A kind of organic electroluminescent device of bipyridine compound and its preparation method

Abstract

The application provides a kind of biscalbazoles compound and its organic electroluminescent device, belong to organic electroluminescent technical field.The biscalbazoles compound provided by the application has suitable HOMO energy level and triplet energy gap, can make the device inside have higher internal quantum efficiency, and further improve the luminous efficiency of organic electroluminescent device, while the compound has good thermal stability, when it is applied to organic electroluminescent device, can further prolong the service life of device.The biscalbazoles compound and its organic electroluminescent device have good application effect and industrialization prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescence, in particular to a kind of biscalbazoles compound and organic electroluminescent device thereof. BACKGROUND

[0002] Organic Light-Emitting Diode (OLED) as a new generation of display technology, with ultra-thin, self-luminous, wide viewing angle, fast response, high luminous efficiency, good temperature adaptability, simple production process, low driving voltage, low energy consumption and other advantages, has been widely used in flat panel display, flexible display, solid-state lighting and vehicle display industries.

[0003] Organic electroluminescence is the phenomenon of converting electrical energy into light energy using organic materials. An organic electroluminescent device utilizing the organic electroluminescence phenomenon generally has the following structure: an anode, a cathode, and an organic material layer between or outside the anode and the cathode. The organic material layer is usually formed in a multi-layer structure composed of different materials to improve the brightness, efficiency and lifetime of the organic electroluminescent device. The organic material layer can be composed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cover layer.

[0004] Currently, 4,4'-N,N'-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host material, and Pioneer (Japan) and other companies use bathocuproine (BCP) and aluminum (III) bis(2-methyl-8-quinolinate) (4-phenylphenolate) (BAlq) as hole blocking materials, which are also good host materials. However, although conventional materials provide good light emitting characteristics, they have the following disadvantages: (1) degradation occurs during high temperature deposition in vacuum, and the lifetime of the device is shortened. (2) The luminous efficiency still cannot meet the requirements of large area display.

[0005] The most important problem in existing organic electroluminescent devices is the problem of lifetime and efficiency. With the large area of display, the driving voltage increases, the luminous efficiency also needs to be improved, and a certain service life must be ensured. Therefore, it is necessary to continue to develop new organic electroluminescent materials to further improve the performance of organic electroluminescent devices. SUMMARY

[0006] In order to further improve the performance of organic electroluminescent devices and adapt to the large area of display, the present application provides a kind of biscalbazoles compound and organic electroluminescent device thereof. The biscalbazoles compound of the present application has high stability, and the compound has high HOMO energy level and triplet energy gap (E TWhen applied to organic electroluminescent devices, it can effectively improve the luminous efficiency of the devices and extend their service life.

[0007] This invention provides a bicarbazole compound, characterized in that the bicarbazole compound has the structure shown in Chemical Formula 1.

[0008]

[0009] The x that is the same or different is selected from CR3 or N, wherein the x that is bonded to Ar0 or L0 is selected from C;

[0010] The R3 is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C25 heteroaryl, or substituted or unsubstituted silyl, or adjacent R3s are connected to each other to form a substituted or unsubstituted ring; when there are two or more R3s, the two or more R3s are the same or different from each other;

[0011] The Ar0 is selected from the structure shown in chemical formula 2.

[0012]

[0013] The z that are the same or different are selected from CR2 or N;

[0014] The R1 and R2 are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic group, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C25 heteroaryl, substituted or unsubstituted silyl, or adjacent R2 are connected to each other to form a substituted or unsubstituted ring;

[0015] The L0, L1, and L2 are the same or different and are selected from any one of the following: single bond, substituted or unsubstituted C6-C24 arylene, substituted or unsubstituted C2-C25 heteroarylene, and substituted or unsubstituted C3-C12 alicyclic group;

[0016] The Ar1 and Ar2 are the same or different and are selected from any one of the following: substituted or unsubstituted C3-C12 alicyclic groups, substituted or unsubstituted C6-C24 aryl groups, substituted or unsubstituted C2-C25 heteroaryl groups, and substituted or unsubstituted silyl groups.

[0017] At least one group in the chemical formula 1 is substituted with Si(R4)3, wherein the same or different R4 is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C18 aryl, or substituted or unsubstituted C2-C12 heteroaryl.

[0018] The present invention also provides an organic electroluminescent device comprising an anode, an organic layer, and a cathode, wherein the organic layer comprises one or a combination of at least two of the bicarbazole compounds.

[0019] The beneficial effects of this invention are:

[0020] The bicarbazole compounds provided by this invention have high HOMO levels and triplet band gaps (E0). T This invention ensures high internal quantum efficiency and higher energy transfer efficiency within the device. Furthermore, the excellent molecular stereochemistry of this type of structure enables the material to possess good thermal stability and amorphous morphology. Therefore, when the bicarbazole compounds provided by this invention are applied to organic electroluminescent devices, the luminous efficiency of the device can be effectively improved and the lifespan of the device can be extended. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Furthermore, the embodiments and features in the embodiments of the present invention can be combined with each other without conflict. Based on the described embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0023] In the compounds of the present invention, any atom not specified as a particular isotope is included as any stable isotope of that atom, and includes atoms at both their natural and non-natural isotopic abundances.

[0024] In this specification, "*-" refers to the portion connected to another substituent.

[0025] In this specification, when the position of the substituent on the ring is not fixed, it means that it can be attached to any of the corresponding optional sites on the ring. For example, Can represent Can represent Can represent And so on.

[0026] In this specification, when a substituent or linking site is located on a bond that extends through two or more rings, it indicates that it can be linked to any one of the two or more rings, specifically to any one of the corresponding optional sites on the ring. For example Can represent Can represent Can represent And so on.

[0027] The halogens mentioned in this invention refer to fluorine, chlorine, bromine, and iodine;

[0028] The alkyl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from an alkane molecule. It can be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 25 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples may include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, etc., but are not limited thereto.

[0029] The alicyclic group mentioned in this invention refers to a monovalent group formed by removing one less hydrogen atom from an alicyclic hydrocarbon molecule. It can be cycloalkyl, cycloalkenyl, etc., preferably having 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. Examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornel, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc., but are not limited thereto.

[0030] The aryl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from the aromatic carbon atom of an aromatic hydrocarbon molecule. It can be a monocyclic aryl, polycyclic aryl, or fused-ring aryl, preferably having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. Examples may include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, indene, dihydroindene, dihydronaphthyl, tetrahydronaphthyl, anthracene, phenanthrene, pyrene, triphenylene, perylene, etc., but are not limited thereto.

[0031] The heteroaryl group described in this invention refers to a monovalent group formed by removing a hydrogen atom from the core carbon of an aromatic heterocycle composed of carbon and heteroatoms. The heteroatoms can be one or more of N, O, and S, and can be monocyclic, polycyclic, or fused-ring heteroaryl groups. Preferably, it has 3 to 30 carbon atoms, more preferably 3 to 22 carbon atoms, more preferably 3 to 16 carbon atoms, and most preferably 3 to 8 carbon atoms. Examples include pyridyl, pyrimidinyl, triazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, naphthidyl, furanyl, thiophene, pyrroleyl, benzofuranyl, benzothiophene, indoleyl, and pyridofuranyl. The following are listed: nylonyl, pyridothiophenyl, pyridopyrroleyl, pyrimidinofuranyl, pyrimidinothiophenyl, naphthofuranyl, naphthothiophenyl, phenanthrofuranyl, phenanthiophenyl, dibenzofuranyl, dibenzothiophenyl, carbazoleyl, benzonaphthofuranyl, benzonaphthothiophenyl, dinaphthofuranyl, dinaphthothiophenyl, oxazolyl, thiazolyl, imidazolyl, benzooxazolyl, benzothiazolyl, benzoimidazolyl, naphthooxazolyl, naphthothiazolyl, naphthoimidazolyl, phenanthoxazolyl, phenanthiazolyl, pyridinooxazolyl, pyridinothiazolyl, azacarbazoleyl, quinolinooxazolyl, quinolinothiazolyl, quinolinoimidazolyl, etc., but not limited to these.

[0032] In this specification, "substituted or unsubstituted silyl group" refers to -Si(R k )3 groups, wherein each R k The same or different groups are selected from the following: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C6-C60 aromatic ring, and fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C2-C60 heteroaryl. Preferably, each R k The same or different groups are selected from the following: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, and substituted or unsubstituted C3-C30 cycloalkyl. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, even more preferably 1 to 10, and most preferably 1 to 8. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, even more preferably 3 to 10, and most preferably 3 to 7. Preferably, each R... kThe same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornel.

[0033] The arylene group described in this invention refers to a divalent group formed by removing two hydrogen atoms from the aromatic carbon atom of an aromatic hydrocarbon molecule. Apart from being divalent groups, they are subject to the same description of aryl groups as described above.

[0034] The heteroaryl group described in this invention refers to a divalent group formed by removing two hydrogen atoms from the nucleus carbon of an aromatic heterocycle composed of carbon and heteroatoms. Apart from being divalent groups, they are subject to the above description of heteroaryl groups.

[0035] The term "substitution" as used in this invention refers to the replacement of hydrogen atoms in a compound group with other atoms or groups, and the substitution position is not limited.

[0036] In this invention, "substituted or unsubstituted" means either unsubstituted or substituted by one or more substituents selected from the group consisting of: protium, deuterium, tritium, cyano, halogen atom, amino, nitro, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C30 alicyclic group, substituted or unsubstituted C1-C25 heterocyclic alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 alicyclic and C6-C30 aromatic ring fused cycloyl groups, substituted or unsubstituted C1-C25 heterocyclic alkanes and C6-C30 aromatic ring fused cycloyl groups, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C25 alicyclic and C2-C30 heteroaromatic ring fused cycloyl groups, substituted or Unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C30 aryloxy group, preferably protium, deuterium, tritium, halogen atom, cyano, C1-C12 alkyl, C3-C18 alicyclic, C6-C25 aryl, C2-C25 heteroaryl, specific examples may include protium, deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl alkyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, cyclopentenyl, cyclohexenyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocyclopentenyl, benzocyclohexenyl, trifluoromethyl, phenyl, tolyl, mesityleleyl, pentadeuterated phenyl, pentafluorophenyl, biphenyl, naphthyl, anthracene, phenanthrene, benzophenanthrene, pyrene, triphenylene alkyl, peryl, fluoranyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, carbazole, 9-phenylcarbazole, spirodifluorenyl, carbazole-indole, pyrrole, furanyl, thiophene, indole, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, oxadiazinyl The substituents include, but are not limited to, azole, thiazolyl, imidazole, benzoxazolyl, benzothiazolyl, benzotriazolyl, benzoimidazolyl, pyridinozolyl, pyridinozothiazolyl, pyridinozothiazolyl, pyrimidinozolyl, pyrimidinozothiazolyl, pyrimidinozolyl, quinolinyl, isoquinolinyl, quinolinozolyl, quinolinozothiazolyl, quinolinozolyl, phenothiazinyl, phenothiazinyl, acridineyl, etc. Alternatively, when there are two or more substituents, adjacent substituents may bond to form a ring; when there are two or more substituents, the two or more substituents may be the same as or different from each other.

[0037] In this invention, "two adjacent groups joining to form a ring" refers to the formation of a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle by combining adjacent groups with each other and optionally aromatizing them. The hydrocarbon ring can be an aliphatic or aromatic hydrocarbon ring. The heterocycle can be an aliphatic or aromatic heterocycle. The aliphatic hydrocarbon ring can be a saturated or unsaturated aliphatic hydrocarbon ring, and the aliphatic heterocycle can be a saturated or unsaturated aliphatic heterocycle. The hydrocarbon ring and heterocycle can be monocyclic or polycyclic groups. Furthermore, the ring formed by the combination of adjacent groups can be connected to another ring to form a spirostructure. An example is shown below:

[0038]

[0039] In this specification, the rings formed by the linkage can be aromatic or non-aromatic rings, and can be three-membered, four-membered, five-membered, six-membered, seven-membered, eight-membered, fused rings, etc., such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, adamantane, norbornene, benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, quinoline, isoquinoline, quinazoline, quinoxaline, fluorene, dibenzofuran, dibenzothiophene, carbazole, etc., but not limited to these.

[0040] The following describes embodiments of the organic electroluminescent device of the present invention. However, the embodiments of the present invention can be modified into other forms, and the scope of the present invention is not limited to the embodiments described below.

[0041] In describing the structural elements of this invention, the terms "comprising" or "including" as used herein mean that the device or object preceding the term covers the device or object listed after the term and its equivalents, without excluding other devices or objects. Terms such as "connected" or "linked" are not limited to physical or mechanical connections, but can include electrical connections, whether direct or indirect. Terms such as "inner," "outer," "upper," and "lower" are used only to indicate relative positional relationships; when the absolute position of the described structural element changes, the relative positional relationship may also change accordingly. Furthermore, when a structural element such as a layer, membrane, region, or plate is located "on" other structural elements, it can be understood not only as being "directly above" other structural elements, but also as having other structural elements in between. Conversely, when a structural element is located "directly above" other structural elements, it should be understood as having no other structural elements in between.

[0042] In this invention, "at least one" includes one, two, three, four, five or more.

[0043] In this invention, "one or more" includes one, two, three, four, five or more.

[0044] This invention provides a bicarbazole compound having the structure shown in Chemical Formula 1.

[0045]

[0046] The x that is the same or different is selected from CR3 or N, wherein the x that is bonded to Ar0 or L0 is selected from C;

[0047] The R3 is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C25 heteroaryl, or substituted or unsubstituted silyl, or adjacent R3s are connected to each other to form a substituted or unsubstituted ring; when there are two or more R3s, the two or more R3s are the same or different from each other;

[0048] The Ar0 is selected from the structure shown in chemical formula 2.

[0049]

[0050] The z that are the same or different are selected from CR2 or N;

[0051] The R1 and R2 are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic group, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C25 heteroaryl, substituted or unsubstituted silyl, or adjacent R2 are connected to each other to form a substituted or unsubstituted ring;

[0052] The L0, L1, and L2 are the same or different and are selected from any one of the following: single bond, substituted or unsubstituted C6-C24 arylene, substituted or unsubstituted C2-C25 heteroarylene, and substituted or unsubstituted C3-C12 alicyclic group;

[0053] The Ar1 and Ar2 are the same or different and are selected from any one of the following: substituted or unsubstituted C3-C12 alicyclic groups, substituted or unsubstituted C6-C24 aryl groups, substituted or unsubstituted C2-C25 heteroaryl groups, and substituted or unsubstituted silyl groups.

[0054] At least one group in the chemical formula 1 is substituted with Si(R4)3, wherein the same or different R4 is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C18 aryl, or substituted or unsubstituted C2-C12 heteroaryl.

[0055] Preferably, the chemical formula 1 has the structure shown in chemical formula 1-1 or chemical formula 1-2.

[0056]

[0057] Preferably, at least one of the groups L1, L2, Ar1, Ar2, L0, and Ar0 is substituted with Si(R4)3;

[0058] More preferably, one, two, three, four, five or six of the groups L1, L2, Ar1, Ar2, L0, and Ar0 are replaced by Si(R4)3;

[0059] More preferably, at least one of the groups L1, L2, Ar1, and Ar2 is substituted with Si(R4)3;

[0060] More preferably, one, two, three or four of the groups L1, L2, Ar1, and Ar2 are replaced by Si(R4)3;

[0061] More preferably, at least one group in Ar1 and Ar2 is replaced by Si(R4)3;

[0062] Most preferably, one or two groups in Ar1 and Ar2 are replaced by Si(R4)3;

[0063] Preferably, the R4 is the same or different from any one of hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, phenyl, biphenyl, naphthyl, pyridyl, and pyrimidinyl.

[0064] The R4 may be replaced by one or more substituents selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, phenyl, deuterated phenyl, pentafluorophenyl, and naphthyl; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

[0065] Preferably, the Si(R4)3 is selected from any one of the following structures.

[0066]

[0067] Preferably, the Ar0 is selected from any one of the following structures.

[0068]

[0069]

[0070]

[0071] a1 is selected from 1, 2, 3, 4, 5, 6, 7 or 8; a2 is selected from 1, 2, 3, 4, 5, 6 or 7; a3 is selected from 1, 2, 3, 4, 5 or 6; a4 is selected from 1, 2, 3, 4 or 5; a5 is selected from 1, 2, 3 or 4; when there are two or more R2, the two or more R2 are the same as or different from each other.

[0072] Preferably, the same or different R2 in this invention is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, and Si(R4)3;

[0073] The R2 may be replaced by one or more substituents selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, phenyl, biphenyl, deuterated phenyl, pentafluorophenyl, naphthyl, Si(R4)3; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

[0074] Preferably, the R1s mentioned in this invention are the same or different from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, and Si(R4)3;

[0075] R1 can be replaced by one or more substituents R 11 The substituent R is replaced 11 It is selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, trimethylsilyl, phenyl, biphenyl, deuterated phenyl, pentafluorophenyl, naphthyl, Si(R4)3; when two or more substituents are present, the two or more substituents are the same as or different from each other.

[0076] Preferably, when Si(R4)3 replaces Ar0, it replaces the corresponding number of R... 11 And / or R2.

[0077] Preferred, R 11 One, two, or more of them are selected from Si(R4)3.

[0078] Preferably, one, two or more of R2 are selected from Si(R4)3.

[0079] Preferably, the Ar1 and Ar2 are the same or different and are selected from Si(R4)3 or any of the structures shown below.

[0080]

[0081] The same or different v is selected from CH or N;

[0082] The Y is selected from any one of O, S, C(Ra)2, and N(Rb);

[0083] The Ra is the same as or different from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C25 heteroaryl, and substituted or unsubstituted silyl. The Ra can be directly connected to L1 and / or L2.

[0084] The Rb is selected from any one of substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C12 alicyclic groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C25 heteroaryl groups, and substituted or unsubstituted silyl groups. The Rb can be directly connected to L1 and / or L2.

[0085] The R5 is the same as or different from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C25 heteroaryl, and substituted or unsubstituted silyl.

[0086] The n1 is selected from 1, 2, 3, 4 or 5; the n2 is selected from 1, 2, 3, 4, 5, 6 or 7; the n3 is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; the n4 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; the n5 is selected from 1, 2, 3, 4, 5 or 6; when there are two or more R5s, the two or more R5s are the same or different from each other, or adjacent R5s are connected to each other to form substituted or unsubstituted rings.

[0087] Preferably, the Ar1 and Ar2 are the same or different and are selected from Si(R4)3 or any of the structures shown below.

[0088]

[0089]

[0090] The R5, whether identical or different, is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, and Si(R4)3;

[0091] The R5 may be replaced by one or more substituents selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, phenyl, biphenyl, deuterated phenyl, pentafluorophenyl, naphthyl, Si(R4)3; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

[0092] The n1 is selected from 1, 2, 3, 4, or 5; the n2 is selected from 1, 2, 3, 4, 5, 6, or 7; the n3 is selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; the n4 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; the n5 is selected from 1, 2, 3, 4, 5, or 6; the n6 is selected from 1, 2, 3, or 4; the n7 is selected from 1, 2, or 3; the n8 is selected from 1 or 2; the n9 is selected from 1, 2, 3, 4, 5, 6, 7, or 8; the n 10 Choose from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; when there are two or more R5s, the two or more R5s are the same as or different from each other.

[0093] Preferably, when Si(R4)3 replaces Ar1 and Ar2, it replaces the corresponding number of R5.

[0094] Preferably, one, two, three, four or more of R5 are selected from Si(R4)3.

[0095] More preferably, one or both of the R5 in Ar1 are selected from Si(R4)3.

[0096] More preferably, one or both of the R5 in Ar2 are selected from Si(R4)3.

[0097] More preferably, one or two of the R5 atoms in Ar1 and zero, one or two of the R5 atoms in Ar2 are selected from Si(R4)3. Alternatively, zero, one or two of the R5 atoms in Ar1 and one or two of the R5 atoms in Ar2 are selected from Si(R4)3.

[0098] Preferably, L0, L1, and L2, whether the same or different, are selected from single bonds or any of the structures shown below.

[0099]

[0100] The u that is the same or different is selected from CH or N;

[0101] The E is selected from any one of O, S, C(Rc)2, and N(Rd);

[0102] The Rc is the same as or different from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C25 heteroaryl, and substituted or unsubstituted silyl. The Rc can be directly connected to Ar1 and / or Ar2 and / or x.

[0103] The Rd is selected from any one of substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C12 alicyclic groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C25 heteroaryl groups, and substituted or unsubstituted silyl groups. The Rb can be directly connected to Ar1 and / or Ar2 and / or x.

[0104] The R6 may be the same as or different from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C25 heteroaryl, or substituted or unsubstituted silyl.

[0105] The m1 is selected from 1, 2, 3 or 4; the m2 is selected from 1, 2, 3, 4, 5 or 6; the m3 is selected from 1, 2, 3, 4, 5, 6, 7 or 8; the m4 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the m5 is selected from 1, 2 or 3; the m6 is selected from 1 or 2; the m7 is selected from 1, 2, 3, 4 or 5; when there are two or more R6, the two or more R6 are the same or different from each other, or adjacent R6 are connected to each other to form a substituted or unsubstituted ring.

[0106] Preferably, L0, L1, and L2, whether the same or different, are selected from single bonds or any of the structures shown below.

[0107]

[0108] The E is selected from any one of O, S, C(Rc)2, and N(Rd);

[0109] The Rc that is the same or different is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, and Si(R4)3, and the Rc can be directly connected to Ar1 and / or Ar2 and / or x;

[0110] The Rc may be replaced by one or more substituents selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, phenyl, biphenyl, deuterated phenyl, pentafluorophenyl, naphthyl, Si(R4)3; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

[0111] The Rd is selected from any one of methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, and Si(R4)3, and the Rd can be directly connected to Ar1 and / or Ar2 and / or x;

[0112] The Rd may be replaced by one or more substituents selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, phenyl, biphenyl, deuterated phenyl, pentafluorophenyl, naphthyl, Si(R4)3; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

[0113] The R6 that is the same or different is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, and Si(R4)3;

[0114] The R6 may be replaced by one or more substituents selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, phenyl, biphenyl, deuterated phenyl, pentafluorophenyl, naphthyl, Si(R4)3; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

[0115] The m1 is selected from 1, 2, 3, or 4; the m2 is selected from 1, 2, 3, 4, 5, or 6; the m3 is selected from 1, 2, 3, 4, 5, 6, 7, or 8; the m4 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; the m5 is selected from 1, 2, or 3; the m6 is selected from 1 or 2; the m7 is selected from 1, 2, 3, 4, or 5; the m8 is selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; the m9 is selected from 1, 2, 3, 4, 5, 6, or 7; when there are two or more R6s, the two or more R6s are the same as or different from each other, or adjacent R6s are connected to each other to form substituted or unsubstituted rings.

[0116] Preferably, when Si(R4)3 is substituted on L0, L1, and L2, it replaces the corresponding number of R6.

[0117] Preferably, one, two, three, four or more of R6 are selected from Si(R4)3.

[0118] More preferably, one or both of R6 are selected from Si(R4)3.

[0119] Preferably, the R3 is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, and Si(R4)3, or adjacent R3s are connected to each other to form substituted or unsubstituted rings; when there are two or more R3s, the two or more R3s are the same or different from each other;

[0120] The R3 may be replaced by one or more substituents selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, phenyl, biphenyl, deuterated phenyl, pentafluorophenyl, naphthyl, Si(R4)3; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

[0121] Preferably, the bicarbazole compound contains one, two, three, four or more Si(R4)3.

[0122] Preferably, the bicarbazole compound contains one, two, three, or four Si(R4)3.

[0123] Preferably, the bicarbazole compound is selected from any one of the structures shown below.

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153] This invention also provides a method for preparing bicarbazole compounds, but the preparation method of this invention is not limited thereto. The core structure of Formula 1 can be prepared by the reaction route shown below:

[0154]

[0155] Preparation of chemical formula 1-1:

[0156]

[0157] Preparation of chemical formulas 1-2:

[0158]

[0159] The Xa that is the same or different is selected from any one of I, Br, and Cl;

[0160] The above-mentioned substituents can be bonded by methods known in the art, and the type and position or number of substituents can be changed according to techniques known in the art.

[0161] The present invention provides an organic electroluminescent device comprising an anode, a cathode, and one or more organic layers disposed between or outside the anode and cathode, the organic layers comprising one or more of the bicarbazole compounds described in the present invention.

[0162] Preferably, the organic layer of the present invention includes a capping layer, which contains one or a combination of at least two of the bicarbazole compounds of the present invention.

[0163] The organic layer described in this invention may further include a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron injection layer, an electron transport layer, a hole blocking layer, an encapsulation layer, etc. However, the structure of the organic electroluminescent device of this invention is not limited to the above structure. If necessary, multiple organic layers can be omitted or simultaneously included, and organic layers with the same function can be made into a stacked structure of two or more layers.

[0164] The organic electroluminescent device of the present invention preferably has the following structure:

[0165] Substrate / Anode / Hole transport layer / Light emission layer / Electron transport layer / Cathode / Cover layer;

[0166] Substrate / Anode / Hole injection layer / Hole transport layer / Light emission layer / Electron transport layer / Cathode / Capping layer;

[0167] Substrate / Anode / Hole transport layer / Light emission layer / Electron transport layer / Electron injection layer / Cathode / Capping layer;

[0168] Substrate / Anode / Hole injection layer / Hole transport layer / Light emission layer / Electron transport layer / Electron injection layer / Cathode / Capping layer;

[0169] Substrate / Anode / Hole injection layer / Hole transport layer / Light emission layer / Hole blocking layer / Electron transport layer / Electron injection layer / Cathode / Capping layer;

[0170] Substrate / Anode / Hole injection layer / Hole transport layer / Electron blocking layer / Light emitting layer / Hole blocking layer / Electron transport layer / Electron injection layer / Cathode / Capping layer;

[0171] Substrate / Anode / Hole injection layer / Hole transport layer / Light emission auxiliary layer / Light emission layer / Hole blocking layer / Electron transport layer / Electron injection layer / Cathode / Capping layer;

[0172] However, the structure of organic electroluminescent devices is not limited to this. The organic electroluminescent devices described in this invention can be selected and combined according to device parameter requirements and material properties. Some organic layers can be added or omitted, and organic layers with the same function can be made into a stacked structure of two or more layers.

[0173] The organic electroluminescent device of the present invention is typically formed on a substrate. The substrate can be any material that remains unchanged when forming electrodes or organic layers, such as glass, plastic, polymer films, silicon, etc.

[0174] In the organic electroluminescent device of the present invention, the anode material is preferably a high work function material that can promote hole injection into the organic layer. Specific examples of anode materials that can be used in the present invention may include: metals, such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides, such as ITO-Ag-ITO; conductive polymers, such as poly(3-methylthiophene), polypyrrole, polyaniline, poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), etc., but are not limited thereto.

[0175] In the organic electroluminescent device of the present invention, the hole injection material is preferably a material with good hole-accepting ability. Specific examples of hole injection materials that can be used in the present invention may include: metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, and titanium oxide; phthalocyanine compounds; benzidine compounds; phenazine compounds; etc., such as copper phthalocyanine (CuPc), titanium phthalocyanine, N,N'-diphenyl-N,N'-di-[4-(N,N-diphenylamine)phenyl]benzidine (NPNPB), N,N,N',N'-tetra(4-methoxyphenyl)benzidine... Aniline (MeO-TPD), diquinoxolino[2,3-a:2',3'-c]phenazine (HATNA), 4,4',4”-tris[2-naphthylphenylamino]triphenylamine (2T-NATA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HAT-CN), 4,4',4”-tris(N,N-diphenylamino)triphenylamine (TDATA), etc., but not limited to these.

[0176] In the organic electroluminescent device of the present invention, the hole transport material is preferably a material with excellent hole transport performance and a HOMO energy level that matches the corresponding anode material. Specific examples of hole transport materials that can be used in this invention may include diphenylamine compounds, triphenylamine compounds, fluorene compounds, and carbazole compounds, such as N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N,N'-di(naphthyl-1-yl)-N,N'-di(phenyl)-2,2'-dimethylbenzidine (α-NPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), 4-[1-[4-[di(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC), etc., but are not limited thereto.

[0177] In the organic electroluminescent device of the present invention, the light-emitting auxiliary layer is preferably made of a material with good hole transport performance and electron blocking performance. Specific examples of luminescent auxiliary materials that can be used in this invention may include materials such as triarylamine derivatives, spirofluorene derivatives, and furan derivatives, such as TPD, NPB, N4,N4-bis([1,1'-biphenyl]-4-yl)-N4'-phenylN4'-[1,1':4',1”-terphenyl]-4-yl-[1,1'-biphenyl]-4,4'-diamine, N-([1,1'-diphenyl]-4-yl)-N-(9,9-dimethyl-9H-furan-2-yl)-9,9'-spirodifluorene-2-amine, N,N-bis([1,1'-biphenyl]-4-yl)-3'-(dibenzo[b,d]furan-4-yl)-[1,1'-biphenyl]-4-amine, etc., but are not limited thereto.

[0178] In the organic electroluminescent device of the present invention, the light-emitting layer material includes a host material and a dopant material. The host material can be selected from 4,4'-bis(9-carbazole)biphenyl (CBP), 9,10-bis(2-naphthyl)anthracene (ADN), 4,4-bis(9-carbazole)biphenyl (CPB), 9,9'-(1,3-phenyl)bis-9H-carbazole (mCP), 4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA), 9,10-bis(1-naphthyl)anthracene (α-ADN), N,N'-bis-(1- Naphthyl)-N,N'-diphenyl-[1,1':4',1”:4”,1”'-tetraphenyl]-4,4”'-diamino (4PNPB), 1,3,5-tris(9-carbazole)benzene (TCP), etc., but not limited thereto. Preferably, the main material of the light-emitting layer of the present invention is selected from 9,10-bis(2-naphthyl)anthracene (ADN), 9,9'-(1,3-phenyl)bis-9H-carbazole (mCP), 4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA), 9,10-bis(1-naphthyl)anthracene (α-AND), etc. The doping material of the light-emitting layer can be selected from (6-(4-(diphenylamino(phenyl)-N,N-diphenylpyrene-1-amine)(DPAP-DPPA), 2,5,8,11-tetra-tert-butylperylene (TBPe), 4,4'-bis[4-(diphenylamino)styryl]biphenyl (BDAVBi), 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (DPAVBi), bis(2-hydroxyphenylpyridine)beryllium (Bepp2), bis(4,6-difluorophenylpyridine-C2,N)pyridinecarboxyiridium (FIrpic), tris(2-phenylpyridine)iridium (Ir(ppy)3), bis(2-phenylpyridine)iridium acetylacetonate (Ir(ppy)2(acac)), 9,10-bis[N-(p-tolyl)aniline] Anthracene (TPA), 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), tris[1-phenylisoquinoline-C2,N]iridium(III)(Ir(piq)3), bis(1-phenylisoquinoline)(acetylacetone)iridium (Ir(piq)2(acac)), etc., but not limited thereto. Preferably, the luminescent layer guest of the present invention is selected from 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe), 9,10-bis[N-(p-tolyl)aniline]anthracene (TPA), 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), etc.

[0179] The optimal doping ratio of the light-emitting layer host material and the light-emitting layer dopant material varies depending on the material used. Typically, the doping ratio of the light-emitting layer dopant material is 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

[0180] In the organic electroluminescent device of the present invention, the hole blocking material has strong hole blocking ability and suitable HOMO and LUMO energy levels. Specific examples of hole blocking materials that can be used in the present invention may include imidazole, triazole, phenanthroline derivatives, etc., such as 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), bis(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum(III) (BAlq), etc., but are not limited thereto.

[0181] In the organic electroluminescent device of the present invention, the electron transport material is preferably a material with strong electron-withdrawing ability and low HOMO and LUMO energy levels. Specific examples of electron transport materials that can be used in the present invention may include imidazole, triazole, phenanthroline derivatives, quinoline, etc., such as 2,9-(dimethyl)-4,7-biphenyl-1,10-o-phenanthroline (BCP), 1,3,5-tris[(3-pyridyl)-phenyl]benzene (TmPyPB), 4,4'-diphenyl... (4,6-Diphenyl-1,3,5-triazinyl)biphenyl (BTB), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 2-(naphthyl-2-yl)-4,7-(diphenyl)-1,10-o-phenanthroline (HNBphen), 8-hydroxyquinoline-lithium, etc. (LiQ), etc., but not limited to these.

[0182] In the organic electroluminescent device of the present invention, the electron injection material is preferably a material with a small potential barrier difference between itself and the adjacent organic transport material or host material, and simultaneously has the effect of injecting electrons from the cathode. Examples of electron injection materials that can be used in the present invention include, but are not limited to, alkali metal salts (such as LiF, CsF), alkaline earth metal salts (such as MgF2), and metal oxides (such as Al2O3, MoO3).

[0183] In the organic electroluminescent device of the present invention, the cathode material is preferably a low work function material that can promote electron injection into the organic layer. Specific examples of cathode materials that can be used in the present invention may include: metals such as aluminum, magnesium, silver, indium, tin, titanium, and their alloys; multilayer metal materials such as LiF / Al, Mg / Ag, Li / Al, LiO2 / Al, BaF2 / Al, etc., but are not limited thereto.

[0184] In the organic electroluminescent device of the present invention, the capping layer material is preferably a material that improves optical coupling. Specific examples of capping layer materials that can be used in the present invention may include arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, and bicarbazole compounds described in the present invention, etc., preferably bicarbazole compounds described in the present invention. The capping layer can be formed simultaneously on the outside of the anode and the outside of the cathode, or it can be disposed on the outside of the anode or the outside of the cathode. Preferably, the capping layer described in the present invention is disposed on the outside of the cathode.

[0185] The present invention does not impose any special restrictions on the thickness of each organic layer of the organic electroluminescent device; thicknesses commonly used in the field can be adopted.

[0186] The organic electroluminescent device of the present invention can be made using any one of the following methods: vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray coating, slot coating, and dip coating. In the present invention, vacuum evaporation is preferred.

[0187] The organic electroluminescent device described in this invention can be widely used in panel displays, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photosensitive materials or organic thin-film transistors, signs, signal lights and other fields.

[0188] The invention is explained in more detail through the following examples, but is not intended to limit the invention. Based on this description, those skilled in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the entire scope disclosed without inventive effort.

[0189] Preparation and characterization of compounds

[0190] Description of raw materials, reagents, and characterization equipment:

[0191] The present invention does not impose any particular restrictions on the source of raw materials and reagents used in the following embodiments, which can be commercially available products or prepared using preparation methods well known to those skilled in the art.

[0192] Mass spectrometry was performed using a Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer, with chloroform as the solvent.

[0193] Elemental analysis was performed using a Vario EL cube organic elemental analyzer from Elementar GmbH, Germany, with sample masses ranging from 5 to 10 mg.

[0194] Synthesis Example 1: Preparation of Intermediate A-54

[0195]

[0196] Preparation of intermediate c-54:

[0197] Under nitrogen protection, intermediate a-54 (29.12 g, 100 mmol), toluene (500 mL), b-54 (22.18 g, 110 mmol), Pd2(dba)3 (0.92 g, 1.00 mmol), BINAP (1.89 g, 3.00 mmol), and sodium tert-butoxide (19.22 g, 200 mmol) were added to a reaction flask, stirred to dissolve, and refluxed for 7.5 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the organic solvent was removed by vacuum distillation of the filtrate. The obtained solid was recrystallized from methanol to give intermediate c-54 (32.13 g, yield 78%) with an HPLC purity ≥99.81%. Mass spectrometry m / z: 411.0564 (theoretical value: 411.0597).

[0198] Preparation of intermediate A-54:

[0199] Under nitrogen protection, C-54 (30.89 g, 75.00 mmol), pinacol diborate (19.05 g, 75.00 mmol), potassium acetate (16.19 g, 165.00 mmol), PdCl2 (dppf) (0.54 g, 0.75 mmol), and 1,4-dioxane (250 mL) were added to a reaction flask. The mixture was stirred and refluxed for 6 hours. After the reaction was complete and cooled to room temperature, the filter cake was obtained by suction filtration and washed with ethanol. Finally, the filter cake was recrystallized from toluene to obtain intermediate A-54 (31.34 g, 83%); HPLC purity ≥99.85%. Mass spectrometry m / z: 503.1833 (theoretical value: 503.1839).

[0200] By substituting the raw materials accordingly and following the preparation method of Synthesis Example 1, the following intermediates can be prepared. The specific details of the raw materials and intermediates are shown in the table below:

[0201]

[0202]

[0203] Synthesis Example 2: Preparation of Intermediate B-2

[0204]

[0205] Preparation of intermediate g-2

[0206] Under an argon atmosphere, 700 mL of dehydrated tetrahydrofuran and 46.62 g (200.00 mmol) of starting material d-2 were added to a reaction flask. The mixture was cooled to -78 °C, and a 2.5 M n-butyllithium solution in n-hexane (100 mL, 250 mmol) was slowly added dropwise, while the mixture was stirred for 2.5 hours. Then, 66.67 g (200.00 mol) of starting material e-2 dissolved in 650 mL of tetrahydrofuran was added to the mixture, and the mixture was stirred for 5.5 hours. Afterward, the mixture was kept at room temperature and stirred overnight. Then, 300 mL of 1 M hydrochloric acid was added to the mixture, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous MgSO4, filtered, and the filtrate was concentrated under reduced pressure to remove the solvent, yielding an oily substance. The obtained oily substance, 250 mL of glacial acetic acid, and 4 mL of concentrated hydrochloric acid were added to a reaction flask. The mixture was heated to reflux for 6 hours. After the reaction was complete, distilled water was added to the mixture, followed by extraction with ethyl acetate. The organic phase was collected, washed with saturated sodium bicarbonate aqueous solution and saturated brine, dried over anhydrous MgSO4, filtered, and the filtrate was concentrated under reduced pressure to obtain an oily substance. Purification was performed by column chromatography (using n-hexane:toluene = 10:2 as eluent) to finally obtain intermediate g-2 (72.30 g, yield 77%), with an HPLC purity ≥99.21%. Mass spectrometry m / z: 469.0976 (theoretical value: 468.0909).

[0207] Preparation of intermediate h-2:

[0208] Under an argon atmosphere, intermediate g-2 (70.42 g, 150.00 mmol) and 500 mL of dehydrated tetrahydrofuran were added to a reaction flask. The reaction solution was then cooled to -78 °C, and 75 mL (120 mmol) of a 1.6 M n-butyllithium solution in n-hexane was slowly added dropwise. After stirring at -78 °C for 4 hours, 75 mL of a dehydrated tetrahydrofuran solution of trimethyl borate (39.49 g, 380.00 mmol) was added dropwise. After stirring for 2.5 hours, the mixture was slowly heated to room temperature. 400 mL of 3 M hydrochloric acid was added, and after stirring for 4 hours, distilled water was added. The mixture was then extracted with dichloromethane, and the organic phase was collected. The organic phase was dried over anhydrous MgSO4, and after removing the solvent by vacuum distillation, it was recrystallized from dichloromethane to give intermediate h-2 (48.22 g, yield 74%) with an HPLC purity ≥99.61%. Mass spectrometry m / z: 434.1810 (theoretical value: 434.1873).

[0209] Preparation of intermediate j-2:

[0210] Intermediate h-2 (43.44 g, 100.00 mmol), starting material i-2 (29.79 g, 100.00 mmol), dried Cu(OAc)₂·H₂O (1.82 g, 10.00 mmol), and n-decanoic acid (3.45 g, 20.00 mmol) were added to a reaction flask protected with CaCl₂. Then, DBU (18.27 g, 120.00 mmol) and anhydrous toluene (350 mL) were added sequentially to the reaction mixture, and the mixture was stirred at room temperature for 26 hours. After the reaction was complete, the reaction mixture was diluted with water and extracted with ethyl acetate. The combined ethyl acetate fraction was washed with brine, dried over anhydrous Na₂SO₄, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by column chromatography (n-hexane:ethyl acetate = 95:5 as eluent) to give intermediate j-2 (48.74 g, yield 71%) with an HPLC purity ≥99.37%. Mass spectrometry m / z: 685.0244 (theoretical value: 685.0297).

[0211] Preparation of intermediate B-2:

[0212] Intermediate J-2 (48.06 g, 70.00 mmol), anhydrous toluene (350 mL), Pd(OAc)2 (0.79 g, 3.5 mmol), and DBU (60.90 g, 400.00 mmol) were successively added to a reaction flask. The reaction mixture was degassed with argon and heated at 100 °C for 10 hours. After the reaction was complete, the mixture was cooled to room temperature, diluted with water, and extracted with ethyl acetate. The combined ethyl acetate fraction was washed with brine solution, dried over anhydrous Na2SO4, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by column chromatography (using n-hexane:ethyl acetate = 80:20 as eluent) to give intermediate B-2 (29.33 g, 75% yield) with an HPLC purity ≥99.72%. Mass spectrometry m / z: 557.1121 (theoretical value: 557.1174).

[0213] By substituting the raw materials accordingly and following the preparation method of Synthesis Example 2, the following intermediates can be prepared. The specific details of the raw materials and intermediates are shown in the table below:

[0214]

[0215]

[0216] Synthesis Example 3: Preparation of Intermediate C-2

[0217]

[0218] Under argon protection, A-2 (22.32 g, 52 mmol), intermediate B-2 (27.93 g, 50 mmol), Pd(PPh3)4 (0.58 g, 0.50 mmol), potassium acetate (10.80 g, 110 mmol), toluene (300 mL), ethanol (100 mL), and water (100 mL) were added sequentially to a reaction flask. The mixture was stirred and refluxed for 5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, and washed with ethanol. Finally, the filter cake was recrystallized from toluene / ethanol at a ratio of 10:1 to obtain intermediate C-2 (31.52 g, yield 79%) with an HPLC purity ≥99.65%. Mass spectrometry m / z: 797.3227 (theoretical value: 797.3226).

[0219] By substituting the raw materials or intermediates accordingly, and following the preparation method of Synthesis Example 3, the following intermediates can be prepared. The specific details of the raw materials and intermediates are shown in the table below:

[0220]

[0221]

[0222]

[0223]

[0224]

[0225] Synthesis Example 4: Preparation of Compound 2

[0226]

[0227] Under nitrogen protection, intermediate C-2 (19.95 g, 25.00 mmol), toluene (175 mL), D-2 (6.83 g, 25.00 mmol), Pd2(dba)3 (0.27 g, 0.30 mmol), BINAP (0.37 g, 0.60 mmol), and sodium tert-butoxide (7.21 g, 75.00 mmol) were added to a reaction flask, stirred to dissolve, and refluxed for 7.5 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the organic solvent was removed by vacuum distillation. The obtained solid was recrystallized from methanol to give compound 2 (16.84 g), with an HPLC purity ≥99.94%. Mass spectrometry m / z: 989.4152 (theoretical value: 989.4165). Theoretical elemental content (%) C 72 H 55 N3Si: C, 87.32; H, 5.60; N, 4.24. Measured elemental content (%): C, 87.35; H, 5.62; N, 4.23.

[0228] Synthesis Example 5: Preparation of Compound 8

[0229]

[0230] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-8 and D-8, respectively, to obtain compound 8 (16.39 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 922.3759 (theoretical value: 922.3743). Theoretical elemental content (%) C 68 H 50 N₂Si: C, 88.46; H, 5.46; N, 3.03. Measured elemental content (%): C, 88.48; H, 5.43; N, 3.02.

[0231] Synthesis Example 6: Preparation of Compound 28

[0232]

[0233] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-8 and D-28, respectively, to obtain compound 28 (16.77 g); HPLC purity ≥ 99.93%. Mass spectrometry m / z: 1000.3988 (theoretical value: 1000.3961). Theoretical elemental content (%) C 72 H 52 N4Si: C, 86.37; H, 5.23; N, 5.60. Measured elemental content (%): C, 86.38; H, 5.26; N, 5.62.

[0234] Synthesis Example 7: Preparation of Compound 54

[0235]

[0236] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-54 and D-54, respectively, to obtain compound 54 (17.67 g); HPLC purity ≥ 99.91%. Mass spectrometry m / z: 1086.3232 (theoretical value: 1086.3246). Theoretical elemental content (%) C 74 H 50 N4S2Si: C, 81.73; H, 4.63; N, 5.15. Measured elemental content (%): C, 81.77; H, 4.61; N, 5.16.

[0237] Synthesis Example 8: Preparation of Compound 130

[0238]

[0239] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-130 and D-130, respectively, to obtain compound 130 (15.94 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 872.3576 (theoretical value: 872.3587). Theoretical elemental content (%) C 64 H 48 N₂Si: C, 88.03; H, 5.54; N, 3.21. Measured elemental content (%): C, 88.05; H, 5.53; N, 3.24.

[0240] Synthesis Example 9: Preparation of Compound 133

[0241]

[0242] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-133 and D-133, respectively, to obtain compound 133 (15.14 g); HPLC purity ≥ 99.99%. Mass spectrometry m / z: 806.3528 (theoretical value: 806.3513). Theoretical elemental content (%) C 56 H 50 N₂Si₂: C, 83.33; H, 6.24; N, 3.47. Measured elemental content (%): C, 83.31; H, 6.25; N, 3.46.

[0243] Synthesis Example 10: Preparation of Compound 143

[0244]

[0245] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-143 and D-133, respectively, to obtain compound 143 (15.75 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 874.2819 (theoretical value: 874.2803). Theoretical elemental content (%) C 57 H 39 F5N2Si: C, 78.24; H, 4.49; N, 3.20. Measured elemental content (%): C, 78.26; H, 4.45; N, 3.21.

[0246] Synthetic Example 11: Preparation of Compound 158

[0247]

[0248] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-133 and D-158, respectively, to obtain compound 158 (15.86 g); HPLC purity ≥ 99.98%. Mass spectrometry m / z: 868.4222 (theoretical value: 868.4213). Theoretical elemental content (%) C 63 H 56 N₂Si: C, 87.05; H, 6.49; N, 3.22. Measured elemental content (%): C, 87.08; H, 6.45; N, 3.25.

[0249] Synthesis Example 12: Preparation of Compound 161

[0250]

[0251] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-161 and D-133, respectively, to obtain compound 161 (15.21 g); HPLC purity ≥ 99.99%. Mass spectrometry m / z: 810.3447 (theoretical value: 810.3430). Theoretical elemental content (%) C 59 H 46 N₂Si: C, 87.37; H, 5.72; N, 3.45. Measured elemental content (%): C, 87.38; H, 5.75; N, 3.43.

[0252] Synthetic Example 13: Preparation of Compound 181

[0253]

[0254] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-133 and D-181, respectively, to obtain compound 181 (15.17 g); HPLC purity ≥ 99.98%. Mass spectrometry m / z: 819.3983 (theoretical value: 819.3995). Theoretical elemental content (%) C 59 H 37 D9N2Si: C, 86.40; H, 6.76; N, 3.42. Measured elemental content (%): C, 86.42; H, 6.73; N, 3.41.

[0255] Synthesis Example 14: Preparation of Compound 201

[0256]

[0257] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-201 and D-201, respectively, to obtain compound 201 (15.21 g); HPLC purity ≥ 99.99%. Mass spectrometry m / z: 810.3443 (theoretical value: 810.3430). Theoretical elemental content (%) C 59 H 46 N₂Si: C, 87.37; H, 5.72; N, 3.45. Measured elemental content (%): C, 87.38; H, 5.75; N, 3.47.

[0258] Synthesis Example 15: Preparation of Compound 253

[0259]

[0260] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-133 and D-253, respectively, to obtain compound 253 (16.04 g); HPLC purity ≥99.97%. Mass spectrometry m / z: 878.3321 (theoretical value: 878.3304). Theoretical elemental content (%) C 60 H 45 F3N2Si: C, 81.98; H, 5.16; N, 3.19. Measured elemental content (%): C, 81.96; H, 5.19; N, 3.15.

[0261] Synthesis Example 16: Preparation of Compound 257

[0262]

[0263] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-161 and D-257, respectively, to obtain compound 257 (15.97 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 886.3761 (theoretical value: 886.3743). Theoretical elemental content (%) C 65 H 50 N₂Si: C, 88.00; H, 5.68; N, 3.16. Measured elemental content (%): C, 88.05; H, 5.64; N, 3.18.

[0264] Synthesis Example 17: Preparation of Compound 296

[0265]

[0266] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-161 and D-296, respectively, to obtain compound 296 (16.95 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 996.3916 (theoretical value: 996.3900). Theoretical elemental content (%) C 74 H 52 N₂Si: C, 89.12; H, 5.26; N, 2.81. Measured elemental content (%): C, 89.13; H, 5.28; N, 2.82.

[0267] Synthesis Example 18: Preparation of Compound 305

[0268]

[0269] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-305 and D-133, respectively, to obtain compound 305 (17.14 g); HPLC purity ≥ 99.95%. Mass spectrometry m / z: 992.3996 (theoretical value: 992.3982). Theoretical elemental content (%) C 71 H 56 N₂Si₂: C, 85.84; H, 5.68; N, 2.82. Measured elemental content (%): C, 85.86; H, 5.65; N, 2.84.

[0270] Synthetic Example 19: Preparation of Compound 315

[0271]

[0272] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-315 and D-315, respectively, to obtain compound 315 (15.24 g); HPLC purity ≥ 99.99%. Mass spectrometry m / z: 801.3571 (theoretical value: 801.3588). Theoretical elemental content (%) C 58 H 39 D5N2Si: C, 86.85; H, 6.16; N, 3.49. Measured elemental content (%): C, 86.86; H, 6.19; N, 3.47.

[0273] Synthesis Example 20: Preparation of Compound 347

[0274]

[0275] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-347 and D-133, respectively, to obtain compound 347 (15.86 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 880.4078 (theoretical value: 880.4089). Theoretical elemental content (%) C 64 H 40 D8N2Si: C, 87.23; H, 6.40; N, 3.18. Measured elemental content (%): C, 87.25; H, 6.41; N, 3.16.

[0276] Synthesis Example 21: Preparation of Compound 361

[0277]

[0278] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-315 and D-130, respectively, to obtain compound 361 (15.94 g); HPLC purity ≥ 99.98%. Mass spectrometry m / z: 872.3572 (theoretical value: 872.3587). Theoretical elemental content (%) C 64 H 48 N₂Si: C, 88.03; H, 5.54; N, 3.21. Measured elemental content (%): C, 88.07; H, 5.53; N, 3.22.

[0279] Synthesis Example 22: Preparation of Compound 375

[0280]

[0281] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-375 and D-130, respectively, to obtain compound 375 (16.75 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 984.4825 (theoretical value: 984.4839). Theoretical elemental content (%) C 72 H 64 N₂Si: C, 87.76; H, 6.55; N, 2.84. Measured elemental content (%): C, 87.78; H, 6.58; N, 2.83.

[0282] Synthesis Example 23: Preparation of Compound 390

[0283]

[0284] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-390 and D-390, respectively, to obtain compound 390 (16.93 g); HPLC purity ≥ 99.95%. Mass spectrometry m / z: 980.4938 (theoretical value: 980.4921). Theoretical elemental content (%) C 69 H 68 N₂Si₂: C, 84.44; H, 6.98; N, 2.85. Measured elemental content (%): C, 84.46; H, 6.95; N, 2.83.

[0285] Synthesis Example 24: Preparation of Compound 437

[0286]

[0287] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-437 and D-257, respectively, to obtain compound 437 (16.85 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 948.3913 (theoretical value: 948.3900). Theoretical elemental content (%) C 70 H 52 N₂Si: C, 88.57; H, 5.52; N, 2.95. Measured elemental content (%): C, 88.55; H, 5.56; N, 2.96.

[0288] Synthesis Example 25: Preparation of Compound 454

[0289]

[0290] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-454 and D-454, respectively, to obtain compound 454 (16.70 g); HPLC purity ≥ 99.95%. Mass spectrometry m / z: 953.4228 (theoretical value: 953.4214). Theoretical elemental content (%) C 70 H 47 D5N2Si: C, 88.10; H, 6.02; N, 2.94. Measured elemental content (%): C, 88.11; H, 6.06; N, 2.92.

[0291] Synthesis Example 26: Preparation of Compound 495

[0292]

[0293] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-495 and D-495, respectively, to obtain compound 495 (16.74 g); HPLC purity ≥ 99.92%. Mass spectrometry m / z: 1013.3815 (theoretical value: 1013.3801). Theoretical elemental content (%) C 73 H 51 N3OSi: C, 86.44; H, 5.07; N, 4.14. Measured elemental content (%): C, 86.46; H, 5.04; N, 4.11.

[0294] Synthesis Example 27: Preparation of Compound 496

[0295]

[0296] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-496 and D-133, respectively, to obtain compound 496 (15.25 g); HPLC purity ≥ 99.99%. Mass spectrometry m / z: 812.3348 (theoretical value: 812.3335). Theoretical elemental content (%) C 57 H 44 N4Si: C, 84.20; H, 5.45; N, 6.89. Measured elemental content (%): C, 84.23; H, 5.44; N, 6.84.

[0297] Synthesis Example 28: Preparation of Compound 499

[0298]

[0299] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-499 and D-133, respectively, to obtain compound 499 (15.70 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 871.4072 (theoretical value: 871.4088). Theoretical elemental content (%) C 61 H 41 D7N4Si: C, 84.00; H, 6.35; N, 6.42. Measured elemental content (%): C, 84.02; H, 6.31; N, 6.46.

[0300] Synthesis Example 29: Preparation of Compound 521

[0301]

[0302] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-521 and D-257, respectively, to obtain compound 521 (15.72 g); HPLC purity ≥ 99.98%. Mass spectrometry m / z: 860.3573 (theoretical value: 860.3587). Theoretical elemental content (%) C 63 H 48 N₂Si: C, 87.87; H, 5.62; N, 3.25. Measured elemental content (%): C, 87.88; H, 5.66; N, 3.23.

[0303] Synthesis Example 30: Preparation of Compound 526

[0304]

[0305] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-526 and D-526, respectively, to obtain compound 526 (17.05 g); HPLC purity ≥ 99.92%. Mass spectrometry m / z: 1032.4789 (theoretical value: 1032.4777). Theoretical elemental content (%) C 76 H 56 D4N2Si: C, 88.33; H, 6.24; N, 2.71. Measured elemental content (%): C, 88.35; H, 6.21; N, 2.74.

[0306] Synthesis Example 31: Preparation of Compound 527

[0307]

[0308] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-527 and D-257, respectively, to obtain compound 527 (16.55 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 972.3912 (theoretical value: 972.3900). Theoretical elemental content (%) C 72 H 52 N₂Si: C, 88.85; H, 5.39; N, 2.88. Measured elemental content (%): C, 88.86; H, 5.34; N, 2.86.

[0309] Synthesis Example 32: Preparation of Compound 534

[0310]

[0311] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-534 and D-133, respectively, to obtain compound 534 (16.67 g); HPLC purity ≥ 99.95%. Mass spectrometry m / z: 965.3931 (theoretical value: 965.3914). Theoretical elemental content (%) C 68 H 51 N5Si: C, 84.53; H, 5.32; N, 7.25. Measured elemental content (%): C, 84.54; H, 5.35; N, 7.22.

[0312] Synthesis Example 33: Preparation of Compound 550

[0313]

[0314] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-550 and D-257, respectively, to obtain compound 550 (16.46 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 926.4042 (theoretical value: 926.4056). Theoretical elemental content (%) C 68 H 54 N₂Si: C, 88.08; H, 5.87; N, 3.02. Measured elemental content (%): C, 88.06; H, 5.88; N, 3.05.

[0315] Synthesis Example 34: Preparation of Compound 564

[0316]

[0317] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-564 and D-257, respectively, to obtain compound 564 (16.83 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 989.3819 (theoretical value: 989.3801). Theoretical elemental content (%) C 71 H 51 N3OSi: C, 86.11; H, 5.19; N, 4.24. Measured elemental content (%): C, 86.15; H, 5.18; N, 4.26.

[0318] Synthesis Example 35: Preparation of Compound 574

[0319]

[0320] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-574 and D-133, respectively, to obtain compound 574 (16.69 g); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 926.3823 (theoretical value: 926.3805). Theoretical elemental content (%) C 66 H 50 N4Si: C, 85.49; H, 5.44; N, 6.04. Measured elemental content (%): C, 85.48; H, 5.47; N, 6.05.

[0321] Synthesis Example 36: Preparation of Compound 600

[0322]

[0323] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-201 and D-600, respectively, to obtain compound 600 (16.58 g); HPLC purity ≥ 99.95%. Mass spectrometry m / z: 960.3916 (theoretical value: 960.3900). Theoretical elemental content (%) C 71 H 52 N₂Si: C, 88.71; H, 5.45; N, 2.91. Measured elemental content (%): C, 88.73; H, 5.46; N, 2.92.

[0324] Synthesis Example 37: Preparation of Compound 607

[0325]

[0326] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-315 and D-607, respectively, to obtain compound 607 (16.38 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 962.3673 (theoretical value: 962.3692). Theoretical elemental content (%) C 70 H 50 N₂OSi: C, 87.28; H, 5.23; N, 2.91. Measured elemental content (%): C, 87.26; H, 5.24; N, 2.93.

[0327] Synthesis Example 38: Preparation of Compound 616

[0328]

[0329] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-616 and D-616, respectively, to obtain compound 616 (16.28 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 916.3323 (theoretical value: 916.3307). Theoretical elemental content (%) C 65 H 48 N₂SSi: C, 85.11; H, 5.27; N, 3.05. Measured elemental content (%): C, 85.12; H, 5.24; N, 3.03.

[0330] Synthesis Example 39: Preparation of Compound 628

[0331]

[0332] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-628 and D-628, respectively, to obtain compound 628 (16.68 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 980.4421 (theoretical value: 980.4402). Theoretical elemental content (%) C 72 H 44 D8N2Si: C, 88.12; H, 6.16; N, 2.85. Measured elemental content (%): C, 88.15; H, 6.14; N, 2.88.

[0333] Synthesis Example 40: Preparation of Compound 632

[0334]

[0335] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-454 and D-632, respectively, to obtain compound 632 (16.74 g); HPLC purity ≥ 99.95%. Mass spectrometry m / z: 969.4126 (theoretical value: 969.4114). Theoretical elemental content (%) C 69 H 55 N3OSi: C, 85.41; H, 5.71; N, 4.33. Measured elemental content (%): C, 85.42; H, 5.73; N, 4.36.

[0336] Synthesis Example 41: Preparation of Compound 648

[0337]

[0338] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-454 and D-648, respectively, to obtain compound 648 (16.84 g); HPLC purity ≥ 99.93%. Mass spectrometry m / z: 1004.3634 (theoretical value: 1004.3620). Theoretical elemental content (%) C 72 H 52 N₂SSi: C, 86.02; H, 5.21; N, 2.79. Measured elemental content (%): C, 86.03; H, 5.24; N, 2.78.

[0339] Synthesis Example 42: Preparation of Compound 660

[0340]

[0341] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-660 and D-130, respectively, to obtain compound 660 (16.85 g); HPLC purity ≥ 99.96%. Mass spectrometry m / z: 948.3916 (theoretical value: 948.3900). Theoretical elemental content (%) C 70 H 52 N₂Si: C, 88.57; H, 5.52; N, 2.95. Measured elemental content (%): C, 88.58; H, 5.54; N, 2.97.

[0342] Synthesis Example 43: Preparation of Compound 675

[0343]

[0344] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-675 and D-675, respectively, to obtain compound 675 (16.63 g); HPLC purity ≥ 99.94%. Mass spectrometry m / z: 977.3421 (theoretical value: 977.3438). Theoretical elemental content (%) C 69 H 47 N3O2Si: C, 84.72; H, 4.84; N, 4.30. Measured elemental content (%): C, 84.71; H, 4.85; N, 4.33.

[0345] Synthesis Example 44: Preparation of Compound 704

[0346]

[0347] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-704 and D-704, respectively, to obtain compound 704 (16.85 g); HPLC purity ≥ 99.92%. Mass spectrometry m / z: 1020.3329 (theoretical value: 1020.3318). Theoretical elemental content (%) C 70 H 48 N4OSSi: C, 82.32; H, 4.74; N, 5.49. Measured elemental content (%): C, 82.36; H, 4.73; N, 5.48.

[0348] Synthetic Example 45: Preparation of Compound 727

[0349]

[0350] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-727 and D-727, respectively, to obtain compound 727 (16.22 g); HPLC purity ≥ 99.95%. Mass spectrometry m / z: 939.3662 (theoretical value: 939.3645). Theoretical elemental content (%) C 67 H 49 N3OSi: C, 85.59; H, 5.25; N, 4.47. Measured elemental content (%): C, 85.54; H, 5.27; N, 4.46.

[0351] Synthesis Example 46: Preparation of Compound 732

[0352]

[0353] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-732 and D-130, respectively, to obtain compound 732 (16.82 g); HPLC purity ≥ 99.92%. Mass spectrometry m / z: 1018.4664 (theoretical value: 1018.4682). Theoretical elemental content (%) C 75 H 62 N₂Si: C, 88.37; H, 6.13; N, 2.75. Measured elemental content (%): C, 88.33; H, 6.16; N, 2.74.

[0354] Synthesis Example 47: Preparation of Compound 735

[0355]

[0356] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-735 and D-735, respectively, to obtain compound 735 (17.52 g); HPLC purity ≥ 99.91%. Mass spectrometry m / z: 1077.4102 (theoretical value: 1077.4114). Theoretical elemental content (%) C 78 H 55 N3OSi: C, 86.87; H, 5.14; N, 3.90. Measured elemental content (%): C, 86.88; H, 5.11; N, 3.93.

[0357] Synthesis Example 48: Preparation of Compound 762

[0358]

[0359] According to the preparation method in Synthesis Example 4, equimolar amounts of C-2 and D-2 were replaced with equimolar amounts of C-762 and D-133, respectively, to obtain compound 762 (17.06 g); HPLC purity ≥ 99.93%. Mass spectrometry m / z: 1017.4461 (theoretical value: 1017.4478). Theoretical elemental content (%) C 74 H 59 N3Si: C, 87.28; H, 5.84; N, 4.13. Measured elemental content (%): C, 87.25; H, 5.86; N, 4.15.

[0360] [Device Examples 1-45]

[0361] Device Example 1: The ITO glass substrate was ultrasonically cleaned twice with a 5% glass cleaning solution for 20 minutes each time, followed by ultrasonic cleaning twice with deionized water for 10 minutes each time. It was then ultrasonically cleaned sequentially with acetone and isoacetone for 20 minutes each, and dried at 120°C. A hole injection layer with a thickness of 15 nm was vacuum-deposited on the ITO substrate using a HI:HT-1 ratio of 97:3 (mass ratio); a hole transport layer with a thickness of 80 nm was vacuum-deposited on the hole injection layer using HT-2; a light-emitting layer with a thickness of 30 nm was vacuum-deposited on the hole transport layer using compound 2 of the present invention with a RD ratio of 95:5 (mass ratio); an electron transport layer with a thickness of 35 nm was vacuum-deposited on the light-emitting layer using ET; an electron injection layer with a thickness of 1 nm was vacuum-deposited on the electron transport layer using LiF; and an electron cathode with a thickness of 80 nm was vacuum-deposited on the electron injection layer using Al.

[0362]

[0363] Device Examples 2-45: Compounds 8, 28, 54, 130, 133, 143, 158, 161, 181, 201, 253, 257, 296, 305, 315, 347, 361, 375, 390, 437, 454, 495, 496, 499, 521, 526, 527, 534, 550, 564, 574, 600, 607, 616, 628, 632, 648, 660, 675, 704, 727, 732, 735, and 762 of the present invention were used to replace compound 2 of the present invention in Device Example 1 as the main material. Otherwise, organic electroluminescent devices were prepared using the same steps as in Device Example 1.

[0364] Comparative Examples 1 and 2: Comparative Compound 1 and Comparative Compound 2 were used to replace Compound 2 of the present invention in Device Example 1 as the main material. Otherwise, the organic electroluminescent device was prepared using the same steps as in Device Example 1.

[0365] A combined IVL testing system was used to test the luminous efficiency of electromechanical light-emitting devices (EMFs), comprising testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectral scanning luminance meter. Lifetime testing was performed using a McScience M6000 OLED lifetime testing system. The testing environment was atmospheric, at room temperature.

[0366] The luminescence characteristics of the obtained organic electroluminescent devices are shown in Table 1. Table 1 shows the luminescence characteristics of the organic electroluminescent devices prepared by the compounds prepared in the embodiments of the present invention and the comparative substances.

[0367] Table 1. Luminescence characteristics test of organic electroluminescent devices

[0368]

[0369]

[0370] As can be seen from the results in Table 1, compared with Comparative Examples 1 and 2, the devices prepared using the bicarbazole compounds described in this invention in Examples 1 to 45 have higher luminous efficiency and longer device lifetime.

[0371] [Device Examples 46-90]

[0372] Device Example 46: The ITO glass substrate was ultrasonically cleaned twice with a 5% glass cleaning solution for 20 minutes each time, and then ultrasonically cleaned twice with deionized water for 10 minutes each time. It was then ultrasonically cleaned sequentially with acetone and isoacetone for 20 minutes each time, and dried at 120°C. A hole injection layer with a mass ratio of HI:HT-1 = 98:2 (mass ratio) and a deposition thickness of 15 nm was vacuum-deposited on the ITO substrate; a hole transport layer with a mass ratio of HT-2 was vacuum-deposited on the hole injection layer for a deposition thickness of 70 nm; a light-emitting layer with a mass ratio of 2:GD = 97:3 (mass ratio) of the present invention was vacuum-deposited on the hole transport layer for a deposition thickness of 40 nm; an electron transport layer with a mass ratio of ET was vacuum-deposited on the light-emitting layer for a deposition thickness of 30 nm; an electron injection layer with a mass ratio of LiF was vacuum-deposited on the electron transport layer for a deposition thickness of 1 nm; and an electron cathode with a mass ratio of Al was vacuum-deposited on the electron injection layer for a deposition thickness of 80 nm.

[0373] Device Examples 47-90: Compound 2 of the present invention in Device Example 46 was replaced with compounds 8, 28, 54, 130, 133, 143, 158, 161, 181, 201, 253, 257, 296, 305, 315, 347, 361, 375, 390, 437, 454, 495, 496, 499, 521, 526, 527, 534, 550, 564, 574, 600, 607, 616, 628, 632, 648, 660, 675, 704, 727, 732, 735, and 762 as the main material. Otherwise, organic electroluminescent devices were prepared using the same steps as in Device Example 46.

[0374] Comparative Examples 3 and 4: Comparative Compound 1 and Comparative Compound 2 were used to replace Compound 2 of the present invention in Device Example 46 as the main material. Otherwise, the organic electroluminescent device was prepared using the same steps as Device Example 46.

[0375] A combined IVL testing system was used to test the luminous efficiency of electromechanical light-emitting devices (EMFs), comprising testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectral scanning luminance meter. Lifetime testing was performed using a McScience M6000 OLED lifetime testing system. The testing environment was atmospheric, at room temperature.

[0376] The luminescence characteristics of the obtained organic electroluminescent devices are shown in Table 2. Table 2 shows the luminescence characteristics of the organic electroluminescent devices prepared by the compounds prepared in the embodiments of the present invention and the comparative substances.

[0377] Table 2. Luminescence characteristics test of organic electroluminescent devices

[0378]

[0379]

[0380] As can be seen from the results in Table 2, compared with comparative Examples 3 and 4, the devices prepared using the bicarbazole compounds described in this invention in Examples 46-90 have higher luminous efficiency and longer device lifetime.

[0381] It should be noted that the present invention has been specifically described with reference to individual embodiments, but those skilled in the art can make various forms or details of improvements to the present invention without departing from the principles of the present invention, and these improvements also fall within the protection scope of the present invention.

Claims

1. A bicarbazole compound, characterized in that, The bicarbazole compounds have the structure shown in chemical formula 1-1. The x that are the same or different are selected from CR3 or N, wherein the x that is bonded to Ar0 or L0 is selected from C; and at most one of the four x in each six-membered ring is selected from N; The R3 is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, and Si(R4)3, or adjacent R3s are connected to each other to form substituted or unsubstituted benzene rings; when there are two or more R3s, the two or more R3s are the same or different from each other. The R3 may be replaced by one or more substituents selected from deuterium; The Ar0 is selected from any of the structures shown below. a1 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; a2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; a3 is selected from 0, 1, 2, 3, 4, 5 or 6; a5 is selected from 1, 2, 3 or 4; when there are two or more R2, the two or more R2 are the same as or different from each other; The same or different R2 is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, and Si(R4)3; The R2 may be replaced by one or more substituents selected from deuterium; The R1s, whether identical or different, are selected from any one of methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, and pyridyl. R1 can be replaced by one or more substituents R 11 When R1 is selected from methyl, ethyl, isopropyl, or tert-butyl, the substituent R... 11 The substituent R is selected from deuterium; when R1 is selected from phenyl, biphenyl, naphthyl, or pyridyl, the substituent R 11 It is selected from any one or a combination of deuterium, cyano, halogen, trifluoromethyl, methyl, isopropyl, tert-butyl, Si(R4)3; when two or more substituents are present, the two or more substituents are the same as or different from each other; The L0, L1, and L2 that are the same or different are selected from single bonds or any of the structures shown below. The R6 may be the same as or different from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1 to C6 alkyl groups; The m1 is selected from 1, 2, 3 or 4; the m2 is selected from 1, 2, 3, 4, 5 or 6; when there are two or more R6, the two or more R6 are the same as or different from each other; The Ar1 and Ar2, whether identical or different, are selected from Si(R4)3 or any of the structures shown below. The Y is selected from any one of O, S, C(Ra)2, and N(Rb); Y1 is selected from any one of O, S, and N(Rb); Y2 is selected from either O or S; The Ra is the same as or different from any one of hydrogen, deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C12 aryl; The Rb is selected from any one of substituted or unsubstituted C6~C12 aryl groups; The R 5a The same or different are selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, and Si(R4)3; The R5, whether identical or different, is selected from any one of hydrogen, deuterium, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, and phenyl. The R 5a R5 may be substituted by one or more substituents selected from deuterium; The n1 is selected from 1, 2, 3, 4, or 5; the n2 is selected from 1, 2, 3, 4, 5, 6, or 7; the n3 is selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; the n4 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; the n5 is selected from 1, 2, 3, 4, 5, or 6; the n6 is selected from 1, 2, 3, or 4; the n8 is selected from 1 or 2; the n9 is selected from 1, 2, 3, 4, 5, 6, 7, or 8; when there are two or more R... 5a At that time, two or more R 5a They may be the same as or different from each other; when there are two or more R5s, they may be the same as or different from each other. The bicarbazole compounds contain one or two Si(R4)3, wherein the same or different R4 are selected from any one of substituted or unsubstituted C1-C6 alkyl groups and substituted or unsubstituted C6-C12 aryl groups; The term "substituted or unsubstituted" refers to either not being substituted or being substituted by deuterium; The condition is that the bicarbazole compound is not... .

2. The bicarbazole compound according to claim 1, characterized in that, The Ar0 is selected from any of the structures shown below. The same or different R2 is selected from any one of hydrogen, deuterium, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, and Si(R4)3; The same or different R1 is selected from any one of methyl, ethyl, isopropyl, tert-butyl, phenyl, and pyridyl; R1 can be replaced by one or more substituents R 11 When R1 is selected from methyl, ethyl, isopropyl, or tert-butyl, the substituent R... 11 The substituent R is selected from deuterium; when R1 is selected from phenyl or pyridyl, the substituent R 11 Selected from any one or a combination of deuterium, Si(R4)3; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

3. A bicarbazole compound according to claim 1, characterized in that, The Ar1 and Ar2, whether identical or different, are selected from Si(R4)3 or any of the structures shown below. The R 5a The same or different are selected from any one of hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, and Si(R4)3; The R5, whether identical or different, is selected from any one of hydrogen, deuterium, methyl, ethyl, isopropyl, and tert-butyl.

4. A bicarbazole compound according to claim 1, characterized in that, The L0, L1, and L2 that are the same or different are selected from single bonds or any of the structures shown below. 。 5. A bicarbazole compound according to claim 1, characterized in that, The R3 is selected from any one of hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, and Si(R4)3.

6. A bicarbazole compound according to claim 1, characterized in that, At least one group in Ar1 and Ar2 is replaced by Si(R4)3; The R4 may be the same or different from any one of methyl, ethyl, isopropyl, tert-butyl, phenyl, and biphenyl. The R4 may be replaced by one or more substituents selected from deuterium.

7. A bicarbazole compound, characterized in that, The bicarbazole compounds are selected from any one of the structures shown below. 。 8. An organic electroluminescent device, comprising an anode, an organic layer, and a cathode, characterized in that, The organic layer comprises one or a combination of at least two of the bicarbazole compounds as described in any one of claims 1 to 7.

9. An organic electroluminescent device according to claim 8, characterized in that, The organic layer includes a light-emitting layer, which comprises one or a combination of at least two of the bicarbazole compounds as described in any one of claims 1 to 7.

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