阅读说明：本技术 有机化合物及其应用和有机电致发光器件 (Organic compound, application thereof and organic electroluminescent device ) 是由 吕瑶 冯美娟 于 2018-07-27 设计创作，主要内容包括：本发明涉及有机电致发光器件领域,公开了有机化合物及其应用和有机电致发光器件,该化合物具有式(I)或式(II)所示的结构。本发明的有机化合物作为发光层的主体材料时,能够提高有机电致发光器件发光层的激子的利用率。特别地,本发明的有机化合物能够作为有机电致发光器件中的荧光或磷光化合物。<Image he="218" wi="700" file="DDA0001746858400000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to the field of organic electroluminescent devices, and discloses an organic compound, application thereof and an organic electroluminescent device, wherein the compound has a structure shown in a formula (I) or a formula (II). When the organic compound is used as a main material of a light-emitting layer, the utilization rate of excitons of the light-emitting layer of the organic electroluminescent device can be improved. In particular, the organic compounds of the inventionCan be used as fluorescent or phosphorescent compound in organic electroluminescent devices.)

1. An organic compound having a structure represented by formula (I) or formula (II),

wherein, in the formula (I) and the formula (II),

x is O or S, and X is O or S,

z is C or Si, and Z is C or Si,

R₁₁、R₁₂、R₂₁and R₂₂Each independently selected from the group consisting of H, a substituted or unsubstituted nitrogen-containing heteroaromatic tricyclic group, a substituted or unsubstituted nitrogen-containing heteroaromatic tetracyclic group, a substituted or unsubstituted nitrogen-containing heteroaromatic pentacyclic group, a substituted phenyl group and-NR₃₁R₃₂A group, and R₁₁And R₁₂Not being H at the same time, and R₂₁And R₂₂Not H at the same time;

in-NR₃₁R₃₂In the radical, R₃₁And R₃₂Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl;

R₁₁、R₁₂、R₂₁、R₂₂、R₃₁and R₃₂The substituents on each are independently selectedFrom C_1-4At least one of an alkyl group, a phenyl group, a biphenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a carbazolyl group, a dianilino group, and a phenyl-substituted carbazolyl group.

2. The organic compound according to claim 1, wherein, in the formula (I) and the formula (II),

the nitrogen-containing aromatic heterocyclic ring in the substituted or unsubstituted nitrogen-containing aromatic heterocyclic tricyclic group is a tricyclic shown in a formula (I1) or a formula (I2), and any position in the tricyclic shown in the formula (I1) and the formula (I2) which can be connected in a bonding manner is connected with a mother nucleus in the formula (I) and the formula (II) through a C-C bond or a C-N bond;

wherein Y in formula (I2) is O, S, C or N atom;

and the C atom and/or the N atom in the tricyclic ring represented by the formula (I1) and the formula (I2) are optionally substituted by a group selected from C_1-4At least one of alkyl, phenyl and diphenylamine groups;

3. the organic compound according to claim 1 or 2, wherein, in the formula (I) and the formula (II), the nitrogen-containing aromatic heterocyclic ring in the substituted or unsubstituted nitrogen-containing aromatic heterocyclic ring group is selected from the tetracyclic rings represented by the formula (II1) and/or the formula (II2),

and the C atom in the tetracyclic ring represented by formula (II1) and formula (II2) is optionally substituted by a group selected from C_1-4Is substituted with at least one of alkyl, phenyl and biphenyl.

4. The organic compound according to any one of claims 1 to 3, wherein, in the formulae (I) and (II), the nitrogen-containing heteroaromatic pentacyclic ring in the substituted or unsubstituted nitrogen-containing heteroaromatic pentacyclic group is selected from pentacycles represented by formulae (III1) to (III12),

and X in the formulae (III1) to (III12)₁、X₂、X₃、X₄、X₅、X₆、X₇、X₈、X₉、X₁₀、X₁₁And X₁₂Each independently selected from O, S, C and an N atom;

and the C atom and/or the N atom in the pentacyclic ring shown in the formulas (III1) to (III12) is/are optionally selected from C_1-4At least one of alkyl and phenyl of (a);

5. the organic compound according to claim 1, wherein the compound having the structure represented by formula (I) or formula (II) is selected from any one of the following compounds:

6. the organic compound according to claim 1, wherein the compound having the structure represented by formula (I) or formula (II) is selected from any one of the following compounds:

7. use of an organic compound according to any one of claims 1 to 6 in an organic electroluminescent device.

8. An organic electroluminescent device comprising one or more compounds of the organic compounds according to any one of claims 1 to 6; preferably, the first and second electrodes are formed of a metal,

the organic compound is present in at least one of an electron transport layer, a light emitting layer and a hole blocking layer of the organic electroluminescent device; preferably, the first and second electrodes are formed of a metal,

the organic electroluminescent device comprises a substrate, an anode, a hole injection layer, a hole transport layer, an optional electron blocking layer, a light emitting layer, an optional hole blocking layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked.

9. The organic electroluminescent device according to claim 8, wherein the organic compound is present in an electron transport layer of the organic electroluminescent device.

10. The organic electroluminescent device according to claim 8, wherein the organic compound is present in a light-emitting layer of the organic electroluminescent device; preferably, the first and second electrodes are formed of a metal,

the organic compound serves as a host material in the light-emitting layer.

Technical Field

The invention relates to the field of organic electroluminescent devices, in particular to an organic compound, application of the organic compound in an organic electroluminescent device, and an organic electroluminescent device containing one or more than two compounds in the organic compound

Background

Compared with the traditional liquid crystal technology, the organic electroluminescence (OLED) technology does not need backlight source irradiation and a color filter, pixels can emit light to be displayed on a color display panel, and the OLED technology has the characteristics of ultrahigh contrast, ultra-wide visual angle, curved surface, thinness and the like.

Organic electroluminescence mainly utilizes the phenomenon that organic substances convert electric energy into light energy, an organic light-emitting element generally comprises a cathode and an anode and an organic layer structure between the cathode and the anode, and the organic layer generally comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer and an electron injection layer. When a voltage is applied to the anode and the cathode, holes are injected from the anode side to the light-emitting layer, electrons are injected from the cathode side to the light-emitting layer, the injected holes and electrons combine in the light-emitting layer to form excitons, and the excitons emit light when returning to the ground state, wherein 25% of excited states return to the ground state through singlet excited states, and the emitted light is called fluorescence; 75% returns to the ground state through the triplet excited state, and the emitted light is called phosphorescence. The singlet excited state forms a triplet excited state by down-conversion, and if phosphorescence is used, the light emission efficiency can theoretically reach 100%.

Materials used as an organic layer in an organic electroluminescent device may be classified into a light emitting material and a charge transport material according to their functions, the light emitting material may be classified into a fluorescent material and a phosphorescent material, a host-guest doping system may be used as the light emitting material, and the charge transport material may be classified into a hole injection material, a hole transport material, an electron blocking material, an electron transport material, and an electron injection material.

The phosphorescent emission properties of OLEDs are not only influenced by triplet emitters, but in particular the materials forming the individual layers of the OLED have a very important influence on the properties of the OLED, for example light-emitting materials, electron-transporting materials. The materials used to form the layers of the OLED at present still have the defects of high driving voltage, short service life, low current efficiency and low brightness, so that an organic electroluminescent device with good performance cannot be obtained.

Disclosure of Invention

The present invention is directed to overcoming the aforementioned drawbacks of the prior art, and providing an organic compound capable of adjusting the HOMO level and the LUMO level of an organic electroluminescent material, and enabling the organic electroluminescent material containing the organic compound to have high electron mobility, thereby improving the light emitting efficiency and reducing the driving voltage.

The inventor of the present invention finds in research that the organic compound having the structure shown in formula (I) and/or formula (II) provided by the present invention has good thermodynamic stability, good film forming property, and appropriate triplet state energy level and energy gap when used as an organic electroluminescent material, and can significantly improve the luminous efficiency and prolong the service life of the material. Accordingly, the inventors have completed the technical solution of the present invention.

In order to achieve the above object, a first aspect of the present invention provides an organic compound having a structure represented by formula (I) or formula (II),

wherein, in the formula (I) and the formula (II),

x is O or S, and X is O or S,

z is C or Si, and Z is C or Si,

R₁₁、R₁₂、R₂₁and R₂₂Each independently selected from the group consisting of H, a substituted or unsubstituted nitrogen-containing heteroaromatic tricyclic group, a substituted or unsubstituted nitrogen-containing heteroaromatic tetracyclic group, a substituted or unsubstituted nitrogen-containing heteroaromatic pentacyclic group, a substituted phenyl group and-NR₃₁R₃₂A group, and R₁₁And R₁₂Not being H at the same time, and R₂₁And R₂₂Not H at the same time;

in-NR₃₁R₃₂In the radical, R₃₁And R₃₂Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl;

R₁₁、R₁₂、R₂₁、R₂₂、R₃₁and R₃₂Each substituent on is independently selected from C_1-4At least one of an alkyl group, a phenyl group, a biphenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a carbazolyl group, a dianilino group, and a phenyl-substituted carbazolyl group.

A second aspect of the present invention provides the use of an organic compound according to the first aspect in an organic electroluminescent device.

A third aspect of the present invention provides an organic electroluminescent device comprising one or more of the organic compounds according to the first aspect of the present invention.

When the organic compound is used as an electron transport material, the transport capability of an electron transport layer in an organic electroluminescent device can be improved.

When the organic compound is used as a main material of a light-emitting layer, the utilization rate of excitons of the light-emitting layer of the organic electroluminescent device can be improved. In particular, the organic compound of the present invention can be used as a fluorescent or phosphorescent compound in an organic electroluminescent device.

The technical scheme of the invention also has the following beneficial technical effects: the organic electronic luminescent device adopting the organic compound can reduce the driving voltage, improve the luminous efficiency and prolong the service life.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

As mentioned previously, a first aspect of the present invention provides an organic compound having a structure represented by formula (I) or formula (II),

wherein, in the formula (I) and the formula (II),

x is O or S, and X is O or S,

z is C or Si, and Z is C or Si,

R₁₁、R₁₂、R₂₁and R₂₂Each independently selected from the group consisting of H, a substituted or unsubstituted nitrogen-containing heteroaromatic tricyclic group, a substituted or unsubstituted nitrogen-containing heteroaromatic tetracyclic group, a substituted or unsubstituted nitrogen-containing heteroaromatic pentacyclic group, a substituted phenyl group and-NR₃₁R₃₂A group, and R₁₁And R₁₂Not being H at the same time, and R₂₁And R₂₂Not H at the same time;

in-NR₃₁R₃₂In the radical, R₃₁And R₃₂Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl;

R₁₁、R₁₂、R₂₁、R₂₂、R₃₁and R₃₂Each substituent on is independently selected from C_1-4At least one of an alkyl group, a phenyl group, a biphenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a carbazolyl group, a dianilino group, and a phenyl-substituted carbazolyl group.

In the present invention, "C_1-4The "alkyl group of (1)" includes methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.

Preferably, in the formula (I) and the formula (II),

the nitrogen-containing aromatic heterocyclic ring in the substituted or unsubstituted nitrogen-containing aromatic heterocyclic tricyclic group is a tricyclic shown in a formula (I1) or a formula (I2), and any position in the tricyclic shown in the formula (I1) and the formula (I2) which can be connected in a bonding manner is connected with a mother nucleus in the formula (I) and the formula (II) through a C-C bond or a C-N bond;

wherein Y in formula (I2) is O, S, C or N atom;

and the C atom and/or the N atom in the tricyclic ring represented by the formula (I1) and the formula (I2) are optionally substituted by a group selected from C_1-4At least one of alkyl, phenyl and diphenylamine groups;

preferably, in the formula (I) and the formula (II), the nitrogen-containing aromatic heterocyclic ring in the substituted or unsubstituted nitrogen-containing aromatic heterocyclic ring group is selected from tetracyclics represented by the formula (II1) and/or the formula (II2),

and the C atom in the tetracyclic ring represented by formula (II1) and formula (II2) is optionally substituted by a group selected from C_1-4Is substituted with at least one of alkyl, phenyl and biphenyl.

Preferably, in the formula (I) and the formula (II), the nitrogen-containing aromatic heterocyclic five ring in the substituted or unsubstituted nitrogen-containing aromatic heterocyclic five ring group is selected from five rings represented by the formulae (III1) to (III12),

and X in the formulae (III1) to (III12)₁、X₂、X₃、X₄、X₅、X₆、X₇、X₈、X₉、X₁₀、X₁₁And X₁₂Each independently selected from O, S, C and an N atom;

and the C atom and/or the N atom in the pentacyclic ring shown in the formulas (III1) to (III12) is/are optionally selected from C_1-4At least one of alkyl and phenyl of (a);

according to a preferred embodiment, in the present invention, the compound having the structure represented by formula (I) or formula (II) is selected from any one of the specific compounds listed in claim 5.

According to still another preferred embodiment, in the present invention, the compound having the structure represented by formula (I) or formula (II) is selected from any one of the specific compounds recited in claim 6 of the present invention.

The specific compounds recited in claims 5 and 6 of the present invention have high electron mobility when used as an organic electroluminescent material, thereby improving the luminous efficiency.

The synthesis method of the organic compound provided by the present invention is not particularly limited, and those skilled in the art can determine an appropriate synthesis method by combining the structural formula of the organic compound provided by the present invention with the preparation method of the preparation example.

Further, some preparation methods of the organic compound are exemplarily given in the preparation examples of the present invention, and those skilled in the art can obtain the organic compound provided by the present invention according to the preparation methods of these exemplary preparation examples. The present invention will not be described in detail herein with respect to specific methods of preparing the various compounds of the present invention, which should not be construed as limiting the invention to those skilled in the art.

As mentioned above, the second aspect of the present invention provides the use of the organic compound described in the first aspect in an organic electroluminescent device.

As described above, the third aspect of the present invention provides an organic electroluminescent device comprising one or two or more of the organic compounds described in the first aspect.

Preferably, the organic compound is present in at least one of an electron transport layer, a light emitting layer and a hole blocking layer of the organic electroluminescent device.

In particular, the specific compound provided by the invention can regulate and control the HOMO energy level and LUMO energy level of an organic electroluminescent material when being used in at least one of an electron transport layer, a light-emitting layer and a hole blocking layer of an organic electroluminescent device.

More preferably, when the specific compound provided by the invention is used in an electron transport layer of an organic electroluminescent device, the organic electroluminescent material containing the organic compound can have obviously higher electron mobility, so that obviously higher luminous efficiency is provided. Thus, according to a preferred embodiment, the organic compound is present in the electron transport layer of the organic electroluminescent device.

According to another preferred embodiment, the organic compound is present in an electron transport layer of the organic electroluminescent device.

More preferably, the organic compound is used as a host material in the light-emitting layer.

Preferably, the organic electroluminescent device includes a substrate, an anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an optional electron blocking layer, an emission layer (EML), an optional hole blocking layer, an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode, which are sequentially stacked.

Preferably, the organic electroluminescent device further comprises a first cover layer and/or a second cover layer, wherein the first cover layer is arranged on the outer surface of the anode, and the second cover layer is arranged on the outer surface of the cathode.

For example, the organic electroluminescent device may sequentially stack a first capping layer, an anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), a cathode, and a second capping layer.

Preferably, the first capping layer and the second capping layer each independently contain the organic compound according to the first aspect of the present invention.

The substrate of the present invention may use a glass substrate, a plastic substrate, or a metal substrate.

Preferably, the anode material forming the anode is selected from one or more of indium tin oxide, indium zinc oxide and tin dioxide. The thickness of the anode active layer formed by the anode material can be, for example, 100-1700 angstroms.

Preferably, the material forming the hole injection layer is a hole injection material, and the material forming the hole transport layer is a hole transport material, and the hole injection material and hole transport material are selected from aromatic amine derivatives (e.g. NPB, SqMA1), hexaazatriphenylene derivatives (e.g. HACTN), indolocarbazole derivatives, conductive polymers (e.g. PEDOT/PSS), phthalocyanine or porphyrin derivatives, dibenzoindenofluorenamine, spirobifluorenylamine.

The Hole Injection Layer (HIL) and the Hole Transport Layer (HTL) can be formed, for example, using an aromatic amine derivative of the following general formula:

the groups R1 to R9 in the above general formula are each independently selected from a single bond, hydrogen, deuterium, alkyl, benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, triphenylene, pyrene, fluorene, dimethylfluorene, spirobifluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolocarbazole, indenocarbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine.

Preferably, the hole injection layer has a thickness of 100-2000 angstroms, more preferably 200-600 angstroms.

Preferably, the hole transport layer has a thickness of 100-1000 angstroms, more preferably 200-400 angstroms.

Preferably, the material forming the electron transport layer can also be selected from at least one of a metal complex, a benzimidazole derivative, a pyrimidine derivative, a pyridine derivative, a quinoline derivative, and a quinoxaline derivative. Preferably, the thickness of the electron transport layer is 100-600 angstroms.

The material for forming the electron blocking layer is not particularly limited, and in general, any compound capable of satisfying the following conditions 1 and/or 2 can be considered:

1, the method comprises the following steps: the luminescent layer has a higher LUMO energy level, and the purpose of the luminescent layer is to reduce the number of electrons leaving the luminescent layer, so that the recombination probability of the electrons and holes in the luminescent layer is improved.

And 2, a step of: the light emitting layer has larger triplet energy, and the purpose of the light emitting layer is to reduce the number of excitons which leave the light emitting layer, thereby improving the efficiency of exciton conversion and light emission.

Materials forming the electron blocking layer include, but are not limited to, aromatic amine derivatives (e.g., NPB), spirobifluorene amines (e.g., SpMA2), in which the structures of a portion of the electron blocking material and the hole injecting material and the hole transporting material are similar. The electron blocking layer preferably has a thickness of 50 to 600 angstroms.

The material forming the hole blocking layer is preferably a compound having the following conditions 1 and/or 2:

1, the method comprises the following steps: the organic electroluminescent device has a higher HOMO energy level, and the purpose of the organic electroluminescent device is to reduce the number of holes leaving a light-emitting layer, so that the recombination probability of electrons and holes in the light-emitting layer is improved.

And 2, a step of: the light emitting layer has larger triplet energy, and the purpose of the light emitting layer is to reduce the number of excitons which leave the light emitting layer, thereby improving the efficiency of exciton conversion and light emission.

The material forming the hole blocking layer may further contain, for example, phenanthroline derivatives (e.g., Bphen, BCP), triphenylene derivatives, benzimidazole derivatives. Preferably, the hole blocking layer has a thickness of 50 to 600 angstroms.

Preferably, the material of the electron injection layer is LiF or Al₂O₃MnO, etc. Preferably, the electron injection layer has a thickness of 1 to 50 angstroms.

Preferably, the cathode material is one or more of Al, Mg and Ag. Preferably, the cathode layer has a thickness of 800-.

The organic electroluminescent device of the invention is preferably coated in one layer or in a plurality of layers by means of a sublimation process. In this case, in the vacuum sublimation system, the temperature is less than 10 DEG^-3Pa, preferably less than 10^-6At an initial pressure of Pa by vapor depositionThe compounds provided by the invention are applied.

The organic electroluminescent device of the invention is preferably coated with one layer or a plurality of layers by an organic vapor deposition method or sublimation with the aid of a carrier gas. In this case, 10^-6The material is applied under a pressure of Pa to 100 Pa. A particular example of such a process is an organic vapor deposition jet printing process, wherein the compounds provided by the present invention are applied directly through a nozzle and form a device structure.

The organic electroluminescent device of the present invention is preferably formed into one or more layers by photo-induced thermal imaging or thermal transfer.

The organic electroluminescent device according to the invention is preferably prepared by formulating the compounds according to the invention in solution and forming the layer or the layer structure by spin coating or by means of any printing means, such as screen printing, flexographic printing, ink-jet printing, lithographic printing, more preferably ink-jet printing. However, when a plurality of layers are formed by this method, the layers are easily damaged, that is, when one layer is formed and another layer is formed by using a solution, the formed layer is damaged by a solvent in the solution, which is not favorable for device formation. The compound provided by the invention can be substituted by structural modification, so that the compound provided by the invention can generate crosslinking action under the condition of heating or ultraviolet exposure, and an integral layer can be kept without being damaged. The compounds according to the invention can additionally be applied from solution and fixed in the respective layer by subsequent crosslinking in the polymer network.

Preferably, the organic electroluminescent device of the invention is manufactured by applying one or more layers from a solution and one or more layers by a sublimation method.

Preferred solvents for the preparation of organic electroluminescent devices according to the invention are selected from the group consisting of toluene, anisole, o-xylene, m-xylene, p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, phenoxytoluene, in particular 3-phenoxytoluene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, benzothiazole, butyl benzoate, isopropanol, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, cyclohexanol, Methyl benzoate, NMP, p-methylisobenzene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, 2-heptanol, 3-heptanol, or a mixture of these solvents.

Preferably, in the preparation of the organic electroluminescent device according to the invention, the compound according to the invention and the further compound are first mixed thoroughly and then applied by the above-described application method to form a layer or layers. More preferably, in the vacuum sublimation system, less than 10^-3Pa, preferably less than 10^-6Pa, to form a layer or layers by applying the respective compounds by vapour deposition.

The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.

Preparation example 1: preparation of Compound 1-1

Synthesis of intermediate 1-1-1-1: 300ml of a 1M n-butyllithium n-hexane solution was put into a 250ml reaction flask, cooled to-78 ℃ under the protection of nitrogen, and stirred for 10 minutes. A solution of 3,3 '-dibromo-2, 2' -bipyridine (0.1mol) in THF (500ml) was slowly added dropwise thereto over about 45 minutes, and after completion of the addition, the temperature was controlled to-78 ℃ and the mixture was stirred for 2 hours. Adding 0.2mol of silicon tetrachloride, and controlling the temperature to be not more than 5 ℃. After the feeding is finished, the temperature is naturally raised to the room temperature, and the mixture is stirred for 5 hours. The content of the raw materials of the center control index is lower than 0.5 percent. After completion of the reaction, 300ml of a saturated ammonium chloride solution was added dropwise thereto, and the mixture was stirred for 30 minutes, followed by extraction to obtain an organic phase, which was completely concentrated under reduced pressure, and then subjected to column chromatography to obtain intermediate 1-1-1-1 (yield 67%).

Calcd for C10H6Cl2N2 Si: 253.16 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta 7.14-7.15 (2H, m), 7.57-7.58 (2H, m), 8.53-8.54 (2H, m).

Synthesis of intermediate 1-1-1-2: 0.01mol of cuprous oxide, 0.04mol of Chxn-Py-Al, 0.2mol of phenol, 0.4mol of cesium carbonate and 60 g of ground and activated molecular sieves are introduced in succession into a single-neck flask and stirred at 100 ℃ under nitrogen. 0.3mol of iodobenzene was added using a syringe, followed by 120ml of acetonitrile. The reactor was placed in an oil bath at 82 ℃ and stirred for 24 hours. Thereafter, the reaction mixture was diluted with 25ml of dichloromethane, filtered through celite, completely concentrated under reduced pressure, and subjected to column chromatography to obtain intermediate 1-1-1-2 (yield 79%).

Calcd for C12H6Br2Cl 2O: 396.89 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta 7.10-7.11 (2H, m), 7.23-7.23 (2H, s), 7.50-7.51 (2H, d).

Synthesis of intermediate 1-1-1-3: the synthesis method is the same as the synthesis of the intermediate 1-1-1-1, and the intermediate 1-1-1-3 is obtained (yield 60%).

Calcd for C22H12Cl2N2 OSi: 419.33 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta 7.24-7.44 (8H, m), 7.94-7.95 (2H, m), 8.63-8.64 (2H, m).

Synthesis of Compound 1-1-1: dissolving 0.04mol of intermediate 1-1-1-3 in 160ml of toluene solvent, sequentially adding 0.08mol of carbazole, 0.2mol of sodium tert-butoxide, 0.0004mol of tri-tert-butylphosphine and 0.0004mol of tris (dibenzylideneacetone) dipalladium under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 4 hours, carrying out reduced pressure spin drying on reaction liquid, and carrying out column chromatography to obtain the compound 1-1-1 (yield is 58%).

Calcd for C46H28N4 OSi: 680.83 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 7.20-7.50 (16H, m), 7.63-7.64 (2H, m), 7.94-7.95 (4H, m), 8.12-8.13 (2H, m), 8.55-8.63 (4H, m).

Preparation example 2: preparation of Compounds 1-1-15

Synthesis of Compounds 1-1-15: dissolving 0.01mol of intermediate 1-1-1-3 in 50ml of toluene solvent, sequentially adding 0.02mol of di (4-isopropylphenyl) amine, 0.05mol of sodium tert-butoxide, 0.0002mol of tri-tert-butylphosphine and 0.0002mol of tris (dibenzylideneacetone) dipalladium under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 4 hours, carrying out reduced pressure spin drying on reaction liquid, and carrying out column chromatography to obtain the compound 1-1-1 (yield is 58%).

Calcd for C58H56N4 OSi: 853.18 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 1.29-1.29 (24H, d), 3.12-3.12 (4H, m), 6.22-6.23 (2H, m), 6.28-6.29 (2H, m), 6.38-6.39 (8H, m), 6.88-6.89 (8H, m), 7.22-7.24 (4H, m), 7.84-7.85 (2H, m), 8.69-8.70 (2H, m).

Preparation example 3: preparation of Compounds 1-2-20

And (3) synthesizing an intermediate 1-2-20-1: 0.1mol of 2-bromo-5-chlorobenzenethiol, 0.1mol of 2-bromo-5-chloroiodobenzene, 0.01mol of KOH, 0.1mol of tetrabutylammonium bromide and 0.01mol of nickel dichloride are put into a 500ml reaction bottle, stirred in 200ml of DMF, heated to 110 ℃, reacted for 16 hours, and after the reaction is finished, water is added to extrude the product, and the intermediate 1-1-1-1 is obtained by column chromatography (yield is 61%).

Calcd for C12H6Br2Cl 2S: 412.96 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta 7.12-7.13 (2H, m), 7.34-7.35 (2H, m), 7.48-7.48 (2H, s).

And (3) synthesizing an intermediate 1-2-20-2: the synthesis method is the same as the synthesis of the intermediate 1-1-1-3, and the intermediate 1-2-20-2 is obtained (yield 64%).

Calcd for C22H12Cl2N2 SSi: 435.40 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta 7.20-7.33 (6H, m), 7.69-7.69 (2H, s), 7.94-7.95 (2H, m), 8.63-8.64 (2H, m).

Synthesis of Compounds 1-2-20: synthesis method Synthesis of Compound 1-1-1 gave Compound 1-2-20 (yield 52%).

Calcd for C66H44N4 SSi: 953.23 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.47-6.48 (2H, m), 6.69-6.70 (4H, m), 7.01-7.02 (2H, d), 7.24-7.25 (2H, m), 7.36-7.52 (22H, m), 7.74-7.94 (10H, m), 8.62-8.63 (2H, m).

Preparation example 4: preparation of Compounds 1-2-32

Synthesis of Compounds 1-2-32: dissolving 0.10mol of 1-2-20-2 in 400ml of toluene solvent, and sequentially adding 0.20mol of 5, 7-dihydro-7, 7-dimethyl-indeno [2,1-b ] carbazole, n,

0.50mol of sodium tert-butoxide, 0.002mol of tri-tert-butylphosphine and 0.002mol of tris (dibenzylideneacetone) dipalladium are stirred and heated to reflux reaction, the reaction of the raw materials is detected to be finished after 5h, the reaction liquid is decompressed and dried by spinning, and the compound 1-2-32 is obtained by column chromatography (yield is 62%).

Calcd for C64H44N4 SSi: 929.21 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 1.67-1.67 (12H, s), 7.08-7.10 (6H, m), 7.22-7.44 (14H, m), 7.55-7.61 (4H, m), 7.69-7.69 (2H, s), 7.94-7.95 (2H, m), 8.06-8.07 (2H, m), 8.69-8.70 (2H, m).

Preparation example 5: preparation of Compound 2-1

And (3) synthesizing an intermediate 2-1-1-1: 0.1mol of 4, 5-diazafluoren-9-one is added into 200ml of o-dichlorobenzene and stirred to be dissolved completely, then added into 1mol of methane sulfonic acid dropwise, and stirred for 1 hour at room temperature. And dropwise adding an o-dichlorobenzene solution containing 0.5mol of m-iodophenol, keeping the temperature at 35 ℃ for 2h, heating to 150 ℃, reacting for 24h, detecting that the raw materials are completely reacted, concentrating and rotary-steaming the reaction solution, and performing column chromatography to obtain an intermediate 2-1-1-1 (yield is 48%).

Calcd for C23H12I2N 2O: 586.16 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.82 (2H, t), 6.96-6.96 (2H, d), 7.28-7.29 (2H, d), 7.48-7.49 (4H, m), 8.51-8.52 (2H, m).

Synthesis of Compound 2-1-1: synthesis method Synthesis of Compound 1-1-1 gave Compound 2-1-1 (yield 57%).

Calcd for C47H28N 4O: 664.75 +/-1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.82 (2H, t), 6.96-6.99 (4H, m), 7.19-7.33 (8H, m), 7.48-7.50 (4H, m), 7.63-7.64 (2H, m), 7.94-7.95 (2H, m), 8.12-8.13 (2H, m), 8.51-8.55 (4H, m).

Preparation example 6: preparation of Compounds 2-1-5

And (3) synthesizing an intermediate 2-1-5-1: dissolving 0.1mol of iodobenzene in 200ml of toluene solvent, sequentially adding 0.1mol of 3-bromocarbazole, 0.25mol of sodium tert-butoxide, 0.01mol of tri-tert-butylphosphine and 0.01mol of tris (dibenzylideneacetone) dipalladium under the protection of nitrogen, stirring, heating to reflux reaction, detecting that the reaction of the raw materials is finished after 6 hours, decompressing and spin-drying the reaction liquid, and obtaining an intermediate 2-1-5-1 (yield 65%) by column chromatography.

Calcd for C18H12 BrN: 322.2 + -1. 1H-NMR (400MHz, CDCl3) (ppm)

δ＝7.0～7.08(2H，m)，7.25～7.32(7H，m)，7.40～7.41(1H，m)，7.55～7.56(1H，m)，7.72～7.73(1H，m)。

Synthesis of intermediate 2-1-5-2: dissolving 0.065mol of intermediate 2-1-5-1 in 200ml of dioxane solvent, sequentially adding 0.065mol of diboron pinacol ester, 0.163mol of potassium acetate and 0.0065mol of 1, 1' -bis (diphenylphosphine) ferrocene palladium dichloride under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 4 hours, decompressing and spin-drying reaction liquid, and obtaining the intermediate 2-1-5-2 (the yield is 80%) through column chromatography.

Calcd for C24H24BNO 2: 369.26 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 1.26-1.26 (12H, s), 7.00-7.1 (3H, m), 7.3-7.32 (5H, m), 7.40-7.41 (2H, m), 7.55-7.60 (2H, m).

Synthesis of Compounds 2-1-5: dissolving 0.04mol of intermediate 2-1-5-2 in 200ml of dioxane solvent, sequentially adding 0.02mol of intermediate 2-1-1-1, 0.1mol of potassium carbonate and 0.0004mol of 1, 1' -bis (diphenylphosphine) ferrocene palladium dichloride under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 4 hours, carrying out reduced pressure spin drying on reaction liquid, and carrying out column chromatography to obtain the compound 2-1-5 (yield is 78%).

Calcd for C59H36N 4O: 816.94 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 7.0-7.08 (12H, m), 7.3-7.32 (12H, m), 7.40-7.46 (4H, m), 7.55-7.60 (4H, m), 7.77-7.78 (2H, m), 8.57-8.58 (2H, m).

Preparation example 7: preparation of Compounds 2-1-10

Synthesis of intermediate 2-1-10-1: 0.1mol of 4, 5-diazafluoren-9-one is added into 200ml of o-dichlorobenzene and stirred to be dissolved completely, then added into 1mol of methane sulfonic acid dropwise, and stirred for 1 hour at room temperature. And dropwise adding an o-dichlorobenzene solution containing 0.5mol of m-iodophenol, keeping the temperature at 35 ℃ for 2h, heating to 150 ℃, reacting for 24h, detecting that the raw materials are completely reacted, concentrating and rotary-steaming the reaction solution, and performing column chromatography to obtain an intermediate 2-1-10-1 (the yield is 48%).

Calcd for C23H12I2N 2O: 586.16 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.82 (2H, t), 6.96-6.96 (2H, d), 7.28-7.29 (2H, d), 7.48-7.49 (4H, m), 8.51-8.52 (2H, m).

Synthesis of Compounds 2-1-10: dissolving 0.04mol of intermediate 2-1-10-1 in 250ml of toluene solvent, sequentially adding 0.08mol of 11H-benzo [ a ] carbazole, 0.2mol of sodium tert-butoxide, 0.0008mol of tri-tert-butylphosphine and 0.0008mol of tris (dibenzylideneacetone) dipalladium under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 4 hours, carrying out reduced pressure spin drying on reaction liquid, and carrying out column chromatography to obtain the compound 2-1-10 (yield is 57%).

Calcd for C55H32N 4O: 764.87 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.82 (2H, d), 6.96-6.99 (4H, m), 7.19-7.33 (5H, m), 7.48-7.67 (9H, m), 7.88-7.94 (2H, m), 8.12-8.16 (4H, m), 8.51-8.55 (6H, m).

Preparation example 8: preparation of Compounds 2-1-13

Synthesis of Compounds 2-1-13: the synthesis method is the same as the synthesis of the intermediate 1-2-20, and the compound 2-1-13 is obtained (yield 57%).

Calcd for C47H32N 4O: 668.78 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.21-6.23 (4H, d), 6.63-6.64 (8H, m), 6.81-6.82 (6H, m), 6.94-6.95 (2H, m), 7.20-7.21 (8H, m), 7.48-7.49 (2H, m), 8.51-8.52 (2H, m).

Preparation example 9: preparation of Compounds 2-1-22

Synthesis of Compounds 2-1-22: dissolving 0.10mol of intermediate 2-1-10-1 in 400ml of toluene solvent, sequentially adding 0.20mol of dibenzo-1, 4-thiazine, 0.50mol of sodium tert-butoxide, 0.002mol of tri-tert-butylphosphine and 0.002mol of tris (dibenzylideneacetone) dipalladium under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 5h, carrying out reduced pressure spin drying on reaction liquid, and carrying out column chromatography to obtain the compound 2-1-22 (yield is 57%).

Calcd for C47H28N4OS 2: 728.88 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.21-6.23 (4H, d), 6.81-6.82 (2H, m), 6.94-6.97 (6H, m), 7.16-7.21 (12H, m), 7.48-7.49 (2H, m), 8.51-8.52 (2H, m).

Preparation example 10: preparation of Compounds 2-1-27

Synthesis of Compounds 2-1-27: dissolving 0.04mol of intermediate 2-1-10-1 in 250ml of toluene solvent, sequentially adding 0.08mol of 5-phenyl-5, 12-indolino [3,2-A ] carbazole, 0.2mol of sodium tert-butoxide, 0.0008mol of tri-tert-butylphosphine and 0.0008mol of tris (dibenzylideneacetone) dipalladium under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 4 hours, carrying out reduced pressure spin drying on reaction liquid, and carrying out column chromatography to obtain the compound 2-1-27 (yield 57%).

Calcd for C71H42N 6O: 995.13 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.82 (2H, m), 6.96-6.98 (4H, m), 7.19-7.33 (12H, m), 7.48-7.58 (12H, m), 7.94-7.95 (4H, m), 8.12-8.13 (2H, d), 8.51-8.55 (6H, m).

Preparation example 11: preparation of Compounds 2-1-29

Synthesis of Compounds 2-1-29: synthesis method Synthesis of Compound 2-1-27 was carried out to obtain Compound 2-1-29 (yield 57%).

Calcd for C59H32N4OS 2: 877.04 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.82 (2H, m), 6.96-6.98 (4H, m), 7.19-7.33 (8H, m), 7.48-7.52 (6H, m), 7.94-8.05 (6H, m), 8.45-8.55 (6H, m).

Preparation example 12: preparation of Compounds 2-1-34

Synthesis of Compounds 2-1-34: synthesis method Synthesis of Compound 2-1-27 was carried out to give Compound 2-1-34 (yield 55%).

Calcd for C65H44N 4O: 897.07 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 1.72-1.72 (4H, s) 6.81-6.81 (2H, m), 6.98-6.96 (4H, m), 7.19-7.33 (10H, m), 7.44-7.48 (4H, m), 7.69(2H, m), 7.94-7.94 (2H, m), 8.09(2H, m), 8.51-8.55 (4H, m).

Preparation example 13: preparation of Compound 2-2

And (3) synthesizing an intermediate 2-2-2-1: dissolving 0.105mol of 2-bromo-5-chlorobenzenethiol in 200ml of toluene solvent, sequentially adding 0.1mol of m-chloroiodobenzene, 0.11mol of sodium tert-butoxide, 0.001mol of tri-tert-butylphosphine and 0.001mol of tris (dibenzylideneacetone) dipalladium under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 4 hours, carrying out reduced pressure spin drying on reaction liquid, and carrying out column chromatography to obtain an intermediate 2-2-2-1 (yield is 90%).

Calcd for C12H7BrCl 2S: 334.06 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta 7.12-7.34 (5H, m), 7.48-7.48 (1H, s), 7.59-7.59 (1H, s).

And (3) synthesizing an intermediate 2-2-2-2: a solution of 0.05mol of intermediate 2-2-2-1 in 20ml of o-dichlorobenzene was added dropwise to 5ml of trifluoromethanesulfonic acid as a ketone solution. Adding 0.06mol of intermediate 1-2-1-1 into 130ml of anhydrous THF, stirring, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 0.06mol of 2.5mol/L n-butyllithium, keeping the temperature for 1 hour at-78 ℃, heating to room temperature, keeping for 2 hours, cooling to-78 ℃, adding the prepared ketone solution, heating to room temperature, adding water for quenching and filtering after 3 hours, extracting the filtrate for three times by using chloroform, drying by using anhydrous sodium sulfate, filtering, performing reduced pressure spin drying on the filtrate, and performing column chromatography to obtain intermediate 2-2-2-2 (the yield is 40%).

Calcd for C23H12Cl2N 2S: 419.33 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.81 (2H, m), 6.97-6.97 (2H, m), 7.11-7.11 (2H, m), 7.47-7.48 (4H, m), 8.51-8.51 (2H, m).

Synthesis of Compound 2-2-2: dissolving 0.02mol of intermediate 2-2-2-2 in 100ml of toluene solvent, sequentially adding 0.02mol of 2-phenyl-9H-carbazole, 0.05mol of sodium tert-butoxide, 0.0002mol of tri-tert-butylphosphine and 0.0002mol of tris (dibenzylideneacetone) dipalladium under the protection of nitrogen, stirring and heating until reflux reaction is carried out, detecting that the reaction of the raw materials is finished after 4 hours, carrying out reduced pressure spin drying on reaction liquid, and carrying out column chromatography to obtain the compound 2-2-2 (yield is 75%).

Calcd for C59H36N 4S: 833.01 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.81 (2H, m), 6.98-7.03 (4H, m), 7.24-7.51 (18H, m), 7.62-7.62 (2H, m), 7.79-7.79 (2H, m), 7.94-7.94 (2H, m), 8.18-8.18 (2H, m), 8.51-8.55 (4H, m).

Preparation example 14: preparation of Compounds 2-2-17

Synthesis of Compounds 2-2-17: synthesis method Synthesis of Compound 2-2-2 gave Compound 2-2-17 (yield 57%).

Calcd for C71H48N 4S: 989.23 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.08-6.09 (2H, m), 6.28-6.29 (2H, m), 6.42-6.43 (4H, m), 6.68-6.69 (6H, m), 6.84-6.85 (4H, m), 7.03-7.07 (6H, m), 7.22-7.32 (12H, m), 7.48-7.49 (8H, m), 7.60-7.61 (2H, m), 8.57-8.58 (2H, m).

Preparation example 15: preparation of Compounds 2-2-27

Synthesis of Compounds 2-2-27: synthesis method Synthesis of Compound 2-2-2 gave Compound 2-2-27 (yield 57%).

Calcd for C59H32N4O 2S: 860.98 + -1. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.90-6.91 (4H, m), 7.00-7.19 (14H, m), 7.40-7.60 (12H, m), 8.57-8.58 (2H, m).

Preparation of organic light emitting device