a combination of at least two of the star-shaped triamine compounds disclosed by the invention.

Preferably, the hole transport region comprises at least one layer of a hole injection layer, a hole transport layer and an electron blocking layer, and the hole transport layer contains any one or a combination of at least two of the star-shaped triamine compounds of the present invention.

Preferably, the hole transport layer comprises a hole transport layer and a light-emitting auxiliary layer (second hole transport layer), the light-emitting auxiliary layer is located between the hole transport layer and the light-emitting layer, and at least one of the hole transport layer and the light-emitting auxiliary layer contains any one or a combination of at least two of the star-shaped triamine compounds of the present invention.

Preferably, the organic layer comprises a cover layer, and the cover layer contains any one or a combination of at least two of the star-shaped triamine compounds.

Preferably, the coating layer according to the present invention may be a single-layer structure, a two-layer structure or a multi-layer structure, and the coating layer material according to the present invention may be at least one selected from star-shaped triamine compounds according to the present invention, or may contain conventional coating layer materials well known to those skilled in the art.

The light emitting device of the present invention is generally formed on a substrate. The substrate may be a substrate made of glass, plastic, polymer film, silicon, or the like, as long as it is not changed when an electrode is formed or an organic layer is formed. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.

The anode material is preferably a metal, an alloy, a conductive compound, or a mixture thereof having a large work function (for example, 4.0eV or more). Such as indium-tin Oxide (ITO); indium oxide-tin oxide containing silicon or silicon oxide; indium oxide-zinc oxide; indium oxide containing tungsten oxide and zinc oxide; graphene, and the like. Gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), or a nitride of the above metals (for example, titanium nitride), or the like.

The anode may have a single-layer structure or a multi-layer 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 adopts a transparent ITO substrate. The anode may be formed by depositing or spraying a material for forming the anode on the substrate.

The hole transport region may include a single layer structure of a plurality of different materials, a structure of a hole injection layer/hole transport layer/buffer layer, a structure of a hole injection layer/buffer layer, a structure of a hole transport layer/buffer layer, or a structure of a hole injection layer/hole transport layer/electron blocking layer, wherein layers of the respective structures are sequentially stacked in the stated order from the anode, but the structure of the hole transport region is not limited thereto.

The hole injection layer material is preferably a material having high hole injection properties (hole injection material), for example, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, or the like; low molecular organic compounds such as 4,4',4 "-tris (N, N-diphenylamino) triphenylamine (abbreviation: TDATA), 4' -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), 4 '-bis [ N- (4-diphenylaminophenyl) -N-phenylamino ] biphenyl (abbreviated as DPAB), 4' -bis (N- {4- [ N '- (3-methylphenyl) -N' -phenylamino ] phenyl } -N-phenylamino) biphenyl (abbreviated as DNTPD), 3- [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviated as PCzPCA 1), 3, 6-bis [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviated as PCzPCA 2), and the like. The material may be a single structure formed of a single substance or a single layer or a multi-layer structure formed of different substances, and other known materials suitable for the hole injection layer may be selected in addition to the above materials and combinations thereof.

The hole transport layer material is preferably a material having high hole transport properties (hole transport material), and an aromatic amine compound, a carbazole derivative, an anthracene derivative, or the like can be used. As the aromatic amine compound, for example, 4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (abbreviation: NPB), N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1,1' -biphenyl ] -4,4' -diamine (abbreviated as TPD), 4-phenyl-4 ' - (9-phenylfluoren-9-yl) triphenylamine (abbreviated as BAFLP), 4' -bis [ N- (9, 9-dimethylfluoren-2-yl) -N-phenylamino ] biphenyl (abbreviated as DFLDPBi), 4',4 "-tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4',4" -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), 4' -bis [ N- (spiro-9, 9' -bifluor-2-yl) -N-phenylamino ] biphenyl (abbreviated as BSPB). Examples of carbazole derivatives include 4,4' -bis (9-carbazolyl) biphenyl (abbreviated as CBP), 9- [4- (9-carbazolyl) phenyl ] -10-phenylanthracene (abbreviated as CzPA), 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl ] -9H-carbazole (abbreviated as PCzPA), and the like; examples of the anthracene derivative include 2-t-butyl-9, 10-bis (2-naphthyl) anthracene (abbreviated as t-BuDNA), 9, 10-bis (2-naphthyl) anthracene (abbreviated as DNA), 9, 10-diphenylanthracene (abbreviated as DPAnth), and the like. Polymer compounds such as poly (N-vinylcarbazole) (PVK for short) may also be used. Preferably, the hole transport layer material is any one or a combination of at least two of the star-shaped triamine compounds.

The light-emitting layer is a layer having a light-emitting function, and includes a host material and a dopant material, and emits light by fluorescence or phosphorescence. The light emitting layer may be formed to have a layer thickness in the range of 10nm to 60 nm. The light emitting layer may be formed to have a layer emitting light of a specific color. For example, the light emitting layer may be formed as a red light emitting layer, a green light emitting layer, or a blue light emitting layer.

As the blue-based fluorescent light-emitting material of the light-emitting layer, a pyrene derivative, a styrylamine derivative, a fluoranthene derivative, a fluorene derivative, a diamine derivative, a triarylamine derivative, or the like can be used. Such as N4- (9H-carbazol-9-yl) -4'- (10-phenyl-9-anthryl) triphenylamine (abbreviated as YGAPA), 4- (10-phenyl-9-anthryl) -4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated as:PCBAPA), and the like. As the blue-based phosphorescent light-emitting material of the light-emitting layer, a metal complex such as an iridium complex, an osmium complex, or a platinum complex can be used. Such as bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2 ] ']Iridium (III) tetrakis (1-pyrazolyl) borate (FIr 6 for short), bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2 ] ']Iridium (III) picolinate (abbreviated as FIrpic), bis [2- (3 ',5' -bis (trifluoromethyl) phenyl) pyridine-N, C2 ] ' ]Iridium (III) picolinate (abbreviated Ir (CF) ₃ ppy) ₂ (pic)), bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2 ] ']Iridium (III) acetylacetonate (abbreviated as FIracac) and the like. Besides the above materials, other known luminescent materials suitable for blue may be selected.

As the green-based fluorescent light-emitting material of the light-emitting layer, an aromatic amine derivative or the like can be used. Such as N- (9, 10-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazole-3-amine (abbreviated as 2 PCAPA), N- [9, 10-bis (1, 1' -biphenyl-2-yl) -2-anthryl]-N, 9-diphenyl-9H-carbazol-3-amine (abbreviated as 2 PCABPhA), N- (9, 10-diphenyl-2-anthryl) -N, N ', N ' -triphenyl-1, 4-phenylenediamine (abbreviated as 2 DPAPA), N- [9, 10-bis (1, 1' -biphenyl-2-yl) -2-anthryl]-N, N ', N' -triphenylene-1, 4-phenylenediamine (abbreviated as "2 DPABPhA"), N, 9-triphenylanthracene-9-amine (abbreviated as "DPhAPHA"), and the like. As the green-based phosphorescent material of the light-emitting layer, iridium complex or the like can be used. Such as tris (2-phenylpyridine-N, C2') iridium (III) (Ir (ppy) for short) ₃ ) Bis (2-phenylpyridine-N, C2') iridium (III) acetylacetonate (abbreviation: ir (ppy) ₂ (acac)), bis (1, 2-diphenyl-1H-benzimidazole) iridium (III) acetylacetonate (abbreviation: ir (pbi) ₂ (acac)), bis (benzo [ h)]Quinoline) iridium (III) acetylacetonate (abbreviation: ir (bzq) ₂ (acac)) and the like. Besides the above materials, other known luminescent materials suitable for green may be selected.

As the red-based fluorescent light-emitting material of the light-emitting layer, a naphthacene derivative, a diamine derivative, or the like can be used. Such as N, N, N ', N' -tetrakis (4-methylphenyl) tetracene-5, 11-diamine (abbreviated as p-mPHTD), 7, 14-diphenyl-N, N, N ', N' -tetrakis (4-methylphenyl) acenaphtho [1,2-a]Fluoranthene-3, 10-diamine (abbreviated as p-mPHAFD), and the like. As the red-based phosphorescent material of the light-emitting layer, a metal complex such as iridium complex, platinum complex, terbium complex, europium complex, or the like can be used. Such as bis [2- (2' -benzo [4, 5-alpha ]]Thienyl) pyridine-N, C3']Iridium (III) acetylacetonate (Ir (btp) for short) ₂ (acac)), bis (1-phenylisoquinoline-N, C2') iridium (III) acetylacetonate (abbreviation: ir (piq) ₂ (acac)), (acetylacetonate) bis [2, 3-bis (4-fluorophenyl) quinoxaline]Iridium (III) (Ir (Fdpq) for short) ₂ (acac)), 2,3,7,8, 12, 13, 17, 18-octaethyl-21 h,23 h-porphyrin platinum (II) (abbreviation: ptOEP), and the like. In addition to the above materials, other known luminescent materials suitable for red color may be selected.

The light-emitting layer may be formed by dispersing the above-described dopant material in another material (host material). Host materials, e.g., (1) metal complexes such as aluminum complexes, beryllium complexes, or zinc complexes, e.g., tris (8-hydroxyquinoline) aluminum (III) (abbreviated as Alq), tris (4-methyl-8-hydroxyquinoline) aluminum (III) (abbreviated as Almq) ₃ ) Bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (II) (abbreviation: beBq ₂ ) Bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (abbreviation: BAlq), bis (8-hydroxyquinoline) zinc (II) (abbreviation: znq); (2) Heterocyclic compounds such as oxadiazole derivatives, benzimidazole derivatives, phenanthroline derivatives, and the like, for example, heterocyclic compounds such as 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (abbreviated as PBD), 2' - (1, 3, 5-trimethoyl) tris (1-phenyl-1H-benzimidazole) (abbreviated as TPBI), bathophenanthroline (abbreviated as BPhen), bathocuproine (abbreviated as BCP), and the like; (3) Condensed aromatic compounds such as carbazole derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, etc., e.g. 9- [4- (10-phenyl-9-anthryl) phenyl group]-9H-carbazole (abbreviated as CzPA), 9, 10-bis (3, 5-diphenylphenyl) anthracene (abbreviated as DPPA), 9, 10-bis (2-naphthyl) anthracene (abbreviated as DNA), 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene (abbreviated as t-BuDNA), 9 '-dianthracene (abbreviated as BANT), 9' - (stilbene-3, 3 '-diyl) phenanthrene (abbreviated as DPNS), 3' - (benzene-1, 3, 5-diyl) tripyrene (abbreviated as TPB) ₃ ) 9, 10-diphenylanthracene (abbreviation: DPAnth) and the likeA condensed aromatic compound; (4) Aromatic amine compounds such as triarylamine derivatives or condensed polycyclic aromatic amine derivatives, e.g. N, N-diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl]-9H-carbazol-3-amine (abbreviated as CzA PA), 4- (10-phenyl-9-anthryl) triphenylamine (abbreviated as DPhPA), N, 9-diphenyl-N- [4- (10-phenyl-9-anthryl) phenyl]-9H-carbazol-3-amine (abbreviated as PCAPA), N- (9, 10-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazol-3-amine (abbreviated as 2 PCAPA), 4' -bis [ N- (1-naphthyl) -N-phenylamino]Biphenyl (NPB), N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1,1' -biphenyl]-4,4 '-diamine (TPD for short), 4' -bis [ N- (9, 9-dimethylfluoren-2-yl) -N-phenylamino ]]Biphenyl (DFLDPBi), 4 '-bis [ N- (spiro-9, 9' -bifluorene-2-yl) -N-phenylamino]Aromatic amine compounds such as biphenyl (BSPB). Other known materials suitable for the body may be selected in addition to the above materials.

The doping ratio of the host material and the guest material of the light-emitting layer may be varied depending on the materials used, and the doping ratio of the guest material of the light-emitting layer is usually 0.01 to 20%, preferably 0.1 to 15%, more preferably 1 to 10%.

The electron transport layer material is selected from materials having high electron transport properties (electron transport materials). The electron transport layer may include a first electron transport layer material and a second electron transport layer material. The electron transport layer material can be selected from (1) aluminum complex, beryllium complex, zinc complex, etc., such as tris (8-hydroxyquinoline) aluminum (III) (Alq), bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (abbreviation: beBq ₂ ) Bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (abbreviation: BAlq), bis (8-hydroxyquinoline) zinc (II) (abbreviation: znq), bis [2- (2-benzoxazolyl) phenol]Zinc (II) (ZnPBO for short). (2) Heteroaromatic compounds such as imidazole derivatives, benzimidazole derivatives, azine derivatives, carbazole derivatives, phenanthroline derivatives, etc., e.g., 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (abbreviated as PBD), 1, 3-bis [5- (p-tert-butylphenyl) -1,3, 4-oxadiazol-2-yl]Benzene (abbreviated as OXD-7), 3- (4-tert-butylphenyl) -4-phenyl-5- (4-biphenylyl) -1,2,4-triazole (TAZ for short), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenyl) -1,2, 4-triazole (p-EtTAZ for short), bathophenanthroline (BPhen for short) and bathocuproine (BCP for short). (3) Macromolecular compounds, e.g. poly [ (9, 9-dihexylfluorene-2, 7-diyl) -co- (pyridine-3, 5-diyl) ]In addition to the above materials, other known materials suitable for use as electron transport layers may be selected.

The electron injection layer material is selected from materials having high electron injection properties. The electron injection layer may be lithium (Li), cesium (Cs), calcium (Ca), lithium fluoride (LiF), cesium fluoride (CsF), or calcium fluoride (CaF) ₂ ) Alkali metal, alkaline earth metal, or a compound thereof, such as lithium oxide (LiOx). In addition to the above materials, other known materials suitable for the electron injection layer may be selected as the electron injection layer material.

The cathode material preferably uses a metal, an alloy, a conductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8eV or less). Such as elements belonging to the first or second group of the periodic table, that is, alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca) and strontium (Sr), alloys containing them (for example, mgAg, alLi), rare earth metals such as europium (Eu) and ytterbium (Yb), alloys containing them, and the like.

The cladding material is to reduce total emission loss and waveguide loss in the OLED device and to improve light extraction efficiency. The coating material of the present invention may be Alq ₃ TPBi, etc., other known materials suitable for the coating layer may be selected, and the star triamine compound of the present invention may be selected.

The organic light-emitting device can be selected and combined according to the device parameter requirements and the characteristics of materials, and partial organic layers can be added or omitted. For example, an electron buffer layer may be further added between the electron transport layer and the electron injection layer; the organic layer having the same function may be formed into a stacked structure of two or more layers, and for example, the electron transport layer may further include a first electron transport layer and a second electron transport layer.

The method for preparing and forming each layer in the organic light emitting device is not particularly limited, and any one of vacuum evaporation method, spin coating method, vapor deposition method, blade coating method, laser thermal transfer method, electrospray coating method, slit coating method, and dip coating method may be used, and in the present invention, a vacuum evaporation method is preferably used.

The organic light-emitting device can be widely applied to the fields of panel display, illumination light sources, flexible OLED, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, indication boards, signal lamps and the like.

The present invention is explained more fully by the following examples, but is not intended to be limited thereby. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue burden.

Preparation and characterization of the Compounds

Description of the starting materials, reagents and characterization equipment:

the source of the raw materials used in the following examples is not particularly limited and may be commercially available products or prepared by a preparation method well known to those skilled in the art.

The mass spectrum uses a Wotes G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer in UK, chloroform as a solvent;

the elemental analysis was carried out using a Vario EL cube organic elemental analyzer from Elementar, germany, and the sample mass was 5 to 10mg.

Synthesis example 1: preparation of Compound 3

Step1: synthetic intermediate A-3

A reaction flask was charged with a-3 (13.35 g,85.00 mmol), b-3 (7.92 g,85.00 mmol), sodium t-butoxide (12.25 g,127.50 mmol) in 400ml toluene under nitrogen and Pd (dppf) Cl with stirring ₂ (0.75 g,1.02 mmol) the mixture of the above reactants was heated under reflux for 4h. ReactionAfter completion of cooling to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallisation from ethyl acetate gives intermediate A-3 (12.51 g, 87%) which has a purity of > 99.79% as measured by HPLC. Mass spectrum m/z:169.0880 (theory: 169.0891).

Step2: synthetic intermediate C-3

E-3 (8.02 g,35.00 mmol), f-3 (7.33 g,35.00 mmol), sodium tert-butoxide (5.05 g,52.50 mmol) were dissolved in 200ml toluene under nitrogen and Pd (OAc) was added with stirring ₂ (0.08g，0.35mmol)、P(t-Bu) ₃ (1.40 mL,0.70mmol,0.5M in toluene) and the mixture of the above reactants was heated at reflux for 5h. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallisation from toluene/methanol (volume ratio 7:1) gives intermediate C-3 (10.64 g, 85%) which has a purity of > 99.83% as measured by HPLC. Mass spectrum m/z:357.1925 (theory: 357.1913).

Step3: synthesis of intermediate I-3

Intermediate A-3 (11.85 g,70.00 mmol), g-3 (9.46 g,35.00 mmol), sodium tert-butoxide (6.73 g,70.00 mmol) were dissolved in 320ml toluene under nitrogen and Pd (OAc) was added with stirring ₂ (0.16g，0.70mmol)、P(t-Bu) ₃ (2.80 mL,1.40mmol,0.5M in toluene) and the mixture of the above reactants was heated at reflux for 4.5h. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Purification by column chromatography on silica gel using n-hexane/dichloromethane (volume ratio 8:1) afforded intermediate I-3 (12.67 g, 81%), which was found to have a purity of > 99.89% by HPLC. Mass spectrum m/z:446.1559 (theory: 446.1550).

Step4: synthesis of Compound 3

Intermediate I-3 (11.17 g,25.00 mmol), intermediate C-3 (8.94 g,25.00 mmol) and sodium tert-butoxide (3.60 g,37.50 mmol) were dissolved in 150ml toluene under nitrogen and Pd was added under stirring ₂ (dba) ₃ (0.23 g,0.25 mmol), X-Phos (0.24 g,0.50 mmol), and reacting the aboveThe mixture of the reactants was heated to reflux for 5h. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallisation from toluene gives compound 3 (14.59 g, 76%) which has a purity of > 99.94% as measured by HPLC. Mass spectrum m/z:767.3685 (theory: 767.3696). Theoretical element content (%) C ₅₄ H ₄₉ N ₃ Si: c,84.44; h,6.43; n,5.47. Measured element content (%): c,84.47; h,6.41; n,5.44.

Synthesis example 2: preparation of Compound 11

The procedure was otherwise identical except for changing a-3 to equimolar a-11, e-3 to equimolar e-11 and f-3 to equimolar f-11 in Synthesis example 1 to give Compound 11 (16.62 g) with a purity of 99.90% as measured by HPLC. Mass spectrum m/z:897.4488 (theory: 897.4478). Theoretical element content (%) C ₆₄ H ₅₉ N ₃ Si: c,85.57; h,6.62; n,4.68. Measured element content (%): c,85.55; h,6.65; n,4.64.

Synthesis example 3: preparation of Compound 19

The procedure was otherwise identical except for changing a-3 in Synthesis example 1 to equimolar a-19 and e-3 to equimolar e-11 to give Compound 19 (17.30 g) with a purity of 99.92% as measured by HPLC. Mass spectrum m/z:947.2736 (theory: 947.2754). Theoretical element content (%) C ₅₄ H ₃₉ F ₁₀ N ₃ Si: c,68.42; h,4.15; n,4.43. Measured element content (%): c,68.39; h,4.18; n,4.41.

Synthesis example 4: preparation of Compound 25

The procedure was otherwise identical except for changing e-3 to equimolar e-11 and f-3 to equimolar f-25 in Synthesis example 1 to give Compound 25 (14.73 g), which was found to have a solid purity of ≡ 99.94% by HPLC. Mass spectrum m/z:817.3870 (theory: 817.3852). Theoretical element content (%) C ₅₈ H ₅₁ N ₃ Si: c,85.15; h,6.28; n,5.14. Measured element content (%): c,85.17; h,6.31; n,5.11.

Synthesis example 5: preparation of Compound 32

The procedure was otherwise identical except for changing a-3 in Synthesis example 1 to equimolar a-32 and e-3 to equimolar e-11 to give Compound 32 (17.26 g), and the purity of the solid was ≡ 99.97% by HPLC. Mass spectrum m/z:919.4337 (theory: 919.4322). Theoretical element content (%) C ₆₆ H ₅₇ N ₃ Si: c,86.14; h,6.24; n,4.57. Measured element content (%): c,86.12; h,6.23; n,4.59.

Synthesis example 6: preparation of Compound 44

The procedure was otherwise identical except for changing a-3 to equimolar a-44 and e-3 to equimolar e-44 in Synthesis example 1 to give Compound 44 (19.31 g), which was found to have a solid purity of ≡ 99.93% by HPLC. Mass spectrum m/z:1071.5325 (theory: 1071.5343). Theoretical element content (%) C ₇₅ H ₇₃ N ₃ Si ₂ : c,83.99; h,6.86; n,3.92. Measured element content (%): c,83.96; h,6.84; n,3.95.

Synthesis example 7: preparation of Compound 49

The procedure was otherwise as for changing a-3 from synthesis example 1 to equimolar a-32, e-3 to equimolar e-49 and f-3 to equimolar b-3, to give compound 49 (17.03 g), and the purity of the solid was ≡ 99.94% by HPLC. Mass spectrum m/z:919.4336 (theory: 919.4322). Theoretical element content (%) C ₆₆ H ₅₇ N ₃ Si: c,86.14; h,6.24; n,4.57. Measured element content (%): c,86.17; h,6.26; n,4.53.

Synthesis example 8: preparation of Compound 152

The procedure was otherwise as except for changing a-3 in Synthesis example 1 to equimolar e-11, b-3 to equimolar b-152 and e-3 to equimolar e-152, to give compound 152 (19.03 g) having a purity of 99.91% or higher as measured by HPLC. Mass spectrum m/z:1041.4859 (theory: 1041.4874). Theoretical element content (%) C ₇₃ H ₆₇ N ₃ Si ₂ : c,84.10; h,6.48; n,4.03. Measured element content (%): c,84.13; h,6.45; n,4.06.

Synthesis example 9: preparation of Compound 194

The procedure was otherwise as except for changing a-3 in Synthesis example 1 to equimolar e-11, e-3 to equimolar e-194 and f-3 to equimolar b-3, to give compound 194 (15.46 g), and the purity of the solid was not less than 99.92% as measured by HPLC. Mass spectrum m/z:846.4537 (theory: 846.4530). Theoretical element content (%) C ₅₇ H ₅₀ D ₇ N ₃ Si ₂ : c,80.80; h,7.61; n,4.96. Measured element content (%): c,80.82; h,7.59; n,4.93.

Synthesis example 10: preparation of Compound 198

The procedure was otherwise as for changing a-3 from synthesis example 1 to equimolar e-11, e-3 to equimolar e-198 and f-3 to equimolar b-3, to give compound 198 (16.49 g) having a purity of > 99.95% as measured by HPLC. Mass spectrum m/z:915.4414 (theory: 915.4404). Theoretical element content (%) C ₆₃ H ₆₁ N ₃ Si ₂ : c,82.57; h,6.71; n,4.59. Measured element content (%): c,82.55; h,6.68; n,4.61.

Synthesis example 11: preparation of Compound 202

The procedure was otherwise identical except for changing e-3 to equimolar e-11 and f-3 to equimolar f-202 in Synthesis example 1 to give Compound 202 (16.02 g), which was found to have a solid purity of ≡ 99.94% by HPLC. Mass spectrum m/z:901.4774 (theory: 901.4791). Theoretical element content (%) C ₆₄ H ₆₃ N ₃ Si: c,85.19; h,7.04; n,4.66. Measured element content (%): c,85.17; h,7.06; n,4.61.

Synthesis example 12: preparation of Compound 208

The procedure was otherwise as except for changing a-3 in Synthesis example 1 to equimolar a-208, e-3 to equimolar e-208 and f-3 to equimolar b-3, to give compound 208 (19.54 g), and the purity of the solid was ≡ 99.95% by HPLC detection. Mass spectrum m/z:1115.5958 (theory: 1115.5969). Theoretical element content (%) C ₇₈ H ₈₁ N ₃ Si ₂ : c,83.90; h,7.31; n,3.76. Measured element content (%): c,83.93; h,7.28; n,3.79.

Synthesis example 13: preparation of Compound 211

The procedure was otherwise identical except for changing e-3 to equimolar e-11 and f-3 to equimolar f-211 in Synthesis example 1 to give Compound 211 (16.36 g) with a purity of 99.96% as measured by HPLC. Mass spectrum m/z:843.4020 (theory: 843.4009). Theoretical element content (%) C ₆₀ H ₅₃ N ₃ Si: c,85.37; h,6.33; n,4.98. Measured element content (%): c,85.40; h,6.31; n,4.96.

Synthesis example 14: preparation of Compound 261

The procedure was otherwise identical except for changing e-3 to equimolar e-261 and f-3 to equimolar b-3 in Synthesis example 1 to give Compound 261 (16.73 g) with a purity of > 99.94% as measured by HPLC. Mass spectrum m/z:891.4022 (theory: 891.4009). Theoretical element content (%) C ₆₄ H ₅₃ N ₃ Si: c,86.15; h,5.99; n,4.71. Measured element content (%): c,86.17; h,5.97; n,4.68.

Synthesis example 15: preparation of Compound 267

The procedure was otherwise identical except for changing a-3 to equimolar a-267, b-3 to equimolar b-267, e-3 to equimolar e-11 and f-3 to equimolar f-267 in Synthesis example 1 to give 267 (17.68 g) as compound having a purity of 99.96% as measured by HPLC. Mass spectrum m/z:981.5275 (theory: 981.5262). Theoretical element content (%) C ₇₀ H ₅₁ D ₁₀ N ₃ Si: c,85.58; h,7.28; n,4.28. Measured element content (%): c,85.61; h,7.25; n,4.25.

Synthesis example 16: preparation of Compound 289

The procedure was otherwise identical except for changing a-3 to equimolar a-289, e-3 to equimolar e-11 and f-3 to equimolar f-267 in Synthesis example 1 to give compound 289 (18.86 g), which had a purity of 99.93% as measured by HPLC. Mass spectrum m/z:1061.5749 (theory: 1061.5765). Theoretical element content (%) C ₇₆ H ₄₃ D ₁₈ N ₃ Si: c,85.91; h,7.49; n,3.95. Measured element content (%): c,85.88; h,7.52; n,3.93.

Synthesis example 17: preparation of Compound 293

Step1: synthetic intermediate A-293

A-293 (9.72 g,60.00 mmol), b-3 (5.59 g,60.00 mmol), sodium tert-butoxide (8.65 g,90.00 mmol) were dissolved in 300ml toluene under nitrogen and Pd (dppf) Cl was added with stirring ₂ (0.53 g,0.72 mmol) and the mixture of the above reactants was heated under reflux for 4h. After the completion of the reaction, the reaction solution was cooled to room temperature, water was then added thereto, the mixture was extracted with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallisation from ethyl acetate gives intermediate A-293 (9.20 g, 88%) with a purity of > 99.36% as measured by HPLC. Mass spectrum m/z:174.1218 (theory: 174.1205).

Step2: synthetic intermediate B-293

Under nitrogen, c-293 (12.86 g,50.00 mmol), b-3 (4.66 g,50.00 mmol) and sodium tert-butoxide (7.21 g,75.00 mmol) were dissolved in 250ml toluene and Pd (dppf) Cl was added with stirring ₂ (0.44 g,0.60 mmol) and the mixture of the above reactants was heated under reflux for 4.5h. After the completion of the reaction, the reaction solution was cooled to room temperature, water was then added thereto, the mixture was extracted with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallisation from ethyl acetate gives intermediate B-293 (11.58 g, 86%),HPLC detection of solid purity ∈ 99.53%. Mass spectrum m/z:269.1211 (theory: 269.1204).

Step3: synthetic intermediate C-267

E-11 (9.17 g,40.00 mmol), f-267 (13.34 g,40.00 mmol), sodium tert-butoxide (7.68 g,80.00 mmol) were dissolved in 200ml toluene under nitrogen and Pd (OAc) was added under stirring ₂ (0.09g，0.40mmol)、P(t-Bu) ₃ (1.60 mL,0.80mmol,0.5M in toluene) and the mixture of the above reactants was heated at reflux for 4.5h. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallisation from toluene/methanol (volume ratio 10:1) gives intermediate C-267 (15.80 g, 82%) as a solid of > 99.79% purity by HPLC. Mass spectrum m/z:481.2211 (theory: 481.2226).

Step4: synthetic intermediate I-293

Intermediate A-293 (7.84 g,45.00 mmol), g-293 (14.28 g,45.00 mmol) and sodium tert-butoxide (6.49 g,67.50 mmol) were dissolved in 250ml toluene under nitrogen and Pd (OAc) was added with stirring ₂ (0.10g，0.45mmol)、P(t-Bu) ₃ (1.80 mL,0.90mmol,0.5M in toluene) and the mixture of the above reactants was heated at reflux for 5h. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Purification by column chromatography on silica gel using n-hexane/dichloromethane (volume ratio 9:1) afforded intermediate I-293 (12.93 g, 79%) as a solid with a purity of > 99.83% by HPLC. Mass spectrum m/z:362.0248 (theory: 362.0234).

Step5: synthesis of intermediate II-293

Under the protection of nitrogen, intermediate I-293 (12.73 g,35.00 mmol), intermediate B-293 (9.43 g,35.00 mmol) and sodium tert-butoxide (5.05 g,52.50 mmol) were dissolved in 200ml toluene and Pd was added under stirring ₂ (dba) ₃ (0.32g，0.35mmol)、P(t-Bu) ₃ (1.40 mL,0.70mmol,0.5M in toluene) and the mixture of the above reactants was heated at reflux for 5h. After the reaction, cooling to room temperature, adding water, extracting with dichloromethane, and collecting the organic layer with anhydrous sulfurThe magnesium acid was dried, filtered, and the solvent was removed under reduced pressure. Purification by column chromatography on silica gel using n-hexane/dichloromethane (6:1 by volume) afforded intermediate II-293 (14.88 g, 77%) as a solid having a purity of > 99.85% by HPLC. Mass spectrum m/z:551.2159 (theory: 551.2177).

Step6: synthesis of Compound 293

Intermediate II-293 (13.80 g,25.00 mmol), intermediate C-267 (12.04 g,25.00 mmol) and sodium tert-butoxide (3.84 g,40.00 mmol) were dissolved in 150ml toluene under nitrogen and Pd was added under stirring ₂ (dba) ₃ (0.23 g,0.25 mmol) and X-Phos (0.24 g,0.50 mmol), and the mixture of the above reactants was heated under reflux for 6h. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallisation from toluene gives compound 293 (18.45 g, 74%) which has a purity of > 99.94% as measured by HPLC. Mass spectrum m/z:996.4648 (theory: 996.4636). Theoretical element content (%) C ₇₂ H ₅₂ D ₅ N ₃ Si: c,86.71; h,6.27; n,4.21. Measured element content (%): c,86.74; h,6.25; n,4.19.

Synthesis example 18: preparation of Compound 313

The procedure was otherwise identical except for changing a-3 to equimolar e-11, b-3 to equimolar b-313, e-3 to equimolar e-313 and f-3 to equimolar b-3 in Synthesis example 1, to give Compound 313 (19.57 g) having a purity of 99.95% as measured by HPLC. Mass spectrum m/z:1071.5325 (theory: 1071.5343). Theoretical element content (%) C ₇₅ H ₇₃ N ₃ Si ₂ : c,83.99; h,6.86; n,3.92. Measured element content (%): c,83.95; h,6.88; n,3.89.

Synthesis example 19: preparation of Compound 331

The procedure was otherwise as defined except for changing a-3 in Synthesis example 1 to equimolar e-11, e-3 to equimolar e-331 and f-3 to equimolar b-3 to give compound 331 (18.80 g), and the purity of the solid was ≡ 99.96% by HPLC. Mass spectrum m/z:1043.5021 (theory: 1043.5030). Theoretical element content (%) C ₇₃ H ₆₉ N ₃ Si ₂ : c,83.94; h,6.66; n,4.02. Measured element content (%): c,83.97; h,6.64; n,4.04.

Synthesis example 20: preparation of Compound 333

The procedure was otherwise identical except for changing a-3 to equimolar a-333, e-3 to equimolar e-11 and f-3 to equimolar f-333 in Synthesis example 1 to give Compound 333 (18.28 g), which was found to have a solid purity of ≡ 99.92% by HPLC. Mass spectrum m/z:1000.4933 (theory: 1000.4949). Theoretical element content (%) C ₇₂ H ₅₆ D ₅ N ₃ Si: c,86.36; h,6.64; n,4.20. Measured element content (%): c,86.39; h,6.66; n,4.16.

Synthesis example 21: preparation of Compound 334

The procedure was otherwise as except for changing a-3 in Synthesis example 1 to equimolar e-11, e-3 to equimolar e-334 and f-3 to equimolar b-3 to give compound 334 (18.73 g) having a purity of 99.95% or higher as measured by HPLC. Mass spectrum m/z:1039.4729 (theory: 1039.4717). Theoretical element content (%) C ₇₃ H ₆₅ N ₃ Si ₂ : c,84.27; h,6.30; n,4.04. Measured element content (%): c,84.25; the gas phase is taken as H,6.28；N,4.08。

synthesis example 22: preparation of Compound 346

The procedure was otherwise as except for changing e-3 to equimolar e-11, f-3 to equimolar f-267, and g-3 to equimolar g-346 in Synthesis example 1, to give Compound 346 (16.77 g), which was found to have a solid purity of ≡ 99.94% by HPLC. Mass spectrum m/z:905.4156 (theory: 905.4165). Theoretical element content (%) C ₆₅ H ₅₅ N ₃ Si: c,86.15; h,6.12; n,4.64. Measured element content (%): c,86.18; h,6.14; n,4.61.

Synthesis example 23: preparation of Compound 362

The procedure was otherwise as except for changing a-3 in Synthesis example 1 to equimolar a-293, e-3 to equimolar e-11 and f-3 to equimolar f-362 to give compound 362 (15.98 g) having a purity of > 99.93% as measured by HPLC. Mass spectrum m/z:899.4493 (theory: 899.4480). Theoretical element content (%) C ₆₄ H ₄₁ D ₁₀ N ₃ Si: c,85.39; h,6.83; n,4.67. Measured element content (%): c,85.42; h,6.81; n,4.65.

Synthesis example 24: preparation of Compound 405

The synthesis example 1 was conducted in the same manner as described above except that a-3 was replaced with equimolar e-11, e-3 was replaced with equimolar e-11, f-3 was replaced with equimolar f-405, and the obtained product was convertedCompound 405 (18.88 g) has a purity of > 99.94% as measured by HPLC. Mass spectrum m/z:1033.4651 (theory: 1033.4643). Theoretical element content (%) C ₇₀ H ₆₇ N ₃ Si ₃ : c,81.27; h,6.53; n,4.06. Measured element content (%): c,81.30; h,6.55; n,4.02.

Synthesis example 25: preparation of Compound 412

The procedure was otherwise identical except for changing e-3 to equimolar e-11 and f-3 to equimolar f-412 in Synthesis example 1 to give Compound 412 (17.51 g) with a purity of 99.96% as measured by HPLC. Mass spectrum m/z:945.4490 (theory: 945.4478). Theoretical element content (%) C ₆₈ H ₅₉ N ₃ Si: c,86.31; h,6.28; n,4.44. Measured element content (%): c,86.34; h,6.31; n,4.42.

Synthesis example 26: preparation of Compound 458

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The procedure was otherwise identical except for changing a-3 to equimolar a-458, b-3 to equimolar b-458, e-3 to equimolar e-11 and f-3 to equimolar f-458 in Synthesis example 1 to give compound 458 (20.39 g) having a purity of 99.92% as measured by HPLC. Mass spectrum m/z:1131.6712 (theory: 1131.6702). Theoretical element content (%) C ₈₁ H ₇₃ D ₈ N ₃ Si: c,85.89; h,7.92; n,3.71. Measured element content (%): c,85.92; h,7.88; n,3.74.

Synthesis example 27: preparation of Compound 509

The procedure was otherwise identical except for changing e-3 to equimolar e-11 and f-3 to equimolar f-509 in Synthesis example 1 to give Compound 509 (17.01 g), which was found to have a solid purity of ≡ 99.96% by HPLC. Mass spectrum m/z:931.4311 (theory: 931.4322). Theoretical element content (%) C ₆₇ H ₅₇ N ₃ Si: c,86.32; h,6.16; n,4.51. Measured element content (%): c,86.35; h,6.14; n,4.49.

Synthesis example 28: preparation of Compound 542

The procedure was otherwise as except for changing a-3 in Synthesis example 1 to equimolar a-542, e-3 to equimolar e-11 and f-3 to equimolar f-542, to give compound 542 (16.54 g), and the purity of the solid was ≡ 99.96% by HPLC detection. Mass spectrum m/z:881.4732 (theory: 881.4740). Theoretical element content (%) C ₆₁ H ₆₃ N ₃ OSi: c,83.04; h,7.20; n,4.76. Measured element content (%): c,83.06; h,7.17; n,4.79.

Synthesis example 29: preparation of Compound 555

The procedure was otherwise identical except for changing e-3 to equimolar e-555 and f-3 to equimolar f-542 in Synthesis example 1 to give compound 555 (17.40 g), which had a purity of 99.95% as measured by HPLC. Mass spectrum m/z:927.3629 (theory: 927.3645). Theoretical element content (%) C ₆₆ H ₄₉ N ₃ OSi: c,85.40; h,5.32; n,4.53. Measured element content (%): c,85.38; h,5.35; n,4.56.

Synthesis example 30: preparation of Compound 573

The procedure was otherwise identical except for changing a-3 to equimolar a-573, e-3 to equimolar e-573, and f-3 to equimolar b-3 in Synthesis example 1 to give Compound 573 (17.12 g), which had a purity of > 99.93% as measured by HPLC. Mass spectrum m/z:963.4059 (theory: 963.4040). Theoretical element content (%) C ₆₆ H ₅₇ N ₃ OSi ₂ : c,82.20; h,5.96; n,4.36. Measured element content (%): c,82.24; h,5.93; n,4.32.

Synthesis example 31: preparation of Compound 578

The procedure was otherwise identical except for changing a-3 to equimolar a-578, e-3 to equimolar e-11, and f-3 to equimolar f-542 in Synthesis example 1 to give compound 578 (18.44 g) having a purity of 99.94% as measured by HPLC. Mass spectrum m/z:1009.5352 (theory: 1009.5366). Theoretical element content (%) C ₇₁ H ₇₁ N ₃ OSi: c,84.40; h,7.08; n,4.16. Measured element content (%): c,84.37; h,7.11; n,4.14.

Synthesis example 32: preparation of Compound 587

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The procedure was otherwise identical except for changing a-3 to equimolar a-587, e-3 to equimolar a-3 and f-3 to equimolar f-542 in Synthesis example 1 to give Compound 587 (18.51 g) having a purity of 99.93% as measured by HPLC. Mass spectrum m/z:1013.4188 (theory: 1013.4197). Theoretical element content (%) C ₇₀ H ₅₉ N ₃ OSi ₂ : c,82.88; h,5.86; n,4.14. Measured element content (%): c,82.85; h,5.84; n,4.18.

Synthesis example 33: preparation of Compound 592

The procedure was otherwise as except for changing a-3 in Synthesis example 1 to equimolar a-267, e-3 to equimolar e-592 and f-3 to equimolar f-592, to give compound 592 (16.17 g) having a purity of 99.94% as measured by HPLC. Mass spectrum m/z:897.4125 (theory: 897.4114). Theoretical element content (%) C ₆₃ H ₅₅ N ₃ OSi: c,84.24; h,6.17; n,4.68. Measured element content (%): c,84.26; h,6.15; n,4.65.

Synthesis example 34: preparation of Compound 612

The procedure was otherwise as except for changing b-3 to equimolar f-542, e-3 to equimolar e-612 and f-3 to equimolar b-3 in Synthesis example 1, to give Compound 612 (16.80 g) having a purity of > 99.93% as measured by HPLC. Mass spectrum m/z:907.3580 (theory: 907.3594). Theoretical element content (%) C ₆₃ H ₄₉ N ₃ O ₂ Si: c,83.32; h,5.44; n,4.63. Measured element content (%): c,83.35; h,5.40; n,4.66.

Synthesis example 35: preparation of Compound 621

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The procedure was otherwise as defined except for changing a-3 in Synthesis example 1 to equimolar e-11, e-3 to equimolar a-3 and f-3 to equimolar f-542 to give compound 621 (15.27 g) having a purity of not less than 99.96% as measured by HPLC. Mass spectrum m/z:813.3582 (theory: 813.3571). Theoretical element content (%) C ₅₄ H ₅₁ N ₃ OSi ₂ : c,79.66; h,6.31; n,5.16. Measured element content (%): c,79.68; h,6.29; n,5.18.

Synthesis example 36: preparation of Compound 669

Step1: synthetic intermediate C-542

E-11 (17.19 g,75.00 mmol), f-542 (13.74 g,75.00 mmol), sodium tert-butoxide (10.81 g,112.50 mmol) were dissolved in 400ml toluene under nitrogen and Pd (dppf) Cl was added with stirring ₂ (0.66 g,0.90 mmol) and the mixture of the above reactants was heated under reflux for 4.5h. After the completion of the reaction, the reaction mixture was cooled to room temperature, water was then added, the mixture was extracted with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the mixture was recrystallized from ethyl acetate to give intermediate C-542 (20.88 g, yield 84%) which was found to have a solid purity of ≡ 99.71% by HPLC. Mass spectrum m/z:331.1381 (theory: 331.1392).

Step2: synthetic compound 669

Intermediate C-542 (19.89 g,60.00 mmol), g-669 (6.30 g,20.00 mmol) and sodium tert-butoxide (3.84 g,40.00 mmol) were dissolved in 160ml toluene under nitrogen and Pd was added under stirring ₂ (dba) ₃ (0.18g，0.20mmol)、P(t-Bu) ₃ (0.8 mL,0.40mmol,0.5M toluene solution) and the mixture of the above reactants was heated back for 5h. After the completion of the reaction, the reaction mixture was cooled to room temperature, water was added, the mixture was extracted with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and recrystallized from toluene to give compound 669 (15.78 g, 74%), and the purity of the solid was ≡ 99.93% by HPLC detection. Mass spectrum m/z:1065.4185 (theory: 1065.4177). Theoretical element content (%) C ₆₉ H ₆₃ N ₃ O ₃ Si ₃ : c,77.71; h,5.95; n,3.94. Measured element content (%): c,77.74; h,5.91; n,3.98.

Synthesis example 37: preparation of Compound 679

The a-3 in synthesis example 1 was replaced with equimolar e-11,e-3 was changed to equimolar e-679, f-3 was changed to equimolar b-3, and the procedure was the same, except that compound 679 (16.69 g) was obtained, and the purity of the solid was. Mass spectrum m/z:889.3896 (theory: 889.3884). Theoretical element content (%) C ₆₀ H ₅₅ N ₃ OSi ₂ : c,80.95; h,6.23; n,4.72. Measured element content (%): c,80.97; h,6.20; n,4.69.

Synthesis example 38: preparation of Compound 711

The procedure was otherwise identical except for changing a-3 to equimolar a-711, e-3 to equimolar e-11 and f-3 to equimolar f-542 in Synthesis example 1 to give Compound 711 (15.41 g) with a purity of 99.91% as measured by HPLC. Mass spectrum m/z:855.4389 (theory: 855.4367). Theoretical element content (%) C ₅₉ H ₃₃ D ₁₄ N ₃ OSi: c,82.77; h,7.18; n,4.91. Measured element content (%): c,82.79; h,7.15; n,4.89.

Synthesis example 39: preparation of Compound 724

The procedure was otherwise identical except for changing a-3 to equimolar e-11, e-3 to equimolar e-724 and f-3 to equimolar b-3 in Synthesis example 1 to give compound 724 (17.86 g) having a purity of 99.93% as measured by HPLC. Mass spectrum m/z:977.4178 (theory: 977.4197). Theoretical element content (%) C ₆₇ H ₅₉ N ₃ OSi ₂ : c,82.25; h,6.08; n,4.29. Measured element content (%): c,82.29; h,6.05; n,4.27.

Synthesis example 40: preparation of Compound 742

The procedure was otherwise identical except for changing a-3 to equimolar a-742, e-3 to equimolar e-11 and f-3 to equimolar f-742 in Synthesis example 1 to give compound 742 (17.69 g), and the purity of the solid was ≡ 99.94% by HPLC. Mass spectrum m/z:981.5440 (theory: 981.5451). Theoretical element content (%) C ₆₇ H ₇₅ N ₃ SSi: c,81.91; h,7.69; n,4.28. Measured element content (%): c,81.89; h,7.66; n,4.26.

Synthesis example 41: preparation of Compound 923

The procedure was otherwise identical except for changing a-3 to equimolar e-11, b-3 to equimolar b-923, e-3 to equimolar e-923 and f-3 to equimolar b-3 in Synthesis example 1 to give Compound 923 (19.49 g) having a purity of > 99.95% as measured by HPLC. Mass spectrum m/z:1052.5622 (theory: 1052.5609). Theoretical element content (%) C ₇₂ H ₇₆ N ₄ Si ₂ : c,82.08; h,7.27; n,5.32. Measured element content (%): c,82.11; h,7.25; n,5.35.

Synthesis example 42: preparation of Compound 974

The procedure was otherwise identical except for changing a-3 to equimolar e-11, e-3 to equimolar e-974 and f-3 to equimolar b-3 in Synthesis example 1 to give compound 974 (17.86 g) having a purity of 99.92% or higher as measured by HPLC. Mass spectrum m/z:964.4369 (theory: 964.4357). Theoretical element content (%) C ₆₆ H ₆₀ N ₄ Si ₂ : c,82.11; h,6.26; n,5.80. Measured element content (%): c,82.14; h,6.23; n,5.79.

Synthesis example 43: preparation of Compound 1050

The procedure was otherwise identical except for changing a-3 in Synthesis example 1 to equimolar a-1050 and e-3 to equimolar e-11 to give compound 1050 (18.29 g), and the purity of the solid was ≡ 99.93% by HPLC detection. Mass spectrum m/z:1001.4114 (theory: 1001.4125). Theoretical element content (%) C ₆₈ H ₅₅ N ₅ O ₂ Si: c,81.49; h,5.53; n,6.99. Measured element content (%): c,81.51; h,5.51; n,6.96.

Synthesis example 44: preparation of Compound 1099

The procedure was otherwise as except for changing a-3 in Synthesis example 1 to equimolar a-1099, e-3 to equimolar e-11 and f-3 to equimolar f-542, to give compound 1099 (16.39 g) having a purity of 99.94% or higher as measured by HPLC. Mass spectrum m/z:897.3630 (theory: 897.3611). Theoretical element content (%) C ₅₉ H ₄₇ N ₇ OSi: c,78.90; h,5.27; n,10.92. Measured element content (%): c,78.93; h,5.24; n,10.90.

Synthesis example 45: preparation of Compound 1139

The procedure was otherwise identical except for changing a-3 to equimolar a-1139, e-3 to equimolar e-11 and f-3 to equimolar f-742 in Synthesis example 1 to give compound 1139 (18.22 g) having a purity of 99.91% or higher as measured by HPLC. Mass spectrum m/z:1011.3780 (theory: 1011.3791). Theoretical element content (%) C ₆₉ H ₅₃ N ₅ SSi: c,81.86; h,5.28; n,6.92. Measured element content (%): c,81.88; h,5.25; n,6.89.

Green organic light emitting device (hole transport layer)

Comparative examples 1-2 device preparation examples:

comparative example 1: the organic light emitting device is prepared by utilizing a vacuum thermal evaporation method. The experimental steps are as follows: the ITO substrate is put in distilled water for 3 times, washed by ultrasonic waves for 15 minutes, washed by ultrasonic waves sequentially by solvents such as isopropanol, acetone, methanol and the like after the distilled water is washed, dried and dried at 120 ℃, and sent into an evaporator.

Evaporating a hole injection layer 1T-NATA/63nm, an evaporating hole transmission layer HT1-1/100nm and an evaporating main body m-CBP on the prepared ITO transparent electrode in a layer-by-layer vacuum evaporation mode: ir doped (ppy) ₂ acac (mass ratio 94%:6% mixed)/23 nm, then evaporating an electron transport layer TpPyPB and Liq (mass ratio 1:1)/28 nm, an electron injection layer LiF/1nm, and a cathode Al/130nm. And sealing the device in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is shown as follows:

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comparative example 2: the organic light emitting device of comparative example 2 was manufactured in the same manner as comparative example 1, except that the hole transport layer material HT1-1 in comparative example 1 was replaced with HT 1-2.

Application examples 1 to 31

Application examples 1-31: the hole transport layer material HT1-1 of the organic light emitting device was changed to the compound 3, 11, 25, 32, 44, 49, 152, 198, 202, 211, 261, 267, 289, 313, 346, 362, 405, 412, 458, 509, 542, 555, 578, 592, 612, 621, 669, 679, 742, 923, 974 of the present invention in this order, and the other steps were the same as those of comparative example 1.

Test software, a computer, a K2400 digital source list manufactured by Keithley corporation, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research corporation, U.S. were combined into a single integrated IVL test system to test the luminous efficiency of an organic light emitting device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature. The results of the light emission characteristics test of the obtained organic light emitting device are shown in table 1. Table 1 shows the results of the light emitting characteristics test of the light emitting devices prepared with the compounds prepared in the examples of the present invention and the comparative substances.

TABLE 1 test of light emitting characteristics of light emitting device

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Note that: t97 means that the current density is 10mA/cm ² In the case, the time taken for the device brightness to decay to 97%;

as can be seen from the results of Table 1, the star-shaped triamine compound of the present invention is applied to an organic light emitting device, and as a hole transport layer material, compared with comparative examples 1-2, the improvement of the device performance can be seen, and silicon is a main factor affecting the device performance, which shows the advantages of high light emitting efficiency and long service life.

Red organic light emitting device (second hole transport layer)

Comparative examples 3-4 device preparation examples:

comparative example 3: the organic light emitting device is prepared by utilizing a vacuum thermal evaporation method. The experimental steps are as follows: the ITO transparent substrate is put in distilled water for 3 times, washed by ultrasonic waves for 15 minutes, washed by ultrasonic waves sequentially by solvents such as isopropanol, acetone, methanol and the like after the distilled water is washed, dried and dried at 120 ℃, and sent into an evaporator.

Hole injection layer 1T-NATA/63nm, vapor deposition hole transport layer HT/70nm, vapor deposition second hole transport layer HT1-1/30nm, vapor deposition luminescent layer (Main body m-CBP: ir (2-phq) ₂ acac (mass ratio 98%:2% mixing))/24 nm, then evaporation of the electron transport layer TpPyPB with Liq (mass ratio 1:1)/28 nm, electron injection layer LiF/1nm, cathode Al/130nm. And putting the sameThe device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is shown as follows:

comparative example 4: the organic light emitting device of comparative example 4 was manufactured in the same manner as comparative example 3, except that the second hole transport layer material HT1-1 in comparative example 3 was replaced with HT 2-2.

Application examples 32 to 73

Application examples 32-73: the second hole transport layer material of the organic light emitting device was changed to the inventive compounds 3, 11, 19, 25, 32, 44, 49, 152, 194, 198, 202, 208, 211, 261, 267, 289, 293, 313, 331, 333, 334, 346, 362, 405, 412, 458, 509, 542, 555, 573, 578, 587, 592, 612, 621, 669, 679, 711, 724, 742, 923, 974 in this order, and the other steps were the same as comparative example 3.

The driving voltage and the luminous efficiency of the organic luminous device are tested by combining test software, a computer, a K2400 digital source list manufactured by Keithley corporation 923 in U.S. and a PR788 spectrum scanning luminance meter manufactured by Photo Research in U.S. into a combined IVL test system. The results of the light emission characteristics test of the obtained organic light emitting device are shown in table 2. Table 2 shows the results of the light emitting characteristics test of the light emitting devices prepared with the compounds prepared in the examples of the present invention and the comparative substances.

TABLE 2 test of light emitting characteristics of light emitting device

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From the results of Table 2, it is possible toAs can be seen, when the star-shaped triamine compound of the present invention is applied to an organic light-emitting device as a second hole transport layer material, compared with comparative examples 3-4, it can be seen that silicon is a main factor affecting the performance of the device, the light-emitting efficiency and the service life of the organic light-emitting device are significantly improved, and the star-shaped triamine compound is an organic light-emitting material with good performance, particularly when Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ When one or more silane groups are introduced, the hole transport property and the thermal stability of the compound are improved.

Comparative examples 5-6 device preparation examples:

comparative example 5: the organic light emitting device is prepared by utilizing a vacuum thermal evaporation method. The experimental steps are as follows: the ITO-Ag-ITO substrate is put in distilled water for 3 times, ultrasonic washing is carried out for 15 minutes, after the distilled water is washed, solvents such as isopropanol, acetone, methanol and the like are sequentially washed by ultrasonic waves, and then the substrate is dried and dried at 120 ℃ and is sent into an evaporator.

Evaporating a hole injection layer 1T-NATA/63nm, an evaporating hole transmission layer HT/100nm and an evaporating body BH on the prepared ITO-Ag-ITO transparent electrode in a layer-by-layer vacuum evaporation mode: BD (97% by mass: 3% mixed)/25 nm is doped, then an electron transport layer TpPyPB and Liq (1:1 by mass) are evaporated, an electron injection layer LiF/1nm, a cathode Mg-Ag/19nm, and a coating layer CP-1/80nm is evaporated on the cathode. And sealing the device in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is shown as follows:

comparative example 6: the organic light emitting device of comparative example 6 was manufactured in the same manner as comparative example 5, except that the capping layer material CP-1 of comparative example 5 was replaced with CP-2.

Application examples 74 to 90

Application examples 74-90: the capping materials of the organic light-emitting devices were changed to the inventive compounds 19, 25, 32, 152, 198, 313, 405, 555, 573, 578, 621, 669, 724, 974, 1050, 1099, 1139 in this order, and the other steps were the same as comparative example 5.

Test software, a computer, a K2400 digital source meter manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research, U.S. are combined into a combined IVL test system to test the driving voltage and luminous efficiency of the organic light emitting device. The results of the light emission characteristics test of the obtained organic light emitting device are shown in table 3. Table 3 shows the results of the luminescence characteristics test of the light emitting devices prepared from the compounds prepared in the examples of the present invention and the comparative substances.

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Note that: t95 means that the current density is 10mA/cm ² In the case, the time taken for the brightness of the device to decay to 95%;

as can be seen from the results of table 3, the star-shaped triamine compound of the present invention is applied to an organic light emitting device, and as a coating material, the light extraction efficiency can be effectively improved, and thus the light emitting efficiency of the organic light emitting device can be improved, compared with comparative examples 5 to 6, and is an organic light emitting device coating material having good performance.

It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.

Claims

1. A star-shaped triamine compound is characterized in that the molecular structure is shown as a formula I:

the R is _a Identically or differently selected from one of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, substituted or unsubstituted C6-C25 aromatic ring and C3-C25 aliphatic ring condensed ring group, or any adjacent two R _a The groups are bonded together to form a substituted or unsubstituted cyclic structure;

The a is selected from 1, 2 or 3; said b is selected from 1, 2, 3 or 4;

R _c the same or different one selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C25 heterocycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted C2-C25 heteroaryl, or optionally adjacent two R _c The groups may be bonded together to form a substituted or unsubstituted cyclic structure;

the L is ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ Independently selected from a single bond, a substituted or unsubstituted C6-C25 arylene group, a substituted or unsubstituted C2-C25 heteroarylene group, a substituted or unsubstituted C3-C12 alicyclic ring, and One of the sub-condensed ring groups of the C6-C25 aromatic ring;

2. The star triamine compound according to claim 1, wherein the Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ Containing one or more substituted or unsubstituted silyl groups.

3. The star triamine compound according to claim 1, wherein the formula a is selected from one of the following groups:

the R is _a Identically or differently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, one of the following substituted or unsubstituted groups: one of trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, the substituent of the "substituted or unsubstituted" being selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl One or more of phenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, camphene, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, or any two adjacent R _a The groups are bonded together to form a substituted or unsubstituted benzene or naphthalene ring;

the R is _m Identically or differently selected from one of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl, tert-butyldimethylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, tridecylphenylsilyl, dideuterophenylmethylsilyl, deuterated phenyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, or any two adjacent R _m The groups are bonded together to form a substituted or unsubstituted benzene or naphthalene ring; the R is _m Can also be R _mm Substituted, R _mm One or more selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, silyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, camphene, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, where substituted with multiple substituents, the multiple substituents are the same or different from each other;

the m is ₂ Selected from 1, 2, 3 or 4; m is m ₃ Selected from 1, 2, 3, 4, 5 or 6; m is m ₄ Selected from 1, 2, 3, 4, 5, 6, 7 or 8; m is m ₅ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; m is m ₆ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; m is m ₇ Selected from 1, 2, 3, 4, 5, 6,7. 8, 9, 10, 11, 12, 13 or 14.

4. The star triamine compound according to claim 1, wherein the formula a is selected from one of the following groups:

5. The star triamine compound according to claim 1, wherein the formula b is selected from one of the following groups:

the R is _e The same or different one of hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, trimethylsilyl, triphenylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, camphenethyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated phenyl, deuterated naphthyl and deuterated biphenyl; wherein said R is _e Can also be R _ee Substituted, R _ee One or more selected from hydrogen, deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl;

6. According to claimThe star-shaped triamine compound according to claim 1, characterized in that the L ₁ 、L ₂ 、L ₃ 、L ₄ 、L ₅ 、L ₆ Independently selected from single bond, substituted or unsubstituted such groups: phenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, phenyl-naphthyl, naphthyl-naphthyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, and combinations thereof, wherein the substituents are one or more of deuterium, tritium, cyano, halogen, trifluoromethyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, and where substituted with multiple substituents, the multiple substituents are the same or different from each other.

7. The star triamine compound according to claim 1, wherein the star triamine compound represented by the formula i is selected from any one of the chemical structures shown below:

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8. an organic light-emitting device comprising an anode, a cathode, and an organic layer 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 star-shaped triamine compounds according to any one of claims 1 to 7.

9. An organic light-emitting device according to claim 8, wherein the organic layer comprises a hole-transporting region, a light-emitting layer, an electron-transporting region or a cover layer, and wherein at least one of the hole-transporting region and the cover layer contains any one or a combination of at least two of the star-shaped triamine compounds according to any one of claims 1 to 7.

10. An organic light-emitting device according to claim 9, wherein the hole transport region comprises at least one of a hole injection layer, a hole transport layer, and an electron blocking layer, and the hole transport layer contains any one or a combination of at least two of the star-shaped triamine compounds according to any one of claims 1 to 7.