CN117903188A

CN117903188A - Heterocyclic compound and organic electroluminescent device thereof

Info

Publication number: CN117903188A
Application number: CN202410050418.7A
Authority: CN
Inventors: 郭建华; 苗玉鹤; 杜明珠; 孙月
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2024-01-12
Filing date: 2024-01-12
Publication date: 2024-04-19

Abstract

The invention provides a heterocyclic compound and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescent materials. The heterocyclic compound has good film forming property and thermal stability, and can improve electron mobility when being used as an electron transport material; when the material is used as a hole blocking layer material, the material can effectively block holes from transporting to the opposite electrode direction; when the material is used as a material of the light-emitting layer, the material can enable the distribution of carriers in the light-emitting layer to be more balanced and increase the utilization rate of the carriers; when used as a coating material, the material has higher refractive index, and can effectively reduce total reflection loss and waveguide loss in a device; when used as a charge generation layer, the stacked device has low driving voltage, high luminous efficiency and long service life. When the compound is applied to a device, the driving voltage can be effectively reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and meanwhile, the compound has good industrialization prospect.

Description

Heterocyclic compound and organic electroluminescent device thereof

Technical Field

The invention relates to the technical field of organic electroluminescent materials, in particular to a heterocyclic compound and an organic electroluminescent device thereof.

Background

With the development of technology, the requirements for information transmission and display are continuously increased, and in order to make information transmission more efficient and faster, organic electroluminescence is becoming a key point of research to replace inorganic luminescence. The organic electroluminescent device has the advantages of high brightness, high response speed, low driving voltage, light and thin device, convenient processing, easy amplification, wide temperature application range, energy conservation and the like, and becomes an ideal material for display equipment. In particular, its prominence in the field of flexible screens that can be rolled up is known as future fantasy display material.

The organic electroluminescent device is a sandwich structure and is divided into a cathode, an anode and an organic layer sandwiched between the cathode and the anode. The organic layers are classified into a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a charge generation layer, and a capping layer according to functions. The structure of the device can be adjusted as needed to maximize the overall performance of the device.

In an organic electroluminescent device, injection and transport of carriers have a great influence on the performance of the device. In order to balance the injection and transmission of electrons and holes and improve the recombination probability of carriers, an electron transport material with good electron mobility can be introduced, so that the transmission performance of electrons and holes in an organic layer is equivalent. A hole blocking layer material may be introduced that can block the transport of holes to the opposite electrode. The light emitting layer material may be introduced such that carriers are balanced and efficiently recombined within the light emitting layer. A cladding material with a high refractive index may be introduced to reduce total reflection losses and waveguide losses in the device. Alternatively, a stacked organic electroluminescent device can be used, a charge generation layer is introduced, and two or more independent electroluminescent units are connected in series through the charge generation layer to solve the problems of low efficiency and short service life of the organic electroluminescent device.

The introduction of the organic layer material can prolong the service life and improve the luminous efficiency of the organic electroluminescent device. However, the existing organic layer material still has the defects of low electron mobility, poor hole blocking capability, mismatched triplet state energy level, poor thermal stability and film forming property, large driving voltage and the like. However, how to develop an organic electroluminescent material with better performance has been a problem to be solved by those skilled in the art.

Disclosure of Invention

In order to solve the problems, the invention provides a heterocyclic compound and an organic electroluminescent device thereof, and the application of the heterocyclic compound in the organic luminescent device can effectively improve the luminous efficiency of the device and prolong the service life of the device.

Specifically, the invention provides a heterocyclic compound, which has a structure represented by a formula I:

Wherein L is selected from any one of the following structures or from a combination of two or more of the following structures:

Ar ₁、Ar₂、Ar₃、Ar₄ is independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 alicyclic ring, a C6-C30 aromatic ring condensed ring group, a substituted or unsubstituted C1-C25 heterocycloalkyl ring, a C6-C30 aromatic ring condensed ring group, or any one of the following structures:

x is selected from any one of C (R _i) and N, and at most two of X are selected from N;

Y is selected from any one of C (R _j) and N, and at least one of Y is selected from N;

the V is selected from any one of CH and N;

the V' is selected from any one of CH and N;

The Y ₁、Y₂ is independently selected from any one of O, S, C (R _pR_q)、N(R_r);

The Ya and the Y _b、Y_c、Y_d are independently selected from any one of O, S, C (R _eR_f)、N(R_g);

The L ₁、L₂、L₃、L₄ is independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted C3-C30 alicyclic and C6-C30 aromatic ring fused ring-forming group, a substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroaromatic ring fused ring-forming group;

The Ra, ra', R _i、R_j、R_p、R_q、R₀、R_e、R_f, rs are independently selected from hydrogen, deuterium, tritium, halogen, cyano, nitro, substituted or unsubstituted C1-C25 alkyl, -Si (Rn) ₃, substituted or unsubstituted C3-C25 alicyclic, substituted or unsubstituted C1-C25 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 alicyclic and C6-C30 aromatic ring fused ring groups, substituted or unsubstituted C1-C25 heterocycloalkyl and C6-C30 aromatic ring fused ring groups, substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroaromatic ring fused ring groups, or R _p、R_q are connected to form a substituted or unsubstituted ring, or R _e、R_f is connected to each other to form a substituted or unsubstituted ring;

The R _r、R_g is independently selected from any one of halogen, cyano, nitro, substituted or unsubstituted C1-C25 alkyl, -Si (Rn) ₃, substituted or unsubstituted C3-C25 alicyclic group, substituted or unsubstituted C1-C25 heterocycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C2-C30 heteroaryl group, substituted or unsubstituted C3-C30 alicyclic and C6-C30 aromatic ring condensed ring group, substituted or unsubstituted C1-C25 heterocycloalkyl and C6-C30 aromatic ring condensed ring group, substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroaromatic ring condensed ring group;

At least one of said Ar₁、Ar₂、Ar₃、Ar₄、L₁、L₂、L₃、L₄、R_i、R_j is substituted with one, two or more-Si (Rn) ₃;

The Rn is selected from any one of hydrogen, deuterium, tritium, halogen, cyano, nitro, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 alicyclic and substituted or unsubstituted C1-C25 heterocycloalkyl;

Said p is selected from 1,2, 3 or 4;

The a ₀ is selected from 0, 1,2, 3, or 4; when two or more Ra's are present, the two or more Ra's are the same or different from each other, or two Ra's adjacent to each other are linked to each other to form a substituted or unsubstituted alicyclic ring;

The a ₁ is selected from 0,1, 2,3, 4, 5, 6, 7, or 8; the a ₂ is selected from 0,1, 2,3, or 4; the a ₃ is selected from 0,1, 2,3, 4, 5, or 6; when two or more Ra are present, the two or more Ra are the same or different from each other, or two Ra adjacent to each other are linked to each other to form a substituted or unsubstituted ring;

Said m ₁ is selected from 0, 1, 2, 3, 4, or 5; said m ₂ is selected from 0, 1, 2, 3, or 4; when two or more R ₀ are present, two or more R ₀ are the same or different from each other, or two adjacent R ₀ are linked to each other to form a substituted or unsubstituted ring.

The invention also provides an organic electroluminescent device comprising an anode, a cathode, and an organic layer between the anode and the cathode or on the side of the cathode facing away from the anode, the organic layer comprising at least one of the heterocyclic compounds according to the invention.

The beneficial effects are that:

The invention provides a heterocyclic compound which has good film forming property and thermal stability when applied to an organic electroluminescent device. When the polymer is used as an electron transport material, the electron mobility can be improved, so that electrons can be effectively transported into the light-emitting layer; when the light-emitting diode is used as a hole blocking layer material, holes can be effectively blocked from being transported towards the opposite electrode direction, and the recombination probability of excitons in the light-emitting layer is improved; when used as a material of the light-emitting layer, the light-emitting layer has proper energy level, so that the carrier distribution in the light-emitting layer is more balanced and the utilization rate of carriers is increased; when used as a coating material, the material has higher refractive index, and can effectively reduce total reflection loss and waveguide loss in an organic electroluminescent device; when used as a charge generation layer, the stacked device has low driving voltage, high luminous efficiency and long service life.

In conclusion, when the compound is applied to the organic electroluminescent device, the compound has excellent performance, can effectively reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency of the device and prolong the service life of the device, and has simple preparation method, easily obtained raw materials, capability of meeting the industrial requirements and good industrialization prospect.

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. Modifications of the invention which are obvious to those skilled in the art are intended to fall within the scope of the invention.

In the present specification, "-" means a moiety attached to another substituent. "-" may be attached at any optional position of the attached group/fragment.

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 any of the two or more rings, in particular to any of the corresponding selectable sites of the rings. For example, the number of the cells to be processed,Can represent/> Can represent/>And so on.

In this specification, when the position of a substituent or attachment site on a ring is not fixed, it means that it can be attached to any of the optional sites of the ring.

For example, the number of the cells to be processed,Can represent/>Can represent/>Can represent/>And so on.

Examples of halogens described herein may include fluorine, chlorine, bromine and iodine.

The alkyl group according to the present invention is a generic term for monovalent groups obtained by removing one hydrogen atom from an alkane molecule, and may be a straight chain alkyl group or a branched chain alkyl group, preferably having 1 to 25 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples may include methyl, ethyl, n-propyl, isopropyl-n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but are not limited thereto.

The-Si (Rn) ₃ groups of the invention, wherein each Rn is independently selected from the group consisting of: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 alicyclic, substituted or unsubstituted C1-C25 heterocycloalkyl. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms. The cycloaliphatic radical preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, even more preferably 3 to 10 carbon atoms, particularly preferably 3 to 7 carbon atoms. The heterocycloalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms. Preferably, each Rn is independently selected from the group consisting of: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted heptyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted octyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl. Examples may include trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, dimethylt-butylsilyl, tricyclopentylsilyl, tricyclohexylsilyl, and the like, but are not limited thereto.

The alicyclic group in the present invention means a generic term of monovalent groups obtained by removing one hydrogen atom from an alicyclic hydrocarbon molecule, and may be cycloalkyl, cycloalkenyl, or the like, preferably having 3 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, still more preferably 5 to 10 carbon atoms, and most preferably 5 to 7 carbon atoms, such as adamantyl, norbornyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, or the like, but is not limited thereto.

Heterocycloalkyl according to the present invention refers to a group in which one or more carbon atoms in the heterocycloalkyl group are replaced by heteroatoms including, but not limited to, oxygen, sulfur, nitrogen, silicon or phosphorus atoms, preferably having 1 to 15 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms. Such as, but not limited to, tetrahydropyrrolyl, piperidinyl, and the like.

Aryl in the present invention refers to the generic term for monovalent radicals obtained by removing 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 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 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, and specific examples may include 1-phenylnaphthyl, 2-phenylnaphthyl, biphenyl, terphenyl, tetrabiphenyl, etc., but are 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, and specific examples may include, but are not limited to, naphthyl, anthryl, phenanthryl, fluorenyl, benzofluorenyl, spirofluorenyl, spirobifluorenyl, triphenylenyl, pyrenyl, perylenyl, fluoranthryl, and the like.

Heteroaryl according to the present invention refers to the generic term for groups obtained after substitution of one or more aromatic nucleus carbon atoms in the aryl group with heteroatoms including, but not limited to, oxygen, sulfur, nitrogen, silicon or phosphorus atoms, preferably having 2 to 30 carbon atoms, more preferably 2 to 18 carbon atoms, particularly preferably 2 to 15 carbon atoms, most preferably 2 to 12 carbon atoms. The attachment site of the heteroaryl group may be on a ring-forming carbon atom or on a ring-forming heteroatom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a fused ring heteroaryl group. Specific examples of the monocyclic heteroaryl group may include, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, furyl, thienyl, pyrrolyl, and the like; specific examples of the polycyclic heteroaryl group may include phenylpyridyl, phenylpyrimidinyl, bipyridyl, bipyrimidinyl, etc., but are not limited thereto; specific examples of the fused ring heteroaryl group may include quinolinyl, isoquinolinyl, benzoquinolinyl, benzoisoquinolinyl, quinazolinyl, quinoxalinyl, benzoquinazolinyl, benzoquinoxalinyl, phenanthroline, naphthyridinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothienyl, benzodibenzothienyl, dibenzooxazolyl, dibenzoimidazolyl, dibenzothiazolyl, carbazolyl, benzocarbazolyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, spirofluorene oxaanthracenyl, spirofluorene thianthrenyl, acridinyl, 9, 10-dihydroacridinyl, and the like, but are not limited thereto.

The fused ring group of the alicyclic ring and the aromatic ring refers to the generic term of monovalent groups obtained by removing one hydrogen atom after the alicyclic ring and the aromatic ring are fused together. Preferably having 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 13 carbon atoms, specific examples may include benzocyclopropyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocycloheptyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptenyl, naphthocyclopropyl, naphthocyclobutyl, naphthocyclopentyl, naphthocyclohexyl, and the like, but are not limited thereto.

The fused ring group of the heterocycloalkyl ring and the aromatic ring in the present invention refers to a generic term for monovalent groups obtained by fusing the heterocycloalkyl ring and the aromatic ring together and then removing one hydrogen atom. Preferably having 6 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 13 carbon atoms, specific examples may include benzopiperidinyl, phenanthropiperidyl, benzoazetidinyl, benzotetrahydropyrrole, benzoazepanyl, naphthatrahydropyrrolyl, naphthaperidinyl, phenanthropiridyl, and the like, but are not limited thereto.

The fused ring group of the alicyclic ring and the heteroaromatic ring refers to the generic term of monovalent groups obtained by fusing the alicyclic ring and the heteroaromatic ring together and removing one hydrogen atom. Preferably having 5 to 30 carbon atoms, more preferably 5 to 18 carbon atoms, and most preferably 5 to 12 carbon atoms, specific examples may include carbazolocyclopropyl, carbazolocyclobutyl, carbazolocyclopentyl, carbazolocyclohexyl, carbazolocycloheptyl, pyridocyclopropyl, pyridocyclobutyl, pyridocyclopentyl, pyridocyclohexyl, pyridocycloheptyl, pyrimidocyclopropyl, pyrimidocycloputyl, pyrimidocyclopentyl, pyrimidocyclohexyl, pyrimidobenzcycloheptyl, dibenzofuran-cyclopropyl, dibenzofuran-cyclobutyl, dibenzofuran-cyclopentyl, dibenzofuran-cyclohexyl, dibenzofuran-cycloheptyl, dibenzothiophene-cyclopropyl, dibenzothiophene-cyclobutyl, dibenzothiophene-cyclopentyl, dibenzothiophene-cyclohexyl, dibenzothiophene-cycloheptyl, and the like, but are not limited thereto.

The alicyclic group according to the present invention means a generic term of divalent groups obtained by removing two hydrogen atoms from an alicyclic hydrocarbon molecule, and may be a cycloalkylene group, a cycloalkenylene group, or the like, preferably having 3 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, preferably 5 to 10 carbon atoms, and most preferably 5 to 7 carbon atoms, and specific examples may include an adamantylene group, a norbornylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, or the like, but are not limited thereto.

The arylene group according to the present invention means a generic term for divalent groups obtained by removing two hydrogen atoms from an aromatic nucleus of an aromatic hydrocarbon molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, preferably having 6 to 30 carbon atoms, preferably 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms, and specific examples may include phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, pyrenylene, triphenylene, perylene, fluorenylene, phenyleofluorenylene, fluoranthenylene, and the like, but are not limited thereto.

Heteroaryl, as used herein, refers to the generic term for groups obtained after substitution of one or more of the aromatic nucleus carbons in the arylene group with heteroatoms, including but not limited to oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 2 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, the heteroarylene group may be attached to a ring-forming carbon atom or to a ring-forming nitrogen atom, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group or a condensed ring heteroarylene group. Specific examples of the monocyclic and condensed ring heteroarylene groups may include, but are not limited to, a pyridylene group, a pyrimidinylene group, a triazinylene group, a furanylene group, a thienyl group, a carbazolylene group, a benzofuranylene group, a benzothienyl group, a benzocarbazolylene group, a dibenzofuranylene group, a dibenzothiophenylene group, a dibenzocarbazolylene group, and the like; specific examples of the polycyclic heteroarylene group may include bipyridylene group, phenylpyridylene group, bipyrimidiylene group, etc., but are not limited thereto.

The term "fused ring-sub group" of an alicyclic ring and an aromatic ring as used herein refers to a generic term for divalent groups obtained by fusing an alicyclic ring and an aromatic ring together and then removing two hydrogen atoms. Preferably having 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 13 carbon atoms, specific examples may include benzobicyclopropyl, benzobicyclobutyl, benzocyclopentylene, benzocyclohexylene, benzocycloheptylene, benzocyclopentylene, benzocyclohexenylene, benzocycloheptylene, naphthocyclopropyl, naphthocyclobutylene, naphthocyclopentyl, naphthocyclohexyl, and the like, but are not limited thereto.

The term "fused ring-sub-group" as used herein refers to a generic term for divalent radicals obtained by fusing an alicyclic ring to a heteroaromatic ring and then removing two hydrogen atoms. Preferably having 5 to 30 carbon atoms, more preferably 5 to 18 carbon atoms, and most preferably 5 to 12 carbon atoms, specific examples may include carbazolo cyclopropyl, carbazolo cyclobutyl, carbazolo cyclopentyl, carbazolo cyclohexyl, carbazolo cycloheptyl, pyrido cyclopropyl, pyrido cyclobutyl, pyrido cyclopentyl, pyrido cyclohexyl, pyrido benzocycloheptyl, pyrimido cyclopropyl, pyrimido cyclobutyl, pyrimido cyclopentyl, pyrimido cyclohexyl, pyrimido benzocycloheptyl, dibenzo cyclopropyl, dibenzo benzocyclobutene, dibenzo benzocyclopentyl, dibenzo benzocyclohexyl, dibenzo benzocycloheptyl, dibenzo thieno cyclopropyl, dibenzo benzothieno cyclobutyl, dibenzo benzothieno cyclopentyl, dibenzo benzothieno cyclohexyl, dibenzo benzothieno cycloheptyl, and the like, but are not limited thereto.

The substituents in the "substituted or unsubstituted" described herein may be independently selected from deuterium, cyano, nitro, amino, halogen atom, substituted or unsubstituted C1-C12 alkyl, -Si (Rn) ₃, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C6 alkylthio, substituted or unsubstituted C1-C12 alkylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 arylamino, and the like, but are not limited thereto, or two adjacent substituents may be linked to form a ring. Preferably deuterium, cyano, nitro, amino, halogen atom, C1-C12 alkyl, -Si (Rn) ₃, C3-C12 cycloalkyl, C6-C30 aryl, C2-C30 heteroaryl, C1-C12 alkoxy, specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclohexyl, adamantyl, norbornyl, trimethylsilyl, triethylsilyl, phenyl, tolyl, mesityl, pentadeuterophenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, perylene, pyrenyl, fluoranthracenyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, spirofluorenyl, 9' -spirobifluorenyl, carbazolyl, 9-phenylcarbazolyl carbazoloindolyl, pyrrolyl, furanyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothiophenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, benzimidazolyl, isoquinolyl, quinoxalinyl, quinazolinyl, phenothiazinyl, phenoxazinyl, acridinyl, benzocyclobutane, benzocyclobutene, benzocyclopentane, benzocyclopentene, benzocyclohexane, benzocyclohexene, and the like, but is not limited thereto. Or when the substituent is plural, plural substituents are the same or different from each other; or adjacent substituents may be joined to form a ring.

The term "link-forming ring" as used herein means that two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:

In the present invention, the ring formed by the connection may be an aromatic ring system, an aliphatic ring system or a ring system formed by fusing both, and the ring formed by the connection may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentaacene, cyclohexene, cyclohexane acene, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.

The term "at least one", "one or more" as used herein includes one, two, three, four, five, six, seven, eight or more, where permitted.

The invention provides a heterocyclic compound, which has a structure represented by a formula I:

the V is selected from any one of CH and N;

the V' is selected from any one of CH and N;

Said p is selected from 1,2, 3 or 4;

Preferably, the heterocyclic compound is selected from any one of the following structures:

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The R4 is selected from hydrogen, deuterium, cyano, nitro, halogen, substituted or unsubstituted C1-C12 alkyl, -Si (Rn) ₃, substituted or unsubstituted C3-C25 alicyclic group, substituted or unsubstituted C1-C25 heterocycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C30 alicyclic group and C6-C30 aromatic ring condensed ring group, substituted or unsubstituted C1-C25 heterocyclic alkane and C6-C30 aromatic ring condensed ring group;

the k ₁ is selected from 0, 1, or 2; the k ₂ is selected from 0, 1,2, or 3; when two or more R4 s are present, two or more R4 s are the same or different from each other, or two adjacent R4 s are linked to each other to form a substituted or unsubstituted ring.

Still preferably, the heterocyclic compound is selected from any one of the following structures:

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Preferably, ar ₁ contains one or more than two of-Si (Rn) ₃.

Preferably, ar ₂ contains one or more than two of-Si (Rn) ₃.

Preferably, ar ₃ contains one or more than two of-Si (Rn) ₃.

Preferably, ar ₄ contains one or more than two of-Si (Rn) ₃.

Preferably, formula 1 contains one, two, three, four or more-Si (Rn) ₃ groups.

Preferably, the Rn is selected from any one of hydrogen, deuterium, tritium, halogen, cyano, nitro, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted tetrahydropyrrole, substituted or unsubstituted piperidinyl.

Preferably, L is selected from any one of the following structures or from a combination of two or more of the following structures:

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the Rb, rb', rd are independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C25 alicyclic, substituted or unsubstituted C1-C25 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 alicyclic and C6-C30 aromatic fused ring groups, substituted or unsubstituted C1-C25 heterocycloalkyl and C6-C30 aromatic fused ring groups;

Said b ₁ is selected from 0,1, 2,3, or 4; said b ₂ is selected from 0,1, or 2; when two or more Rb's are present, the two or more Rb's are the same or different from each other;

Said b ₃ is selected from 0,1, 2,3, 4, 5, 6, 7, or 8; said b ₄ is selected from 0,1, 2,3, or 4; said b ₅ is selected from 0,1, 2,3, 4, 5, or 6; when two or more Rb are present, two or more Rb are the same or different from each other or two adjacent Rb are linked to each other to form a substituted or unsubstituted ring;

Said g ₁ is selected from 0, 1,2, 3, or 4; said g ₂ is selected from 0, 1,2, 3, 4, 5, or 6; said g ₃ is selected from 0, 1,2, 3, 4, 5, 6, 7, or 8; said g ₄ is selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, or 10; said g ₅ is selected from 0, 1, or 2; when two or more Rd are present, the two or more Rd may be the same or different from each other, or two adjacent Rd may be linked to each other to form a substituted or unsubstituted ring.

Still more preferably, the L is selected from any one of the following structures or from a combination of two or more of the following structures:

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The Rc, rc' are independently selected from hydrogen, deuterium, cyano, nitro, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C25 alicyclic, substituted or unsubstituted C1-C25 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 alicyclic and C6-C30 aromatic ring condensed ring groups, substituted or unsubstituted C1-C25 heterocycloalkyl and C6-C30 aromatic ring condensed ring groups;

Said c ₁ is selected from 0, 1, 2, 3, or 4; said c ₂ is selected from 0, 1, or 2; said c ₃ is selected from 0, 1, 2, or 3; when two or more Rc's are present, the two or more Rc's are the same or different from each other;

The h ₁ is selected from 0,1, 2,3,4, 5, 6, 7, or 8; the h ₂ is selected from 0,1, 2,3, or 4; the h ₃ is selected from 0,1, 2,3,4, 5, or 6; the h ₄ is selected from 0,1, 2,3,4, or 5; the h ₅ is selected from 0,1, 2,3,4, 5, 6, or 7; the h ₆ is selected from 0,1, 2, or 3; when two or more Rc's are present, the two or more Rc's are the same or different from each other, or two Rc's adjacent to each other are joined to form a substituted or unsubstituted ring.

More preferably, L is selected from any one of the following structures or from a combination of two or more of the following structures:

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Preferably, ar ₁、Ar₂、Ar₃、Ar₄ is independently selected from any one of the following structures:

Z is selected from any one of CH and N;

The R ₁ is selected from any one of hydrogen, deuterium, tritium, halogen, cyano, nitro, substituted or unsubstituted C1-C25 alkyl, -Si (Rn) ₃, substituted or unsubstituted C3-C25 alicyclic group, substituted or unsubstituted C1-C25 heterocycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C2-C30 heteroaryl group, substituted or unsubstituted C3-C30 alicyclic ring and C6-C30 aromatic ring condensed ring group, substituted or unsubstituted C1-C25 heterocycloalkyl ring and C6-C30 aromatic ring condensed ring group, substituted or unsubstituted C3-C25 alicyclic ring and C2-C30 heteroaromatic ring condensed ring group;

Said d ₁ is selected from 0, 1,2, 3, 4, or 5; said d ₂ is selected from 0, 1,2, 3, or 4; the d ₃ is selected from 0, 1,2, 3, 4, 5, 6, or 7; the d ₄ is selected from 0, 1,2, 3, 4, 5, 6, 7, 8, or 9; said d ₅ is selected from 0, 1, or 2; the d ₆ is selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; said d ₇ is selected from 0, 1,2, or 3; when two or more R ₁ are present, two or more R ₁ are the same or different from each other, or two adjacent R ₁ are linked to each other to form a substituted or unsubstituted ring.

More preferably, ar ₁、Ar₂、Ar₃、Ar₄ is independently selected from any one of the following structures:

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Preferably, L ₁、L₂、L₃、L₄ is independently selected from a single bond or from any one of the following structures or from a combination of two or more of the following structures:

the R is selected from any one of CH and N;

Each Y ₆、Y₇、Y₈ is independently selected from any one of O, S, C (R _mR_x)、N(R_t);

The R ₃、R_m、R_x、R_t is independently selected from any one of hydrogen, deuterium, cyano, nitro, halogen, substituted or unsubstituted C1-C12 alkyl, -Si (Rn) ₃, substituted or unsubstituted C3-C25 alicyclic group, substituted or unsubstituted C1-C25 heterocycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C30 alicyclic group and C6-C30 aromatic ring condensed ring group, substituted or unsubstituted C1-C25 heterocycloalkyl group and C6-C30 aromatic ring condensed ring group, or R _m、R_x is connected to form a substituted or unsubstituted ring;

Said n is selected from 1,2, 3 or 4;

Said f ₁ is selected from 0, 1,2,3, or 4; said f ₂ is selected from 0, 1,2,3, 4,5, or 6; said f ₃ is selected from 0, 1,2,3, 4,5,6, 7, or 8; said f ₄ is selected from 0, 1, or 2; said f ₅ is selected from 0, 1,2,3, 4,5,6, or 7; when two or more R ₃ are present, two or more R ₃ are the same or different from each other, or two adjacent R ₃ are linked to each other to form a substituted or unsubstituted ring.

Still more preferably, L ₁、L₂、L₃、L₄ is independently selected from a single bond or from any one of the following structures or from a combination of two or more of the following structures:

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most preferably, the heterocyclic compound is selected from any one of the following structures:

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The heterocyclic compounds of formula I of the present invention are shown in the above list of specific structural forms, but the present invention is not limited to the listed chemical structures, and substituents are included in the structures of formula I.

The invention provides an organic electroluminescent device comprising an anode, a cathode, and an organic layer between the anode and the cathode or on the side of the cathode facing away from the anode, the organic layer comprising at least one of the aromatic amine compounds according to the invention.

Preferably, the organic layer comprises at least one of an electron transport layer, a hole blocking layer, a light emitting layer and a cover layer, and at least one of the electron transport layer, the hole blocking layer, the light emitting layer and the cover layer comprises at least one of the heterocyclic compounds of the present invention.

Preferably, the organic layer is located between the anode and the cathode, and the organic layer comprises at least one of an electron transport layer, a hole blocking layer and a light emitting layer, and at least one of the electron transport layer, the hole blocking layer and the light emitting layer comprises at least one of the heterocyclic compounds of the present invention.

Still preferably, the organic layer comprises an electron transport layer comprising at least one of the heterocyclic compounds described herein.

Still preferably, the organic layer comprises a hole blocking layer comprising at least one of the heterocyclic compounds described herein.

Still preferably, the organic layer includes a light-emitting layer including at least one of the heterocyclic compounds described in the present invention.

Preferably, the organic layer comprises a cover layer on a side of the cathode facing away from the anode, the cover layer comprising at least one of the heterocyclic compounds according to the invention.

Preferably, the organic layer is located between the anode and the cathode, the organic layer includes a first light emitting portion, a second light emitting portion, and a charge generating layer, the first light emitting portion is located between the anode and the cathode, the second light emitting portion is located between the first light emitting portion and the cathode, the charge generating layer is located between the first light emitting portion and the second light emitting portion, and the charge generating layer includes at least one of the heterocyclic compounds of the present invention.

Preferably, the charge generation layer is composed of an N-type charge generation layer provided adjacent to the first light emitting portion and a P-type charge generation layer provided adjacent to the second light emitting portion, and the organic layer includes the N-type charge generation layer including at least one of the aromatic amine compounds of the present invention.

The material of each layer of thin film in the organic electroluminescent device is not particularly limited, and materials known in the art can be used. The following describes each organic functional layer of the above-mentioned organic electroluminescent device and the electrodes on both sides of the device, respectively:

The anode material of the present invention is preferably a material having a high work function in order to improve hole injection efficiency. The anode may be a semi-transmissive electrode, transmissive electrode or reflective electrode. When the anode is a semi-transmissive electrode or a reflective electrode, the material used to form the anode may be selected from magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof. When the anode is a transmissive electrode, the material used to form the anode may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin oxide (SnO ₂), zinc oxide (ZnO), or any combination thereof; 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 single-layer structure of Al or a three-layer structure of ITO/Ag/ITO, but the structure of the anode is not limited thereto.

The cathode material according to the present invention, preferably a material having a low work function, is intended to improve electron injection efficiency, and the cathode may be selected from Al, pt, pd, ag, mg, cu, au, ni, nd, ir, cr, li, ca, mo, ti, liF/Ca, liF/Al including their compounds or their mixtures (e.g., a mixture of Ag and Mg), but is not limited thereto.

The hole injection layer material is preferably a material with better hole injection capability and has more proper HOMO energy level so as to reduce interface potential barrier between the anode and the hole transport layer, and the purpose is to improve the hole injection capability. The hole injection layer material may include arylamine derivatives, metalloporphyrins, oligothiophenes, perylene derivatives, hexanitrile hexaazabenzophenanthrene compounds, anthraquinone compounds, quinacridone compounds, and polyaniline-based and polythiophene-based conductive polymers, etc., but is not limited thereto.

The hole transport layer material according to the present invention is preferably a material having high hole mobility, and may include carbazole derivatives, fluorene derivatives, triarylamine derivatives, biphenyldiamine derivatives, stilbene derivatives, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, hexanitrile hexaazabenzophenanthrene compounds, polythiophene, polyaniline, polyvinylcarbazole, and the like, but is not limited thereto.

The electron blocking layer material of the present invention is preferably a material having a good hole transporting ability and an electron blocking ability, in order to efficiently transport holes and to limit the escape of electrons to the light emitting layer interface. The electron blocking layer material can be selected from aromatic amine derivatives, carbazole derivatives, etc. Specific examples may include N- (4 ' - (9H-carbazol-9-yl) - [1,1' -biphenyl ] -4-N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine, N ' -bis (naphthalen-1-yl) -N, N ' -diphenyl-benzidine (NPD), N-bis ([ 1,1' -biphenyl ] -4-yl) - (9H-carbazol-9-yl) - [1,1' -biphenyl ] -4-amine, and the like, but are not limited thereto.

The light-emitting layer material generally comprises a host material (also called a host material) and a doping material (also called a guest material), wherein the light-emitting layer material can comprise a plurality of host materials and a plurality of doping materials, and the guest material can be a pure fluorescent material or a phosphorescent material or is formed by matching and combining fluorescent materials and phosphorescent materials. The host material of the light-emitting layer is required to have a bipolar charge transport property and an appropriate energy level to efficiently transfer excitation energy to the guest light-emitting material, and the host material of the light-emitting layer may include, but is not limited to, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, pentacene derivatives, fluoranthene derivatives, and the like, and heterocyclic ring-containing compounds including carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, pyrimidine derivatives, distyrylaryl derivatives, stilbene derivatives, and the like, in addition to the heterocyclic compounds provided by the present invention. The guest material may comprise: metal complexes (e.g., platinum complex, iridium complex, osmium complex, rhodium complex, europium complex, terbium complex, etc.), anthracene derivatives, carbazole derivatives, pyrene derivatives, perylene derivatives, pyrrole derivatives, indole derivatives, etc., but are not limited thereto.

The hole blocking layer of the present invention is preferably a material having a good electron transporting ability and a hole blocking ability so as to efficiently transport electrons and limit the escape of holes to the light emitting layer interface. The hole blocking layer material may include, in addition to the heterocyclic compound provided by the present invention, triazole derivatives, quinoline derivatives, imidazole derivatives, phenanthrene derivatives, azabenzene derivatives, metal complexes, and the like, and preferably at least one of the heterocyclic compounds described in the present invention. Specific examples may include 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1, 1' -biphenyl-4-hydroxy) aluminum (BAlq), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 3' - [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 "-terphenyl ] -3,3" -diyl ] bipyridine (TmPyPB), and the like, but are not limited thereto.

The electron transport layer material of the present invention is preferably a material having high electron mobility for electron injection, and may include any one or more of the following structures, silicon-containing heterocyclic compounds, boron-containing heterocyclic compounds, thiazole derivatives, quinoline derivatives, benzimidazole derivatives, oxazole derivatives, azabenzene derivatives, diazine derivatives, cyano compounds, phenanthroline derivatives, metal chelates, etc., in addition to the heterocyclic compounds provided by the present invention, but is not limited thereto.

The electron injection layer material of the present invention is preferably a material having a good electron injection capability and a suitable LUMO energy level so as to reduce an interface barrier between the cathode and the electron transport layer and improve the electron injection capability, and may include metals, alkali metals, alkaline earth metals, alkali metal halides, alkaline earth metal halides, alkali metal oxides, alkaline earth metal oxides, alkali metal salts, alkaline earth metal salts, metal complexes, metal oxides, and other substances having high electron injection capability. Specific examples may include, but are not limited to, ：Li、Ca、Sr、LiF、CsF、CaF₂、BaO、Li₂CO₃、CaCO₃、Li₂C₂O₄、Cs₂C₂O₄、CsAlF₄、Al2O₃、MoO₃、MgF₂、LiOx、Yb、Tb、8- cesium hydroxyquinoline, aluminum tris (8-hydroxyquinoline), and the like.

The cladding material of the present invention is preferably a material having a high refractive index in order to improve light extraction efficiency, and may include, but is not limited to, 4 '-bis (9-Carbazole) Biphenyl (CBP), tris (8-hydroxyquinoline) aluminum (Alq ₃), N' -bis (naphthalen-1-yl) -N, N '-bis (phenyl) -2,2' -dimethylbenzidine (NPD), and the like, in addition to the heterocyclic compound provided by the present invention.

The P-type charge generation layer material of the invention comprises: metal oxides such as V ₂O₅、WO₃ and MoO ₃, P-type doped organic layers such as NPB, naCl, rubrene, moO ₃ and TAPC, moO ₃, and P-type organic materials such as TAPC, m-MTDATA and pentacene, etc., but are not limited thereto.

The N-type charge generation layer material of the present invention may include Bphen: li, al: mg and Bphen: cs ₂CO₃, and N-type organic semiconductor materials such as HAT-CN, C60 and C70, etc., in addition to the heterocyclic compound provided by the present invention, but is not limited thereto.

The method for producing the thin films of each layer in the organic electroluminescent device of the present invention is not particularly limited, and vacuum deposition, sputtering, spin coating, spray coating, screen printing, laser transfer, etc. may be used, but are not limited thereto.

The organic electroluminescent device is mainly applied to the technical field of information display and the field of illumination, and is widely applied to various information displays in the aspect of information display, such as mobile phones, tablet computers, flat televisions, smart watches, VR, vehicle-mounted systems, digital cameras, wearable devices and the like.

The following is one preparation method of the compound represented by the formula I of the present invention, but the preparation method of the present invention is not limited thereto. The core structure of the compound of formula I may be prepared by the reaction scheme shown below, substituents may be bonded through methods known in the art, and the kind and position of substituents or the number of substituents may be changed according to techniques known in the art.

[ Synthetic route ]

Preparation of Compounds of formula I

1) When-L1-Ar 1 is different from-L2-Ar 2, the synthetic route of the compound I is as follows:

2) when-L1-Ar 1 is the same as-L2-Ar 2, the synthetic route of Compound I is as follows:

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In addition, the above raw materials may be commercially available products or prepared by a synthesis method commonly used in the art, and taking raw material G as an example, the preparation method may be as follows:

Xa, xb, xc, xd, xe, xf, xg, xh, xi, xj, xk, xm are respectively and independently selected from any one of Cl, br and I; the Ar ₁、Ar₂、Ar₃、Ar₄、L、L₁、L₂、L₃、L₄, X, Y are defined as above.

Description of the starting materials, reagents and characterization equipment:

the raw materials and reagent sources used in the following examples are not particularly limited, and may be commercially available products or prepared by methods 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 VarioELcube-10 mg organic elemental analyzer from Elementar, germany.

Synthesis example 1 Synthesis of Compound 7

Preparation of intermediate A-7:

200mL of tetrahydrofuran, a-7 (113.00 mmol,26.91 g), pinacol biborate (115.00 mmol,29.20 g), pd (dppf) Cl ₂ (0.57 mmol,0.42 g), potassium acetate (283.00 mmol,27.77 g) were added to the reaction flask under nitrogen, and the mixture was stirred and heated under reflux for 5h. After the reaction was completed, 200mL of water was cooled and added, and the mixture was filtered and dried in a vacuum oven. The residue obtained was purified with toluene: ethanol=10:1 recrystallization to afford intermediate a-7 (27.39 g, 85%); HPLC purity is more than or equal to 99.64%. Mass spectrum m/z:285.1962 (theoretical value: 285.1948).

Preparation of intermediate B-7

Adding the intermediate A-7(85.00mmol,24.24g)、c-7(87.00mmol,27.61g)、Pd(PPh₃)₄(0.85mmol,0.98g)、K₂CO₃(127.50mmol,17.62g), 150mL of toluene, 75mL of ethanol and 75mL of water into a reaction bottle under the protection of nitrogen, stirring the mixture, reacting for 6.5h under the condition of heating reflux, cooling to room temperature after the reaction is finished, filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate B-7 (24.60 g, 83%); the HPLC purity is more than or equal to 99.69 percent. Mass spectrum m/z:347.0106 (theoretical value: 347.0125).

Preparation of intermediate C-7:

200mL of tetrahydrofuran, B-7 (55.00 mmol,19.18 g), pinacol biborate (57.20 mmol,14.53 g), pd (dppf) Cl ₂ (0.28 mmol,0.20 g), potassium acetate (138 mmol,13.54 g) were added to the reaction flask under nitrogen, and the mixture was stirred and heated under reflux for 7h. After the reaction was completed, 200mL of water was cooled and added, and the mixture was filtered and dried in a vacuum oven. The residue obtained was purified with toluene: ethanol=20:1 recrystallisation to give intermediate C-7 (17.63 g, 81%); HPLC purity is more than or equal to 99.76%. Mass spectrum m/z:395.1887 (theoretical value: 395.1872).

Preparation of intermediate D-7:

adding the intermediate C-7(40.00mmol,15.83g)、d-7(41.00mmol,9.40g)、Pd(PPh₃)₄(0.40mmol,0.46g)、K₂CO₃(60.00mmol,8.29g), 70mL of toluene, 35mL of ethanol and 35mL of water into a reaction bottle under the protection of nitrogen, stirring the mixture, reacting for 7.5h under the condition of heating reflux, cooling to room temperature after the reaction is finished, filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate D-7 (13.21 g,79 percent); the HPLC purity is more than or equal to 99.82 percent. Mass spectrum m/z:417.1739 (theoretical value: 417.1728).

Preparation of intermediate F-7:

200mL of tetrahydrofuran, E-7 (95.00 mmol,29.47 g), pinacol biborate (97.00 mmol,24.63 g), pd (dppf) Cl ₂ (0.48 mmol,0.35 g), potassium acetate (237.50 mmol,23.31 g) were added to the reaction flask under nitrogen atmosphere, and the mixture was stirred and heated under reflux for 5.5h. After the reaction was completed, 200mL of water was cooled and added, and the mixture was filtered and dried in a vacuum oven. The residue obtained was purified with toluene: ethanol=10:1 recrystallization to afford intermediate F-7 (26.47, 78%); HPLC purity is more than or equal to 99.66%. Mass spectrum m/z:357.1918 (theoretical value: 357.1900).

Preparation of intermediate G-7

To the flask, 117 mM MF, F-7 (70.00 mmol,25.01 g), e-7 (72.00 mmol,20.37 g), pd (dppf) Cl ₂ (0.49 mmol,0.36 g) were added under nitrogen protection, stirred, then K ₃PO₄ (70.00 mmol,14.86 g) aqueous solution was added, heated to 150℃and reacted under reflux for 24 hours, the plates were sampled and the reaction was completed. Naturally cooling, adding distilled water, extracting with 400mL of dichloromethane, layering, drying the extract with anhydrous sodium sulfate, filtering, rotary evaporating the filtrate, and recrystallizing toluene to obtain an intermediate G-7 (20.55G, 76%); HPLC purity is more than or equal to 99.74%. Mass spectrum m/z:385.0478 theory: (385.0466).

Preparation of intermediate H-7

200ML of tetrahydrofuran, G-7 (50.00 mmol, 19.31G), pinacol biborate (52.00 mmol, 13.20G), pd (dppf) Cl ₂ (0.25 mmol, 0.18G), potassium acetate (125.00 mmol, 12.27G) were added to the reaction flask under nitrogen atmosphere, and the mixture was stirred and heated under reflux for 7h. After the reaction was completed, 200mL of water was cooled and added, and the mixture was filtered and dried in a vacuum oven. The residue obtained was purified with toluene: ethanol=20:1 recrystallisation to give intermediate H-7 (16.25 g, 75%); HPLC purity is more than or equal to 99.85%. Mass spectrum m/z:433.2203 (theoretical value: 433.2213).

Preparation of compound 7:

Under the protection of nitrogen, H-7(35.00mmol,15.17g)、D-7(30.00mmol,12.54g)、Pd(PPh₃)₄(0.45mmol,0.52g)、K₂CO₃(60.00mmol,8.29g) and 150mL of toluene/ethanol/water (2:1:1) mixed solvent are added into a reaction bottle, the mixture is stirred, and the reactant system is heated and refluxed for reaction for 8 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain a compound 7 (14.88 g, 72%); HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:688.3338 (theoretical value: 688.3322). Theoretical element content (%) C ₅₀H₃₆D₅ NSi: c,87.16; h,6.73; n,2.03. Measured element content (%): c,87.14; h,6.75; n,2.02.

Synthesis example 2 Synthesis of Compound 110

Preparation of intermediate A-110:

200mL of tetrahydrofuran, d-7 (120.00 mmol,27.50 g), pinacol biborate (122.00 mmol,30.98 g), pd (dppf) Cl ₂ (0.60 mmol,0.44 g), potassium acetate (300.00 mmol,29.44 g) were added to the reaction flask under nitrogen atmosphere, and the mixture was stirred and heated under reflux for 6h. After the reaction was completed, 200mL of water was cooled and added, and the mixture was filtered and dried in a vacuum oven. The residue obtained was purified with toluene: ethanol=10:1 recrystallization to afford intermediate a-110 (25.53 g, 77%); the HPLC purity is more than or equal to 99.73 percent. Mass spectrum m/z:276.1735 (theoretical value: 276.1717).

Preparation of intermediate D-110:

200mL of tetrahydrofuran, A-110 (92 mmol,25.42 g), c-110 (45.00 mmol,12.21 g), pd (dppf) Cl ₂ (0.23 mmol,0.17 g), potassium acetate (112.50 mmol,11.04 g) were added to the reaction flask under nitrogen, and the mixture was stirred and heated under reflux for 6.5h. After the reaction was completed, 200mL of water was cooled and added, and the mixture was filtered and dried in a vacuum oven. The residue obtained was purified with toluene: ethanol=10:1 recrystallization to afford intermediate D-110 (13.84 g, 75%); HPLC purity is more than or equal to 99.83%. Mass spectrum m/z:409.1434 (theoretical value: 409.1449).

Preparation of intermediate H-110

200ML of tetrahydrofuran, G-110 (50.00 mmol, 19.31G), pinacol biborate (52.00 mmol, 13.20G), pd (dppf) Cl ₂ (0.25 mmol, 0.18G), potassium acetate (125.00 mmol, 12.27G) were added to the reaction flask under nitrogen atmosphere, and the mixture was stirred and heated under reflux for 7h. After the reaction was completed, 200mL of water was cooled and added, and the mixture was filtered and dried in a vacuum oven. The residue obtained was purified with toluene: ethanol=10:1 recrystallization to afford intermediate H-110 (16.03 g, 74%); the HPLC purity is more than or equal to 99.87 percent. Mass spectrum m/z:433.2201 (theoretical value: 433.2213).

Preparation of compound 110:

Under the protection of nitrogen, H-110(32.00mmol,13.87g)、D-110(30.00mmol,12.30g)、Pd(PPh₃)₄(0.45mmol,0.33g)、K₂CO₃(60.00mmol,8.29g) and 150mL of toluene/ethanol/water (2:1:1) mixed solvent are added into a reaction bottle, the mixture is stirred, and the reactant system is heated and refluxed for reaction for 8.5 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain a compound 110 (14.91 g, 73%); HPLC purity is more than or equal to 99.99%. Mass spectrum m/z:680.3026 (theoretical value: 680.3043). Theoretical element content (%) C ₄₆H₄₄N₂Si₂: c,81.13; h,6.51; n,4.11. Measured element content (%): c,81.11; h,6.52; n,4.13.

Synthesis example 3 Synthesis of Compound 135

Following the procedure for the preparation of Synthesis example 1, substituting a-7 with equimolar a-135 and G-7 with equimolar G-135, compound 135 (14.80G) was obtained; HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:684.2975 (theoretical value: 684.2961). Theoretical element content (%) C ₄₉H₄₀N₂ Si: c,85.92; h,5.89; n,4.09. Measured element content (%): c,85.93; h,5.86; n,4.07.

Synthesis example 4 Synthesis of Compound 168

According to the production method of Synthesis example 1, G-7 was replaced with equimolar G-168, and D-7 was replaced with equimolar D-168, to obtain Compound 168 (16.75G); HPLC purity is more than or equal to 99.94%. Mass spectrum m/z:832.3652 (theoretical value: 832.3669). Theoretical element content (%) C ₅₈H₅₂N₂Si₂: c,83.61; h,6.29; n,3.36. Measured element content (%): c,83.63; h,6.26; n,3.32.

Synthesis example 5 Synthesis of Compound 283

According to the production method of Synthesis example 1, G-7 was replaced with equimolar G-283 and D-7 was replaced with equimolar D-135 to obtain compound 283 (13.95G); HPLC purity is more than or equal to 99.99%. Mass spectrum m/z:619.3241 (theoretical value: 619.3228). Theoretical element content (%) C ₄₂H₂₅D₁₀N₃ Si: c,81.38; h,7.31; n,6.78. Measured element content (%): c,81.35; h,7.32; n,6.76.

Synthesis example 6 Synthesis of Compound 286

Following the procedure for the preparation of Synthesis example 1, G-7 was replaced with equimolar G-286 and D-7 was replaced with equimolar D-168, yielding compound 286 (14.94G); HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:681.2977 (theoretical value: 681.2996). Theoretical element content (%) C ₄₅H₄₃N₃Si₂: c,79.25; h,6.36; n,6.16. Measured element content (%): c,79.24; h,6.33; n,6.18.

Synthesis example 7 Synthesis of Compound 292

Following the procedure for the preparation of Synthesis example 2, d-7 was replaced with equimolar a-292, c-110 was replaced with equimolar c-292, and G-110 was replaced with equimolar G-292, yielding compound 292 (16.61G); HPLC purity is more than or equal to 99.94%. Mass spectrum m/z:825.3769 (theoretical value: 825.3786). Theoretical element content (%) C ₅₁H₅₉N₃Si₄: c,74.12; h,7.20; n,5.08. Measured element content (%): c,74.13; h,7.24; n,5.06.

Synthesis example 8 Synthesis of Compound 301

Following the procedure for the preparation of Synthesis example 2, d-7 was replaced with equimolar a-301, c-110 was replaced with equimolar c-292, and H-110 was replaced with equimolar H-292, yielding compound 301 (15.96 g); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:781.3325 (theoretical value: 781.3309). Theoretical element content (%) C ₅₃H₄₇N₃Si₂: c,81.39; h,6.06; n,5.37. Measured element content (%): c,81.36; h,6.04; n,5.39.

Synthesis example 9 Synthesis of Compound 305

Following the procedure for the preparation of Synthesis example 2, d-7 was replaced with equimolar a-305, c-110 was replaced with equimolar c-292, and H-110 was replaced with equimolar H-292, yielding compound 305 (17.83 g); HPLC purity is more than or equal to 99.92%. Mass spectrum m/z:913.4264 (theoretical value: 913.4248). Theoretical element content (%) C ₆₃H₅₉N₃Si₂: c,82.76; h,6.50; n,4.60. Measured element content (%): c,82.75; h,6.54; n,4.62.

Synthesis example 10 Synthesis of Compound 306

Following the procedure for the preparation of Synthesis example 1, substituting a-7 with equimolar a-306 and H-7 with equimolar H-292, compound 306 (16.83 g) was obtained; the HPLC purity is more than or equal to 99.93 percent. Mass spectrum m/z:849.3550 (theoretical value: 849.3539). Theoretical element content (%) C ₆₁H₄₇N₃ Si: c,86.18; h,5.57; n,4.94. Measured element content (%): c,86.17; h,5.59; n,4.91.

Synthesis example 11 Synthesis of Compound 348

Following the procedure for the preparation of synthetic example 1, G-7 was replaced with equimolar G-348 and D-7 was replaced with equimolar D-168 to give compound 348 (15.69G); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:757.3322 (theoretical value: 757.3309). Theoretical element content (%) C ₅₁H₄₇N₃Si₂: c,80.80; h,6.25; n,5.54. Measured element content (%): c,80.82; h,6.26; n,5.52.

Synthesis example 12 Synthesis of Compound 369

Following the procedure for the preparation of synthetic example 1, substituting a-7 with equimolar a-369 and H-7 with equimolar H-348 gave compound 369 (15.46 g); HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:735.3055 (theoretical value: 735.3070). Theoretical element content (%) C ₅₂H₄₁N₃ Si: c,84.86; h,5.62; n,5.71. Measured element content (%): c,84.83; h,5.64; n,5.73.

Synthesis example 13 Synthesis of Compound 393

Following the preparation method of Synthesis example 1, substituting a-7 with equimolar a-393 and H-7 with equimolar H-348 gave compound 393 (15.83 g); HPLC purity is more than or equal to 99.94%. Mass spectrum m/z:775.3001 (theoretical value: 775.3019). Theoretical element content (%) C ₅₄H₄₁N₃ OSi: c,83.58; h,5.33; n,5.41; . Measured element content (%): c,83.57; h,5.31; n,5.42; .

Synthesis example 14 Synthesis of Compound 401

Following the procedure for the preparation of Synthesis example 1, substituting a-7 with equimolar a-401 and H-7 with equimolar H-348, compound 401 (15.76 g) was obtained; the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:739.3396 (theoretical value: 739.3383). Theoretical element content (%) C ₅₂H₄₅N₃ Si: c,84.40; h,6.13; n,5.68. Measured element content (%) C,84.42; h,6.14; n,5.69.

Synthesis example 15 Synthesis of Compound 408

Following the procedure for the preparation of synthetic example 1, substituting a-7 with equimolar a-408 and H-7 with equimolar H-348 gave compound 408 (15.36 g); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:741.2646 (theoretical value: 741.2634). Theoretical element content (%) C ₅₀H₃₉N₃ SSi: c,80.93; h,5.30; n,5.66. Measured element content (%): c,80.91; h,5.31; n,5.64.

Synthesis example 16 Synthesis of Compound 426

Following the procedure for the preparation of synthetic example 1, G-7 was replaced with equimolar G-426 and D-7 was replaced with equimolar D-168 to give compound 426 (15.96G); HPLC purity is more than or equal to 99.94%. Mass spectrum m/z:781.3328 (theoretical value: 781.3309). Theoretical element content (%) C ₅₃H₄₇N₃Si₂: c,81.39; h,6.06; n,5.37. Measured element content (%): c,81.37; h,6.05; n,5.38.

Synthesis example 17 Synthesis of Compound 430

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Following the procedure for the preparation of Synthesis example 1, substituting a-7 with equimolar a-430 and G-7 with equimolar G-430, compound 430 (15.76G) was obtained; the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:739.3002 (theoretical value: 739.3019). Theoretical element content (%) C ₅₁H₄₁N₃ OSi: c,82.78; h,5.58; n,5.68. Measured element content (%): c,82.77; h,5.57; n,5.64.

Synthesis of Compound 439

According to the production method of Synthesis example 1, G-7 was replaced with equimolar G-439 and D-7 was replaced with equimolar D-369, to obtain Compound 439 (15.83G); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:775.3371 (theoretical value: 775.3383). Theoretical element content (%) C ₅₅H₄₅N₃ Si: c,85.12; h,5.84; n,5.41. Measured element content (%): c,85.13; h,5.81; n,5.44.

Synthesis example 19 Synthesis of Compound 446

Following the procedure for the preparation of synthetic example 1, E-7 was replaced with equimolar E-446, and D-7 was replaced with equimolar D-168, yielding compound 446 (15.73 g, 69%); HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:759.3229 (theoretical value: 759.3213). Theoretical element content (%) C ₄₉H₄₅N₅Si₂: c,77.43; h,5.97; n,9.21. Measured element content (%): c,77.45; h,5.96; n,9.22. Synthesis example 20 Synthesis of Compound 469

Following the preparation method of Synthesis example 1, E-7 was replaced with equimolar E-469 and D-7 was replaced with equimolar D-168, to give Compound 469 (16.79 g); HPLC purity is more than or equal to 99.94%. Mass spectrum m/z:834.3556 (theoretical value: 834.3574). Theoretical element content (%) C ₅₆H₅₀N₄Si₂: c,80.53; h,6.03; n,6.71. Measured element content (%): c,80.51; h,6.07; n,6.73.

Synthesis example 21 Synthesis of Compound 472

According to the production method of Synthesis example 1, G-7 was replaced with equimolar G-472 and D-7 was replaced with equimolar D-168, to obtain Compound 472 (17.04G); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:834.3560 (theoretical value: 834.3574). Theoretical element content (%) C ₅₆H₅₀N₄Si₂: c,80.53; h,6.03; n,6.71. Measured element content (%): c,80.51; h,6.04; n,6.74.

Synthesis example 22 Synthesis of Compound 477

Following the preparation method of Synthesis example 1, E-7 was replaced with equimolar E-477 and D-7 was replaced with equimolar D-168, to give Compound 477 (17.07 g); the HPLC purity is more than or equal to 99.93 percent. Mass spectrum m/z:861.3215 (theoretical value: 861.3207). Theoretical element content (%) C ₅₇H₄₇N₃O₂Si₂: c,79.41; h,5.49; n,4.87. Measured element content (%): c,79.43; h,5.47; n,4.86.

Synthesis example 23 Synthesis of Compound 499

Following the procedure for the preparation of synthetic example 1, E-7 was replaced with equimolar E-499, E-7 was replaced with equimolar E-499, and D-7 was replaced with equimolar D-168 to give compound 499 (16.45 g); HPLC purity is more than or equal to 99.94%. Mass spectrum m/z:817.3269 (theoretical value: 817.3280). Theoretical element content (%) C ₅₃H₄₃D₄N₃SSi₂: c,77.80; h,6.28; n,5.14. Measured element content (%): c,77.82; h,6.27; n,5.11. Synthesis example 24 Synthesis of Compound 509

Following the procedure for the preparation of Synthesis example 1, E-7 was replaced with equimolar E-509, E-7 was replaced with equimolar E-446, and D-7 was replaced with equimolar D-509 to give Compound 509 (15.69 g); HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:757.3327 (theoretical value: 757.3309). Theoretical element content (%) C ₅₁H₄₇N₃Si₂: c,80.80; h,6.25; n,5.54. Measured element content (%): c,80.82; h,6.26; n,5.52.

Synthesis example 25 Synthesis of Compound 571

Following the procedure for the preparation of synthetic example 1, H-7 was replaced with equimolar H-292 and D-7 was replaced with equimolar D-110 to give compound 571 (14.75 g); HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:682.2962 (theoretical value: 682.2948). Theoretical element content (%) C ₄₄H₄₂N₄Si₂: c,77.37; h,6.20; n,8.20. Measured element content (%): c,77.38; h,6.24; n,8.21.

Synthesis example 26 Synthesis of Compound 598

Following the procedure for the preparation of synthetic example 1, H-7 was replaced with equimolar H-348 and D-7 was replaced with equimolar D-110 to give compound 598 (15.71 g); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:758.3244 (theoretical value: 758.3261). Theoretical element content (%) C ₅₀H₄₆N₄Si₂: c,79.11; h,6.11; n,7.38. Measured element content (%): c,79.13; h,6.12; n,7.37.

Synthesis example 27 Synthesis of Compound 607

Following the preparation method of Synthesis example 1, substituting a-7 with equimolar a-607, c-7 with equimolar c-607, H-7 with equimolar H-348 gave compound 607 (19.14 g); HPLC purity is more than or equal to 99.91%. Mass spectrum m/z:980.4255 (theoretical value: 980.4274). Theoretical element content (%) C ₇₀H₅₆N₄ Si: c,85.68; h,5.75; n,5.71. Measured element content (%): c,85.69; h,5.73; n,5.73.

Synthesis example 28 Synthesis of Compound 613

Following the preparation method of Synthesis example 1, substituting a-7 with equimolar a-613, c-7 with equimolar c-607, H-7 with equimolar H-348 gave compound 613 (15.48 g); the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:726.2832 (theoretical value: 726.2815). Theoretical element content (%) C ₄₉H₃₈N₄ OSi: c,80.96; h,5.27; n,7.71. Measured element content (%): c,80.95; h,5.29; n,7.72.

Synthesis example 29 Synthesis of Compound 640

Following the procedure for the preparation of Synthesis example 1, H-7 was replaced with equimolar H-509 and D-7 was replaced with equimolar D-640 to give compound 640 (15.71 g); HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:758.3278 (theoretical value: 758.3261). Theoretical element content (%) C ₅₀H₄₆N₄Si₂: c,79.11; h,6.11; n,7.38. Measured element content (%): c,79.13; h,6.12; n,7.36.

Synthesis example 30 Synthesis of Compound 647

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Following the procedure for the preparation of synthetic example 1, F-7 was replaced with equimolar F-509, e-7 was replaced with equimolar e-647, and D-7 was replaced with equimolar D-640 to give compound 647 (16.79 g); HPLC purity is more than or equal to 99.94%. Mass spectrum m/z:834.3587 (theoretical value: 834.3574). Theoretical element content (%) C ₅₆H₅₀N₄Si₂: c,80.53; h,6.03; n,6.71. Measured element content (%): c,80.57; h,6.01; n,6.72.

Synthesis example 31 Synthesis of Compound 648

Following the procedure for the preparation of Synthesis example 1, E-7 was replaced with equimolar E-648 and D-7 was replaced with equimolar D-110 to give Compound 648 (16.54 g); the HPLC purity is more than or equal to 99.93 percent. Mass spectrum m/z:834.3559 (theoretical value: 834.3574). Theoretical element content (%) C ₅₆H₅₀N₄Si₂: c,80.53; h,6.03; n,6.71. Measured element content (%): c,80.54; h,6.01; n,6.75.

Synthesis example 32 Synthesis of Compound 651

Following the preparation method of Synthesis example 1, E-7 was replaced with equimolar E-651, E-7 was replaced with equimolar E-446, and D-7 was replaced with equimolar D-640, to give Compound 651 (14.84 g); the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:686.2854 (theoretical value: 686.2866). Theoretical element content (%) C ₄₇H₃₈N₄ Si: c,82.18; h,5.58; n,8.16. Measured element content (%): c,82.15; h,5.57; n,8.18.

Synthesis example 33 Synthesis of Compound 652

Following the preparation method of Synthesis example 1, F-7 was replaced with equimolar F-651, e-7 was replaced with equimolar e-652, and D-7 was replaced with equimolar D-652, to give Compound 652 (14.65 g); HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:687.2832 (theoretical value: 687.2818). Theoretical element content (%) C ₄₆H₃₇N₅ Si: c,80.32; h,5.42; n,10.18. Measured element content (%): c,80.33; h,5.45; n,10.16.

Synthesis example 34 Synthesis of Compound 676

Following the procedure for the preparation of synthetic example 1, substituting A-7 with equimolar A-135, c-7 with equimolar c-676, H-7 with equimolar H-348 gave compound 676 (14.86 g); HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:687.2832 (theoretical value: 687.2818). Theoretical element content (%) C ₄₆H₃₇N₅ Si: c,80.32; h,5.42; n,10.18. Measured element content (%): c,80.33; h,5.45; n,10.16.

Synthesis example 35 Synthesis of Compound 711

According to the production method of Synthesis example 1, G-7 was replaced with equimolar G-711 and D-7 was replaced with equimolar D-509 to obtain Compound 711 (16.61G); HPLC purity is more than or equal to 99.94%. Mass spectrum m/z:825.3772 (theoretical value: 825.3786). Theoretical element content (%) C ₅₁H₅₉N₃Si₄: c,74.12; h,7.20; n,5.08. Measured element content (%): c,74.15; h,7.24; n,5.06.

Synthesis example 36 Synthesis of Compound 725

Following the procedure for the preparation of synthetic example 1 substituting equimolar a-725 for a-7, equimolar c-607 for c-7 and equimolar G-725 for G-7, compound 725 (16.18G) was obtained; HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:792.2759 (theoretical value: 792.2743). Theoretical element content (%) C ₅₃H₄₀N₄ SSi: c,80.27; h,5.08; n,7.06. Measured element content (%): c,80.26; h,5.05; n,7.05.

Synthesis example 37 Synthesis of Compound 729

Following the preparation method of Synthesis example 1, F-7 was replaced with equimolar F-509, e-7 was replaced with equimolar e-729, and D-7 was replaced with equimolar D-652, to give Compound 729 (14.86 g); HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:687.3166 (theoretical value: 687.3152). Theoretical element content (%) C ₄₃H₃₇D₄N₅Si₂: c,75.07; h,6.59; n,10.18. Measured element content (%): c,75.06; h,6.57; n,10.16. Synthesis example 38 Synthesis of Compound 745

Following the procedure for the preparation of synthetic example 2, d-7 was replaced with equimolar a-745, c-110 was replaced with equimolar c-292, and H-110 was replaced with equimolar H-348 to give compound 745 (16.27 g); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:785.3639 (theoretical value: 785.3622). Theoretical element content (%) C ₅₃H₅₁N₃Si₂: c,80.97; h,6.54; n,5.34. Measured element content (%): c,80.95; h,6.57; n,5.37.

Synthesis example 39 Synthesis of Compound 761

Following the preparation method of Synthesis example 1, substituting A-7 with equimolar A-135 and c-7 with equimolar c-761, compound 761 (13.49 g) was obtained; HPLC purity is more than or equal to 99.99%. Mass spectrum m/z:607.2682 (theoretical value: 607.2695). Theoretical element content (%) C ₄₄H₃₇ NSi: c,86.94; h,6.14; n,2.30. Measured element content (%): c,86.96; h,6.13; n,2.32.

Synthesis example 40 Synthesis of Compound 776

Following the preparation method of synthetic example 1, A-7 was replaced with equimolar A-776, d-7 was replaced with equimolar d-776, and F-7 was replaced with equimolar F-776, to give compound 776 (15.14 g); the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:710.2852 (theoretical value: 710.2866). Theoretical element content (%) C ₄₉H₃₈N₄ Si: c,82.78; h,5.39; n,7.88. Measured element content (%): c,82.77; h,5.38; n,7.85.

Synthesis example 41 Synthesis of comparative Compound P-1

Following the procedure for the preparation of Synthesis example 1, E-7 was replaced with equimolar H-651, E-7 was replaced with equimolar E-P-1, and D-7 was replaced with equimolar D-640, to give Compound P-1 (16.10 g); the HPLC purity is more than or equal to 99.93 percent. Mass spectrum m/z:812.3349 (theoretical value: 812.3335). Theoretical element content (%) C ₅₇H₄₄N₄ Si: c,84.20; h,5.45; n,6.89. Measured element content (%): c,84.22; h,5.47; n,6.86.

Device example

Test software, a computer, a K2400 digital source meter manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by PhotoResearch company, U.S. are combined into a combined IVL test system to test the driving voltage and luminous efficiency of the organic electroluminescent device. Life testing an M6000OLED life test system from MCSCIENCE was used.

Device example 1

The glass substrate was cleaned with distilled water and ultrasonic waves. After the distilled water washing is completed, ultrasonic washing is performed using a solvent such as isopropyl alcohol, acetone, methanol, etc., and drying is performed. Drying, transferring to a plasma cleaning machine, washing, and transferring the substrate to an evaporation machine. An anode is formed by coating Indium Tin Oxide (ITO) on a glass substrate. Vapor deposition of HI-1 on anode: HAT-CN (mass ratio 10:1) formed to a thickness ofIs provided. Evaporating HT-1 on the injection layer to form a layer with a thickness of/>Is provided. Evaporating a light-emitting layer on the hole transport layer to obtain EML-1 as a host material of the light-emitting layer and doping 6wt% of EML-2 to obtain a film with a thickness of/>Is provided. Evaporation of inventive compound 7 on the light-emitting layer: liQ (mass ratio 1:1) to form a thickness ofIs provided. Evaporating Al on the electron transport layer to form a film with a thickness of/>Is provided. Thereby forming an organic light emitting device.

Device examples 2to 40

An organic electroluminescent device was produced by the same production method as in device example 1, except that compound 7 in device example 1 was replaced with compound 110, compound 135, compound 168, compound 283, compound 286, compound 292, compound 301, compound 305, compound 306, compound 348, compound 369, compound 393, compound 401, compound 408, compound 426, compound 430, compound 439, compound 446, compound 469, compound 472, compound 477, compound 499, compound 509, compound 571, compound 598, compound 607, compound 613, compound 640, compound 647, compound 648, compound 651, compound 652, compound 676, compound 711, compound 725, compound 729, compound 745, compound 761 and compound 776 according to the present invention.

Comparative device examples 1 to 5

An organic electroluminescent device was produced by the same production method as in device example 1, except that compound P-1, compound P-2, compound P-3, compound P-4, and compound P-5 were used as electron transporting materials in place of compound 7 in device example 1, respectively.

The environment tested was atmospheric and the temperature was room temperature. The results of testing the light emitting characteristics of the devices 1 to 40, and the organic electroluminescent devices obtained in comparative examples 1 to 5 in the examples of the device according to the present invention are shown in table 1 below.

Table 1:

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As can be seen from the results of table 1, when the heterocyclic compound of the present invention is applied to the electron transport layer of an organic electroluminescent device, the device has lower driving voltage, higher luminous efficiency and longer service life, and the compound of the present invention is an electron transport material with good performance.

Device example 41

The glass substrate was cleaned with distilled water and ultrasonic waves. After the distilled water washing is completed, ultrasonic washing is performed using a solvent such as isopropyl alcohol, acetone, methanol, etc., and drying is performed. Drying, transferring to a plasma cleaning machine, washing, and transferring the substrate to an evaporation machine. An anode is formed by coating Indium Tin Oxide (ITO) on a glass substrate. Vapor deposition of HI-1 on anode: HAT-CN (mass ratio 10:1) formed to a thickness ofIs provided. Evaporating HT-2 on the injection layer to form a layer with a thickness of/>Is provided. Evaporating a light-emitting layer on the hole transport layer to obtain EML-3 as a host material of the light-emitting layer and doped with 4wt% of EML-4 to obtain a film with a thickness of/>Is provided. Evaporating the compound 7 of the present invention on the light-emitting layer to form a film having a thickness of/>Is a hole blocking layer of (a). Evaporating ET-2 on the hole blocking layer: liQ (mass ratio 1:1) to form a thickness/>Is provided. Vapor deposition of LiF on electron transport layer to a thickness/>Electron injection layer of (a) is provided. Evaporating Al on the electron injection layer to obtain a film with a thickness of/>Is provided. Thereby forming an organic light emitting device.

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Device examples 42 to 80

An organic electroluminescent device was produced by the same production method as in device example 41, except that compound 7 in device example 41 was replaced with compound 110, compound 135, compound 168, compound 283, compound 286, compound 292, compound 301, compound 305, compound 306, compound 348, compound 369, compound 393, compound 401, compound 408, compound 426, compound 430, compound 439, compound 446, compound 469, compound 472, compound 477, compound 499, compound 509, compound 571, compound 598, compound 607, compound 613, compound 640, compound 647, compound 648, compound 651, compound 652, compound 676, compound 711, compound 725, compound 729, compound 745, compound 761 and compound 776 according to the present invention.

Comparative device examples 6 to 9

An organic electroluminescent device was manufactured by the same manufacturing method as in device example 41, except that compound P-6, compound P-7, compound P-8, and compound P-9 were used as hole blocking materials instead of compound 7 in device example 41, respectively.

The environment tested was atmospheric and the temperature was room temperature. The results of testing the light emitting characteristics of the devices 41 to 80, and the organic electroluminescent devices obtained in comparative examples 6 to 9 in the examples of the device according to the present invention are shown in table 2 below.

Table 2:

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As can be seen from the results in Table 2, when the heterocyclic compound of the present invention is applied to the hole blocking layer of an organic electroluminescent device, the device has lower driving voltage, higher luminous efficiency and longer service life, and the compound of the present invention is a hole blocking material with good performance.

Device example 81

The glass substrate was cleaned with distilled water and ultrasonic waves. After the distilled water washing is completed, ultrasonic washing is performed using a solvent such as isopropyl alcohol, acetone, methanol, etc., and drying is performed. Drying, transferring to a plasma cleaning machine, washing, and transferring the substrate to an evaporation machine. An anode is formed by coating Indium Tin Oxide (ITO) on a glass substrate. Evaporation of HT-3 on anode: HI-3 (mass ratio 97:3), formed to a thickness ofIs provided (1). Evaporating HT-3 on the hole injection layer to form a layer with a thickness of/>Is provided (1). An electron blocking layer EB-3 is vapor deposited on the hole transport layer1 to form a layer with the thickness of/>An electron blocking layer 1 of (a). Evaporating a light-emitting layer 1 on the electron blocking layer 1, wherein the EML-1 is used as a main material of the light-emitting layer and doped with 3wt% of EML-2 to form a light-emitting layer with the thickness ofIs provided. A hole blocking layer HB-3 was vapor deposited on the light-emitting layer 1 to form a film having a thickness/>Is provided. Evaporating ET-3 on the hole blocking layer 1: liQ (mass ratio 1:1) to form a thickness/>Electron transport layer 1 of (a). The electron transport layer 1 was vapor-deposited with the compound 7 of the present invention, doped with 5wt% of Li, to form a film having a thickness/>N-type charge generation layer of (c). Evaporating P-CGL and F4-TCNQ doped with 6wt% on N-type charge generation layer to form a film with a thickness of/>P-type charge generation layer of (c). Evaporating HT-3 on the P-type charge generation layer: HI-3 (mass ratio 97:3), formed to a thickness/>Is provided. HT-3 was vapor deposited on the hole injection layer 2 to a thickness/>Is provided (a) a hole transport layer 2. An electron blocking layer EB-3 is vapor deposited on the hole transport layer2 to form a layer with the thickness of/>An electron blocking layer 2 of (a). Evaporating a light-emitting layer 2 on the electron blocking layer 2, wherein the EML-1 is used as a main material of the light-emitting layer and doped with 5wt% of EML-2 to form a light-emitting layer with a thickness of/>Is provided (a) and a light emitting layer 2 of the same. A hole blocking layer HB-3 was vapor deposited on the light-emitting layer 2 to form a film having a thickness/>Is provided. Evaporating ET-3 on the hole blocking 2: liQ (mass ratio 1:1) to form a thickness/>Is provided (a) an electron transport layer 2. LiF is vapor deposited on the electron transport layer 2 to form a film having a thickness of/>Electron injection layer of (a) is provided. Evaporating Al on the electron injection layer to obtain a film with a thickness of/>Is provided. Thereby forming an organic light emitting device.

Device examples 82 to 120

An organic electroluminescent device was produced by the same production method as in device example 81, except that compound 7 in device example 81 was replaced with compound 110, compound 135, compound 168, compound 283, compound 286, compound 292, compound 301, compound 305, compound 306, compound 348, compound 369, compound 393, compound 401, compound 408, compound 426, compound 430, compound 439, compound 446, compound 469, compound 472, compound 477, compound 499, compound 509, compound 571, compound 598, compound 607, compound 613, compound 640, compound 647, compound 648, compound 651, compound 652, compound 676, compound 711, compound 725, compound 729, compound 745, compound 761 and compound 776, respectively, as N-type charge generation layer materials.

Comparative device examples 10 to 11

An organic electroluminescent device was manufactured by the same manufacturing method as in device example 81, except that compound P-10 and compound P-11 were used as the N-type charge generation layer material instead of compound 7 in device example 81, respectively.

The environment tested was atmospheric and the temperature was room temperature. The results of testing the light emitting characteristics of the devices 81 to 120 in the device examples according to the present invention and the organic electroluminescent devices obtained in the comparative examples 10 to 11 are shown in the following table 3.

Table 3:

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As can be seen from the results of table 3, when the heterocyclic compound of the present invention is applied to an N-type charge generation layer material of an organic electroluminescent device, the device has lower driving voltage, higher luminous efficiency and longer service life, and the compound of the present invention is an N-type charge generation layer material with good performance.

It should be noted that while the present invention has been specifically described with reference to individual embodiments, it will be apparent to those skilled in the art that numerous modifications and variations can be made without departing from the principles of the present invention, and such modifications and variations fall within the scope of the present invention.

Claims

1. A heterocyclic compound, wherein the heterocyclic compound has a structure represented by formula I:

the V is selected from any one of CH and N;

the V' is selected from any one of CH and N;

Said p is selected from 1,2, 3 or 4;

2. A heterocyclic compound according to claim 1, wherein the heterocyclic compound is selected from any one of the following structures:

3. A heterocyclic compound according to claim 1, wherein L is selected from any one of the following structures or from a combination of two or more of the following structures:

4. A heterocyclic compound according to claim 1, wherein L is selected from any one of the following structures or from a combination of two or more of the following structures:

5. The heterocyclic compound according to claim 1, wherein Ar ₁、Ar₂、Ar₃、Ar₄ is independently selected from any one of the following structures:

Z is selected from any one of CH and N;

6. A heterocyclic compound according to claim 1, wherein L ₁、L₂、L₃、L₄ is independently selected from a single bond or from any one of the following structures or from a combination of two or more of the following structures:

the R is selected from any one of CH and N;

Said n is selected from 1,2, 3 or 4;

7. A heterocyclic compound according to claim 1, wherein the heterocyclic compound is selected from any one of the following structures:

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8. An organic electroluminescent device comprising an anode, a cathode, and an organic layer between the anode and the cathode or on a side of the cathode facing away from the anode, characterized in that the organic layer comprises at least one of the heterocyclic compounds according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, wherein the organic layer comprises at least one of an electron transport layer, a hole blocking layer, a light emitting layer, and a capping layer, the at least one of an electron transport layer, a hole blocking layer, a light emitting layer, and a capping layer comprising at least one of the heterocyclic compounds according to any one of claims 1 to 7.

10. The organic electroluminescent device according to claim 8, wherein the organic layer is located between the anode and the cathode, the organic layer comprises a first light-emitting portion located between the anode and the cathode, a second light-emitting portion located between the first light-emitting portion and the cathode, and a charge generation layer located between the first light-emitting portion and the second light-emitting portion, the charge generation layer comprises at least one of the heterocyclic compounds according to any one of claims 1 to 7.