Application of amine derivative and organic electroluminescent device

Abstract

The invention relates to the technical field of organic electroluminescent devices, and discloses application of amine derivatives and an organic electroluminescent device. The amine derivative has a structure as shown in a formula (I). When the amine derivative provided by the invention is applied as a charge generation material in a light-emitting unit, a device containing the material can have the advantages of low driving voltage and high light-emitting efficiency. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescent devices, and in particular to the application of amine derivatives and organic electroluminescent devices. Background Art

[0002] In recent years, OLED has gradually entered people's field of vision as a new generation of display technology. Its broad application prospects and rapid technological progress have made OLED one of the hottest research areas in the display field and scientific research product development.

[0003] At present, OLED or screen still has the defects of high driving voltage and low current efficiency. In order to improve these defects, on the one hand, the device structure and manufacturing process need to be further optimized, and on the other hand, the performance of each functional layer material needs to be improved.

[0004] There are many types of OLED device structures, such as single light-emitting layer, multi-doped light-emitting layer, multiple light-emitting layers, and stacked layers.

[0005] The stacked device has multiple light-emitting parts including a light-emitting layer stacked between the anode and the cathode. Due to the different transmission rates of electrons and holes in OLED devices, the number of carriers in the light-emitting area is unbalanced, which limits the improvement of the exciton recombination rate, resulting in low device efficiency and high driving voltage. Adding a CGL (Charge Generate Layer) structure between the light-emitting units to provide carriers for the upper and lower film layers can effectively improve the problem of unbalanced carrier numbers in the device.

[0006] Therefore, it is of great practical significance to develop high-performance CGL materials to reduce the driving voltage of the device and improve the luminous efficiency of the device. Summary of the invention

[0007] The purpose of the present invention is to overcome the defects of the CGL material provided by the prior art, which has poor performance and causes the device to have high driving voltage and low luminous efficiency.

[0008] In order to achieve the above-mentioned object, the first aspect of the present invention provides a use of at least one of the amine derivatives represented by formula (I) in an effective amount for charge generation as a charge generating material in a light-emitting unit,

[0009]

[0010] Wherein, in formula (I),

[0011] R 11 , R 12 are each independently selected from substituted or unsubstituted C 6-30 substituted or unsubstituted C containing at least one hetero atom selected from O, S6-30 Heteroaryl; R 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains C 1-12 Alkyl, C 1-12 Alkoxy, C 3-8 Cycloalkyl;

[0012] L1 is a C 6-30 The aromatic compound of at least one connecting group provided; Optionally, L1 has a selected from C 1-10 At least one substituent of an alkyl group or a phenyl group.

[0013] A second aspect of the present invention provides an organic electroluminescent device, wherein the organic electroluminescent device is provided with a first electrode, a second electrode and a light-emitting unit located between the first electrode and the second electrode, and the light-emitting unit includes a first light-emitting portion, a second light-emitting portion and a first charge generation layer located between the first light-emitting portion and the second light-emitting portion.

[0014] The first charge generating layer comprises at least one of the amine derivatives represented by formula (I) in the application described in the first aspect as a charge generating material.

[0015] When the amine derivatives provided by the present invention are used as charge generating materials in a light-emitting unit, the device containing the material can have the advantages of low driving voltage and high luminous efficiency. DETAILED DESCRIPTION

[0016] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0017] The following is an explanation of some terms involved in the present invention. To avoid redundancy, terms that differ only in the number of carbon atoms are explained only once.

[0018] The "substituted or unsubstituted C 6-30The term "aryl" refers to a group provided by the removal of at least one hydrogen atom from an aromatic compound having 6 to 30 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbon atoms), which may or may not contain a substituent; the group includes, but is not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl and the like.

[0019] The "substituted or unsubstituted C containing at least one heteroatom selected from O, S" in the present invention 6-30 The definition of "heteroaryl" is the same as that of "substituted or unsubstituted C 6-30 The definition of "aryl" is similar; the difference is that "substituted or unsubstituted C containing at least one heteroatom selected from O, S 6-30 The "heteroaryl" contains at least one heteroatom as a ring-forming atom, and the heteroatom is selected from at least one of O and S.

[0020] The "C containing or not containing at least one heteroatom selected from N, O, S" in the present invention 6-30 The term “aromatic compound” refers to an aromatic compound having a total carbon atom count of 6-30 (e.g., the total carbon atom count may be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30), including but not limited to benzene, diphenyl, terphenyl, naphthalene, anthracene, phenanthrene, etc.

[0021] The present invention's "C 1-12 The term "alkyl" refers to a straight chain alkyl group or a branched chain alkyl group having 1 to 12 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12).

[0022] The present invention's "C 1-12 The term "alkoxy" refers to a straight chain alkoxy or branched alkoxy having 1 to 12 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12).

[0023] The present invention's "C 3-8 The term "cycloalkyl" refers to a cycloalkyl group having 3 to 8 carbon atoms, wherein the number of ring carbon atoms is any one of 3 to 8, such as 3, 4, 5, 6, 7, or 8, and may be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.

[0024] As mentioned above, the first aspect of the present invention provides a charge generating effective amount of at least one of the amine derivatives represented by formula (I) as a charge generating material in a light emitting unit,

[0025]

[0026] Wherein, in formula (I),

[0027] R 11 , R 12 are each independently selected from substituted or unsubstituted C 6-30 substituted or unsubstituted C containing at least one hetero atom selected from O, S 6-30 Heteroaryl; R 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains C 1-12 Alkyl, C 1-12 Alkoxy, C 3-8 Cycloalkyl;

[0028] L1 is a C 6-30 The aromatic compound of at least one connecting group provided; Optionally, L1 has a selected from C 1-10 At least one substituent of an alkyl group or a phenyl group.

[0029] Preferably, in the application of the present invention, in formula (I),

[0030] R 11 , R 12 R is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl; 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains C 1-10 Alkyl, C 1-10 Alkoxy, C 3-6 Cycloalkyl;

[0031] L1 is a C 6-24 The aromatic compound of at least one connecting group provided; Optionally, L1 has a selected from C 1-10 At least one substituent of an alkyl group or a phenyl group.

[0032] More preferably, in the application of the present invention, in formula (I),

[0033] R 11 , R 12R is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl; 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains C 1-8 Alkyl, C 1-8 Alkoxy, C 4-6 of a cycloalkyl group;

[0034] L1 is a C 6-24 The aromatic compound of at least one connecting group provided; Optionally, L1 has a selected from C 1-8 At least one substituent of an alkyl group or a phenyl group.

[0035] Further preferably, in the application of the present invention, in formula (I),

[0036] R 11 , R 12 R is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl; 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains methyl, ethyl, n-propyl, isopropyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl;

[0037] L1 is a connecting group provided by at least one compound selected from benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, dibenzofuran, and pyridine; optionally, L1 has at least one substituent selected from methyl, ethyl, n-propyl, isopropyl, C4 alkyl, C5 alkyl, C6 alkyl, and phenyl.

[0038] According to a particularly preferred embodiment, the amine derivative represented by formula (I) is selected from any one of the following:

[0039]

[0040]

[0041]

[0042]

[0043]

[0044] Preferably, the light-emitting unit is a light-emitting unit in an organic electroluminescent device.

[0045] The present invention has no particular restrictions on the specific method for preparing the amine derivatives shown in the aforementioned formula (I). Those skilled in the art can obtain the aforementioned compounds of the present invention according to the specific structural formula provided by the present invention in combination with the known process routes in the field of organic synthesis, and the present invention hereinafter exemplarily lists several examples to illustrate the preparation method of the compounds of the present invention. Those skilled in the art can also obtain the specific preparation method of all the remaining compounds by replacing the types of raw materials according to the preparation method of the compounds in the following text of the present invention. The present invention no longer describes the preparation methods of all the compounds in detail, and those skilled in the art should not be construed as limiting the present invention.

[0046] As mentioned above, the second aspect of the present invention provides an organic electroluminescent device, wherein the organic electroluminescent device is provided with a first electrode, a second electrode and a light-emitting unit located between the first electrode and the second electrode, and the light-emitting unit includes a first light-emitting portion, a second light-emitting portion and a first charge generation layer located between the first light-emitting portion and the second light-emitting portion.

[0047] The first charge generating layer comprises the amine derivative represented by formula (I) in the application described in the first aspect of the present invention as a charge generating material.

[0048] The present invention has no special requirements on the setting dimensions (such as thickness, etc.) of each component in the light-emitting unit. Those skilled in the art can make routine selections within the size range known in the art. The example part of the present invention only provides an exemplary setting dimension, which should not be understood by those skilled in the art as a limitation on the scheme of the present invention.

[0049] According to a preferred embodiment, the organic electroluminescent device is provided with:

[0050] a first electrode;

[0051] a second electrode, the second electrode facing the first electrode;

[0052] a first light-emitting portion, the first light-emitting portion being located between the first electrode and the second electrode;

[0053] a second light-emitting portion, the second light-emitting portion being located between the first light-emitting portion and the second electrode;

[0054] A first charge generation layer is located between the first light-emitting portion and the second light-emitting portion and includes an amine derivative represented by formula (I) in the application described in the first aspect of the present invention as a charge generation material.

[0055] Preferably, the first light-emitting portion comprises a hole injection layer, a first hole transport layer, a first light-emitting layer, and a first electron transport layer; and

[0056] The second light-emitting portion includes a second hole transport layer, a second light-emitting layer, and a second electron transport layer.

[0057] Preferably, the second light-emitting layer in the second light-emitting portion contains at least one light-emitting layer unit.

[0058] Preferably, the charge generating material contains an n-type charge generating material and a p-type charge generating material, and the n-type charge generating material contains an amine derivative represented by formula (I).

[0059] Preferably, in the charge generating material, the weight ratio of the n-type charge generating material to the p-type charge generating material is 1:0.1-2; more preferably, the weight ratio of the n-type charge generating material to the p-type charge generating material is 1:0.5-1.

[0060] Preferably, the charge generating material further contains at least one doping metal selected from Yb, Li, Ca and Mg.

[0061] Preferably, the ratio of the doping metal is 1-10 wt % based on the total amount of the n-type charge generating material.

[0062] According to a preferred specific implementation manner, the doping metal is located in the layer where the n-type charge generating material of the charge generating material is located.

[0063] According to another preferred specific implementation manner, the doping metal is located on the upper surface and / or lower surface of the layer where the n-type charge generating material of the charge generating material is located.

[0064] The functional compounds in the p-type charge generating material of the present invention may be the same as or similar to the hole transport material and / or the hole injection material, that is, the optional range of the functional compounds in the p-type charge generating material of the present invention is the same as that of the hole transport material and the hole injection material. The present invention will not be elaborated here, and those skilled in the art should not understand it as a limitation of the present invention.

[0065] In the present invention, one of the first electrode and the second electrode is an anode, and the other is a cathode.

[0066] According to some embodiments of the present invention, the anode material forming the anode is generally preferably a material with a large work function. For example, the anode material used in the present invention is selected from one or more of the following materials: metals, such as vanadium, chromium, copper and gold, or other alloys: metal oxides, such as zinc oxide, indium oxide, indium tin oxide, indium zinc oxide and tin dioxide, combinations of metals and oxides, such as zinc oxide: aluminum, but not limited thereto.

[0067] According to some embodiments of the present invention, the cathode material forming the cathode is generally preferably a material with a small work function, which can smoothly inject electrons into the organic material layer. The cathode material that can be used in the present disclosure can be selected from one or more of the following materials, one or more of Al, Mg and Ag.

[0068] According to some embodiments of the present invention, the material forming the hole injection layer has the ability to transport holes, so the material of the hole injection layer has the effect of injecting holes into the anode, has an excellent hole injection effect on the light-emitting layer or the light-emitting material, prevents the excitons generated in the light-emitting layer from moving to the electron injection layer or the electron injection material, and has excellent thin film forming ability. The HOMO of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer.

[0069] The present invention has no particular restrictions on the materials forming the first hole transport layer and the second hole transport layer, which may be the same or different. According to some embodiments of the present invention, the hole injection layer, the first hole transport layer, and the second hole transport layer each independently include aromatic amine derivatives (such as NPB, SqMA1), hexaazatriphenylene derivatives (such as HACTN), indolecarbazole derivatives, conductive polymers (such as PEDOT / PSS), phthalocyanine or porphyrin derivatives, dibenzoindenofluorene amine, spirobifluorene amine at least one, but not limited thereto.

[0070] According to some embodiments of the present invention, the hole injection layer, the first hole transport layer, and the second hole transport layer can each independently be formed using an aromatic amine derivative of the following general formula:

[0071]

[0072] 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, indolecarbazole, indenocarbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine.

[0073] The present invention has no particular limitation on the materials forming the first light-emitting layer and the second light-emitting layer, and the materials may be the same or different. According to some embodiments of the present invention, the light-emitting materials forming the first light-emitting layer and the second light-emitting layer are materials that can emit light in the visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes and the electrons, and are preferably materials that have good quantum efficiency for fluorescence or phosphorescence.

[0074] According to some embodiments of the present invention, the first light-emitting layer and the second light-emitting layer (the second light-emitting layer contains at least one light-emitting layer unit, preferably contains more than two light-emitting layer units) each independently contain a host material and a guest material. According to some embodiments of the present invention, the guest material is preferably a compound that generates emission via at least one of phosphorescence, fluorescence, TADF (thermally activated delayed fluorescence), MLCT (metal to ligand charge transfer), HLCT (with hybrid CT state) and triplet-triplet annihilation methods.

[0075] According to some embodiments of the present invention, the guest material may include derivatives of perylene, derivatives of anthracene, fluorene derivatives, distyryl aromatic derivatives, aromatic amine derivatives, silicone derivatives, boron derivatives, carbazole-triazine derivatives, acridine derivatives, ketone derivatives, sulfone derivatives, cyano derivatives and xanthene derivatives, but are not limited thereto.

[0076] In some preferred embodiments of the present invention, the sulfone derivative has the general formula shown below:

[0077]

[0078] The ketone derivatives have the general formula shown below:

[0079]

[0080] In the general formulas of the above-mentioned sulfone derivatives and ketone derivatives, R 20 , R 21 , R 22 and R 23 Each is independently selected from a single bond, hydrogen, deuterium, alkyl, benzene, diphenyl, terphenyl, quaterphenyl, naphthalene, phenylnaphthalene, anthracene, phenanthrene, triphenylene, pyrene, fluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolecarbazole, indenocarbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine, and a group represented by a substituent thereof.

[0081] According to some embodiments of the present invention, the electron transport layer is a layer that receives electrons from the electron injection layer and transfers the electrons to the light-emitting layer, and as the electron transport material, a material that can receive electrons from the cathode, move the electrons to the light-emitting layer, and has a high mobility for the electrons is suitable. The electron transport material includes, for example, an Al complex of 8-hydroxyquinoline; a complex containing Alq3; an organic free radical compound; a hydroxyflavone-metal complex, etc., but is not limited thereto.

[0082] According to some embodiments of the present invention, the electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound having the following properties: it has the ability to transport electrons, has the effect of injecting electrons from the cathode, has an excellent effect of injecting electrons into the light-emitting layer or the light-emitting material, prevents the excitons generated in the light-emitting layer from moving to the hole injection layer, and also has excellent film forming ability. The electron injection layer material includes, for example, LiF, CsF, Cs2CO3, LiQ, but is not limited thereto.

[0083] According to some embodiments of the present invention, the organic electroluminescent device of the present invention is preferably coated with one or more layers by means of vacuum evaporation. In the vacuum evaporation system, the vacuum degree must reach 10 -3 Pa or less, preferably less than 10 - 4 Pa or less, vacuum evaporation of the organic thin film of the compound provided by the present invention begins. For the thin film growth process, it is necessary to place the high-purity material to be evaporated in the beam source before vacuuming, and the sample must be blocked with a mask first. After the material evaporation rate is appropriate, the corresponding mask plate is replaced to expose the part where the thin film needs to be deposited. After the material is heated and evaporated, the organic material or metal atoms will have a certain initial velocity and will detach from the surface of the material and fly outward. If they encounter gas molecules during the scattering process, these evaporated molecules may be scattered. On the contrary, a part of them will move in a straight line at a uniform speed from the surface of the material to the surface of the sample and deposit to form a thin film. The distribution of the film thickness is related to the relative position of the beam source and the sample and the divergence angle. In the thin film deposition process, it is preferred to control the uniform film thickness and constant evaporation rate.

[0084] According to some embodiments of the present invention, the organic electroluminescent device of the present invention is preferably coated with one or more layers by an organic vapor deposition method or by means of carrier gas sublimation. In organic vapor deposition, the organic small molecule material is placed in an external separate, heat-controllable container unit, and the material evaporated from the heated container unit is carried and transported by an inert carrier gas (such as nitrogen), and the gas flow rate, pressure and temperature are the control parameters of the process. In a hot wall OVDP reaction chamber, the material is ejected from a nozzle several centimeters above the substrate and deposited on a cooled substrate. The deposition rate is mainly controlled by the carrier gas flow rate.

[0085] According to some embodiments of the present invention, the organic electroluminescent device of the present invention is preferably formed into a single-layer or multi-layer structure by light-induced thermal imaging or thermal transfer.

[0086] According to some embodiments of the present invention, the organic electroluminescent device of the present invention preferably prepares the organic compound of the present invention into a solution, and forms a layer or a plurality of layer structures by spin coating or by any printing method, such as screen printing, flexographic printing, inkjet printing, lithography, and more preferably inkjet printing.

[0087] According to some embodiments of the present invention, the preferred solvent for preparing the organic electroluminescent device of the present invention is selected from toluene, anisole, o-xylene, m-xylene, p-xylene, methyl benzoate, mesitylene, 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, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, methyl benzoate, NMP, p-methylisobenzoene, phenethyl ether, 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, 1,1-bis(3,4-dimethylphenyl)ethane, 2-heptanol, 3-heptanol, or a mixture of these solvents.

[0088] In some preferred embodiments of the present invention, when preparing the organic electroluminescent device of the present invention, the organic compound of the present invention and other compounds are first fully mixed, and then applied in the above manner to form one or more layers.

[0089] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all raw materials used are common commercial products. Unless otherwise specified, the room temperature or normal temperature described below refers to 25±1°C.

[0090] Preparation Example 1

[0091]

[0092] Synthesis of intermediate 1-1: In a 500 ml three-necked flask, under nitrogen protection, add 2-amino-4,6-dichloropyrimidine (50 mmol), phenylboric acid (100 mmol), toluene (200 ml), dicyclohexyl (2',4',6'-triisopropyl-(1,1'-biphenyl)-2-yl)phosphonic acid (5 mmol), tris(dibenzylideneacetone)dipalladium (1 mmol), and 100 ml of an aqueous solution containing potassium dihydrogen phosphate (250 mmol). Stirring was started and heated to 90° C. for overnight reaction. After 25 h, the reaction temperature was reduced to 40° C. and then reduced to 0° C. for 3 h. The crude product was filtered to obtain a crude product. The crude product was washed with water (200 ml) and then with ethanol (200 ml) to obtain a gray solid. Ethyl acetate / petroleum ether was used as the eluent and silica gel column chromatography was used to obtain intermediate 1-1 (yield: 84.6%).

[0093] Synthesis of intermediate 1-2: In a 500 ml three-necked flask, nitrogen was introduced to protect the intermediate 1-1 (30 mmol) and dissolved in N,N-dimethylformamide (80 ml). A saturated N,N-dimethylformamide solution (30 ml) containing N-bromosuccinimide (30 mmol) was added dropwise. After the addition was completed, the temperature was raised to 100 ° C and stirred for 20 h. HPLC detected that the reaction of the raw materials was basically completed. The reaction solution was cooled to room temperature and water (180 mL) was added dropwise. After stirring for 30 min, the crude product was filtered and dried. After recrystallization from toluene / ethanol, intermediate 1-2 (yield: 60.8%) was obtained.

[0094] Synthesis of intermediate 1-3: In a 200 ml three-necked flask, under nitrogen protection, add intermediate 1-2 (18 mmol), p-chlorophenylboric acid (18 mmol), isopropanol, water (mixed in a ratio of 3:1) (60 ml), anhydrous potassium carbonate (45 mmol) and bis(triphenylphosphine) palladium dichloride (0.18 mmol) in sequence, start stirring, heat to 80 ° C and reflux for 3 hours. Add deionized water (100 ml) to the reaction solution, stir for 10 minutes, take the organic phase and wash it three times with water, combine the organic phases, and dry it over anhydrous magnesium sulfate. Filter the desiccant, spin dry the organic solvent, and separate the residue through a silica gel column to obtain intermediate 1-3 (yield: 82.3%).

[0095] Synthesis of intermediate 1-4: In a 200 ml three-necked flask, under nitrogen protection, intermediate 1-3 (14 mmol), 1,4-dioxane solvent (50 ml), diboron pinacol ester (14 mmol), potassium acetate (35 mmol) and [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride (0.14 mmol) were added in sequence, and the temperature was raised to reflux for reaction for 3 h. HPLC detected that the reaction of the raw materials was complete. After the reaction solution was cooled to room temperature, the reaction solution was decompressed and dried to obtain a crude product. The crude product was dissolved in toluene solvent, heated and stirred, and the temperature was raised to reflux. It was heated through a silica gel column for decolorization. The filtrate was decompressed and dried to a small amount of solvent. Ethanol (100 ml) was added for slurrying, and recrystallized from toluene / ethanol to obtain intermediate 1-4 (yield: 90.7%).

[0096] Synthesis of compound 1: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 1-4, respectively, to obtain compound 1 (yield: 75.4%).

[0097] Mass spectrum: C34H23N5, theoretical value: 501.20, measured value: 501.28. 1H-NMR (400MHz, CDCl3) (ppm) δ = 1.97 ~ 2.01 (2H, s), 7.22 ~ 7.28 (2H, m), 7.31 ~ 7.36 (1H, d), 7.45 ~ 7.69 (8H, m), 7.77 ~ 7.91 (5H, m), 8.36 ~ 8.48 (2H, m), 8.66 ~ 8.72 (2H, m), 8.77 ~ 8.83 (1H, m).

[0098] Preparation Example 2

[0099]

[0100] Synthesis of intermediate 2-1: The synthesis method is the same as that of intermediate 1-1, except that phenylboronic acid is replaced by 3-methylphenylboronic acid to obtain intermediate 2-1 (yield: 83.5%).

[0101] Synthesis of intermediate 2-2: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 2-1 to obtain intermediate 2-2 (yield: 61.3%).

[0102] Synthesis of intermediate 2-3: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 is replaced by intermediate 2-2 to obtain intermediate 2-3 (yield: 79.6%).

[0103] Synthesis of intermediate 2-4: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 2-3 to obtain intermediate 2-4 (yield: 89.1%).

[0104] Synthesis of compound 2: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 2-4, respectively, to obtain compound 2 (yield: 76.4%).

[0105] Mass spectrum: C36H27N5, theoretical value: 529.23, measured value: 529.25. 1H-NMR (400MHz, CDCl3) (ppm) δ = 1.98 ~ 2.00 (2H, s), 2.48 ~ 2.51 (6H, s), 7.13 ~ 7.19 (2H, d), 7.22 ~ 7.28 (2H, m), 7.32 ~ 7.36 (1H, d), 7.42 ~ 7.50 (2H, m), 7.52 ~ 7.60 (2H, m), 7.71 ~ 7.79 (4H, m), 7.86 ~ 7.90 (1H, m), 8.37 ~ 8.47 (2H, m), 8.66 ~ 8.72 (2H, m), 8.78 ~ 8.82 (1H, m).

[0106] Preparation Example 3

[0107]

[0108] Synthesis of intermediate 42-1: The synthesis method is the same as that of intermediate 1-1, except that phenylboronic acid is replaced by 4-biphenylboronic acid to obtain intermediate 42-1 (yield: 83.7%).

[0109] Synthesis of intermediate 42-2: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 42-1 to obtain intermediate 42-2 (yield: 62.2%).

[0110] Synthesis of intermediate 42-3: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by intermediate 42-2 and m-chlorophenylboronic acid to obtain intermediate 42-3 (yield: 80.3%).

[0111] Synthesis of intermediate 42-4: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 42-3 to obtain intermediate 42-4 (yield: 89.6%).

[0112] Synthesis of compound 42: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 42-4, respectively, to obtain compound 2 (yield: 77.3%).

[0113] Mass spectrum: C46H31N5, theoretical value: 653.26, measured value: 653.20. 1H-NMR (400MHz, CDCl3) (ppm) δ = 2.02 ~ 2.05 (2H, s), 7.31 ~ 7.64 (10H, m), 7.67 ~ 7.78 (5H, m), 7.82 ~ 7.91 (5H, m), 8.27 ~ 8.36 (6H, m), 8.36 ~ 8.41 (1H, m), 8.42 ~ 8.48 (1H, m), 8.78 ~ 8.83 (1H, m).

[0114] Preparation Example 4

[0115]

[0116] Synthesis of intermediate 52-1: The synthesis method is the same as that of intermediate 1-1, except that phenylboronic acid is replaced by 3,5-dimethylphenylboronic acid to obtain intermediate 52-1 (yield: 84.1%).

[0117] Synthesis of intermediate 52-2: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 52-1 to obtain intermediate 52-2 (yield: 62.0%).

[0118] Synthesis of intermediate 52-3: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by intermediate 52-2 and 4'-chlorobiphenyl-4-boronic acid to obtain intermediate 52-3 (yield: 81.2%).

[0119] Synthesis of intermediate 52-4: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 52-3 to obtain intermediate 52-4 (yield: 88.6%).

[0120] Synthesis of compound 52: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 52-4, respectively, to obtain compound 52 (yield: 76.9%).

[0121] Mass spectrum: C44H35N5, theoretical value: 633.29, measured value: 633.33. 1H-NMR (400MHz, CDCl3) (ppm) δ = 1.98 ~ 1.99 (2H, s), 2.29 ~ 2.33 (12H, s), 7.24 ~ 7.26 (4H, s), 7.32 ~ 7.36 (1H, d), 7.43 ~ 7.45 (2H, m), 7.53 ~ 7.60 (2H, m), 7.67 ~ 7.69 (4H, d), 7.83 ~ 7.90 (3H, m), 8.37 ~ 8.41 (1H, m), 8.43 ~ 8.47 (1H, m), 8.67 ~ 8.71 (2H, m), 8.78 ~ 8.82 (1H, m).

[0122] Preparation Example 5

[0123]

[0124] Synthesis of intermediate 62-1: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-5-chlorotoluene and 2-methyl-1,4-terephthalenediboronic acid, respectively, to obtain intermediate 62-1 (yield: 78.3%).

[0125] Synthesis of intermediate 62-2: In a 500 ml three-necked flask, under nitrogen protection, add 2-amino-4,6-dichloropyrimidine (50 mmol), 3-biphenylboric acid (50 mmol), toluene (200 ml), dicyclohexyl (2',4',6'-triisopropyl-(1,1'-biphenyl)-2-yl)phosphonic acid (2.5 mmol), tris(dibenzylideneacetone)dipalladium (0.5 mmol), 60 ml of an aqueous solution containing potassium dihydrogen phosphate (125 mmol), start stirring and heat to 90 ° C overnight reaction, after 20 hours, reduce the reaction temperature to 40 ° C, and then reduce to 0 ° C and maintain for 3 hours, filter to obtain a crude product, wash the crude product with water (200 ml), and then wash with ethanol (200 ml) to obtain a gray solid. Use ethyl acetate / petroleum ether as the eluent and separate by silica gel column chromatography to obtain intermediate 62-2 (yield: 68.5%).

[0126] Synthesis of intermediate 62-3: The synthesis method is the same as that of intermediate 62-2, except that 2-amino-4,6-dichloropyrimidine and 3-biphenylboronic acid are replaced by intermediate 62-2 and phenylboronic acid, respectively, to obtain intermediate 62-3 (yield: 80.3%).

[0127] Synthesis of intermediate 62-4: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 62-3 to obtain intermediate 62-4 (yield: 62.0%).

[0128] Synthesis of intermediate 62-5: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by intermediate 62-4 and intermediate 62-1 to obtain intermediate 62-5 (yield: 80.6%).

[0129] Synthesis of intermediate 62-6: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 62-5 to obtain intermediate 62-6 (yield: 89.6%).

[0130] Synthesis of compound 62: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 62-6, respectively, to obtain compound 62 (yield: 75.7%).

[0131] Mass spectrum: C48H35N5, theoretical value: 681.29, measured value: 681.30. 1H-NMR (400MHz, CDCl3) (ppm) δ = 1.98 ~ 2.00 (2H, s), 2.56 ~ 2.60 (6H, s), 7.13 ~ 7.17 (1H, m), 7.32 ~ 7.39 (1H, m), 7.40 ~ 7.53 (4H, m), 7.55 ~ 7.83 (10H, m), 7.86 ~ 7.98 (6H, m), 8.35 ~ 8.41 (2H, m), 8.43 ~ 8.47 (1H, m), 8.57 ~ 8.61 (1H, m), 8.78 ~ 8.82 (1H, m).

[0132] Preparation Example 6

[0133]

[0134] Synthesis of intermediate 81-1: The synthesis method is the same as that of intermediate 1-1, except that phenylboronic acid is replaced by 3,4-dimethylphenylboronic acid to obtain intermediate 81-1 (yield: 82.5%).

[0135] Synthesis of intermediate 81-2: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 81-1 to obtain intermediate 81-2 (yield: 62.7%).

[0136] Synthesis of intermediate 81-3: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboric acid are replaced by intermediate 81-2 and (4-(4-chloronaphthyl)phenyl)boric acid to obtain intermediate 81-3 (yield: 81.3%).

[0137] Synthesis of intermediate 81-4: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 81-3 to obtain intermediate 81-4 (yield: 87.8%).

[0138] Synthesis of compound 81: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 81-4, respectively, to obtain compound 81 (yield: 75.9%).

[0139] Mass spectrum: C48H37N5, theoretical value: 683.30, found value: 683.35. 1H-NMR (400MHz, CDCl3) (ppm) δ = 1.98 ~ 2.01 (2H, s), 2.21 ~ 2.24 (6H, s), 2.28 ~ 2.31 (6H, s), 7.24 ~ 7.26 (4H, s), 7.30 ~ 7.44 (5H, m), 7.47 ~ 7.52 (2H, m), 7.53~7.60 (3H, m), 7.72~7.74 (2H, d), 7.86~7.90 (1H, m), 8.15~8.19 (1H, d), 8.37 ~8.41(1H,m), 8.43~8.47(1H,m), 8.82~8.78(1H,m), 8.93~8.97(1H,m), 9.00~9.04(1H,m).

[0140] Preparation Example 7

[0141]

[0142] Synthesis of intermediate 92-1: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 9-bromo-10-chloroanthracene and 1,4-phenylenediboronic acid, respectively, to obtain intermediate 92-1 (yield: 79.4%).

[0143] Synthesis of intermediate 92-2: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by intermediate 62-4 and intermediate 92-1 to obtain intermediate 92-2 (yield: 77.5%).

[0144] Synthesis of intermediate 92-3: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 92-2 to obtain intermediate 92-3 (yield: 90.8%).

[0145] Synthesis of compound 92: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 92-3, respectively, to obtain compound 92 (yield: 77.3%).

[0146] Mass spectrum: C54H35N5, theoretical value: 753.29, measured value: 753.36. 1H-NMR (400MHz, CDCl3) (ppm) δ = 2.04~2.06 (2H, s), 7.23~7.27 (4H, s), 7.32~7.36 (1H, d), 7.40~7.53 (8H, m), 7.56~7.83 (10H, m), 7.86~7.96 (2H, m), 8.15~8.25 (5H, m), 8.37~8.47 (2H, m), 8.78~8.82 (1H, m).

[0147] Preparation Example 8

[0148]

[0149] Synthesis of intermediate 108-1: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 5-bromo-2-chloro-6-methylpyridine and 1,4-phenylenediboronic acid, respectively, to obtain intermediate 108-1 (yield: 78.6%).

[0150] Synthesis of intermediate 108-2: The synthesis method is the same as that of intermediate 62-2, except that 2-biphenylboronic acid is replaced by 2-naphthalene borate to obtain intermediate 108-2 (yield: 67.3%).

[0151] Synthesis of intermediate 108-3: The synthesis method is the same as that of intermediate 62-2, except that 2-biphenylboronic acid is replaced by phenylboronic acid to obtain intermediate 108-3 (yield: 77.9%).

[0152] Synthesis of intermediate 108-4: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 108-3 to obtain intermediate 108-4 (yield: 62.5%).

[0153] Synthesis of intermediate 108-5: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by intermediate 108-4 and intermediate 108-1 to obtain intermediate 108-5 (yield: 80.3%).

[0154] Synthesis of intermediate 108-6: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 108-5 to obtain intermediate 108-6 (yield: 90.3%).

[0155] Synthesis of compound 108: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 108-6, respectively, to obtain compound 108 (yield: 75.8%).

[0156] Mass spectrum: C44H30N6, theoretical value: 642.25, measured value: 642.26. 1H-NMR (400MHz, CDCl3) (ppm) δ = 2.02~2.04 (2H, s), 2.90~2.92 (3H, s), 7.23~7.27 (4H, d), 7.47~7.51 (1H, m), 7.54~7.67 (6H, m), 7.79~7.83 (3H, m), 7.93~8.08 (6H, m), 8.43~8.47 (3H, m), 8.79~8.83 (2H, m).

[0157] Preparation Example 9

[0158]

[0159] Synthesis of intermediate 119-1: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 4-bromo-1-chloro-dibenzofuran and 1,4-phenylenediboronic acid, respectively, to obtain intermediate 119-1 (yield: 76.8%).

[0160] Synthesis of intermediate 119-2: The synthesis method is the same as that of intermediate 1-1, except that phenylboronic acid is replaced by 3-biphenylboronic acid to obtain intermediate 119-2 (yield: 84.5%).

[0161] Synthesis of intermediate 119-3: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 119-2 to obtain intermediate 119-3 (yield: 60.9%).

[0162] Synthesis of intermediate 119-4: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by intermediate 119-3 and intermediate 119-1 to obtain intermediate 119-4 (yield: 80.3%).

[0163] Synthesis of intermediate 119-5: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 119-4 to obtain intermediate 119-5 (yield: 90.5%).

[0164] Synthesis of compound 119: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 119-4, respectively, to obtain compound 119 (yield: 75.9%).

[0165] Mass spectrum: C58H37N5O, theoretical value: 819.30, measured value: 819.28. 1H-NMR (400MHz, CDCl3) (ppm) δ = 2.07~2.10 (2H, s), 7.23~7.28 (4H, m), 7.30~7.64 (14H, m), 7.67~7.78 (6H, m), 7.80~7.84 (1H, d), 7.86~8.00 (4H, m), 8.13~8.20 (3H, m), 8.37~8.47 (2H, m), 8.78~8.82 (1H, m).

[0166] Preparation Example 10

[0167]

[0168] Synthesis of intermediate 131-1: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 1-bromo-4-chloro-dibenzofuran and 1,4-phenylenediboronic acid, respectively, to obtain intermediate 131-1 (yield: 76.8%).

[0169] Synthesis of intermediate 131-2: The synthesis method is the same as that of intermediate 62-2, except that 2-biphenylboronic acid is replaced by 4-dibenzofuran boronic acid to obtain intermediate 131-2 (yield: 66.2%).

[0170] Synthesis of intermediate 131-3: The synthesis method is the same as that of intermediate 62-2, except that 2-biphenylboronic acid is replaced by phenylboronic acid to obtain intermediate 131-3 (yield: 78.5%).

[0171] Synthesis of intermediate 131-4: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 131-3 to obtain intermediate 131-4 (yield: 62.5%).

[0172] Synthesis of intermediate 131-5: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by intermediate 131-4 and intermediate 131-1 to obtain intermediate 131-5 (yield: 80.6%).

[0173] Synthesis of intermediate 131-6: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 131-5 to obtain intermediate 131-6 (yield: 89.1%).

[0174] Synthesis of compound 131: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 131-6, respectively, to obtain compound 131 (yield: 75.8%).

[0175] Mass spectrum: C52H31N5O2, theoretical value: 757.25, measured value: 757.28. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 2.03 ~ 2.06 (2H, s), 7.23 ~ 7.28 (4H, m), 7.30 ~ 7.47 (6H, m), 7.47 ~ 7.69 (7H, m), 7.72 ~ 7.83 (4H, m), 7.86 ~ 7.91 (1H, m), 7.96 ~ 8.01 (2H, m), 8.06 ~ 8.10 (1H, m), 8.19 ~ 8.23 ​​(1H, d), 8.37 ~ 8.48 (2H, m), 8.78 ~ 8.82 (1H, m).

[0176] Preparation Example 11

[0177]

[0178] Synthesis of intermediate 136-1: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 1-bromo-4-iodonaphthalene and 1,4-phenylenediboronic acid, respectively, to obtain intermediate 136-1 (yield: 70.3%).

[0179] Synthesis of intermediate 136-2: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 is replaced by intermediate 136-1 to obtain intermediate 136-2 (yield: 69.5%).

[0180] Synthesis of intermediate 136-3: The synthesis method is the same as that of intermediate 1-1, except that phenylboronic acid is replaced by 3,4-dimethylphenylboronic acid to obtain intermediate 136-3 (yield: 82.6%).

[0181] Synthesis of intermediate 136-4: The synthesis method is the same as that of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 136-3 to obtain intermediate 136-4 (yield: 62.8%).

[0182] Synthesis of intermediate 136-5: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by intermediate 136-4 and intermediate 136-1 to obtain intermediate 136-5 (yield: 78.4%).

[0183] Synthesis of intermediate 136-6: The synthesis method is the same as that of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 136-5 to obtain intermediate 136-6 (yield: 90.6%).

[0184] Synthesis of compound 136: The synthesis method is the same as that of intermediate 1-3, except that intermediate 1-2 and p-chlorophenylboronic acid are replaced by 2-bromo-1,10-phenanthroline and intermediate 136-6, respectively, to obtain compound 136 (yield: 78.3%).

[0185] Mass spectrum: C54H41N5, theoretical value: 759.34, measured value: 759.37. 1H-NMR (400MHz, CDCl3) (ppm) δ = 1.96 ~ 1.97 (2H, s), 2.21 ~ 2.31 (12H, d), 7.22 ~ 7.38 (13H, m), 7.47 ~ 7.60 (4H, m), 7.72 ~ 7.74 (2H, d), 7.86 ~ 7.90 (1H, m), 8.37 ~ 8.47 (2H, m), 8.67 ~ 8.72 (2H, m), 8.78 ~ 8.82 (1H, m), 8.97 ~ 9.04 (2H, m).

[0186] Device Example 1

[0187] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent (volume ratio 1:1), baked in a clean environment to completely remove water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0188] The glass substrate with the anode is placed in a vacuum chamber and evacuated to 1×10 -5Pa, vacuum evaporate the first hole injection layer on the above-mentioned anode layer film, use the multi-source co-evaporation method to adjust the evaporation rate of compound HT to 0.1nm / s, the evaporation rate of compound NPD-9 to 3%, and the total evaporation film thickness is 10nm; then evaporate the compound HT as the first hole transport layer, the evaporation rate is 0.1nm / s, and the thickness is 60nm; evaporate the first light-emitting layer on the above-mentioned hole transport layer, the light-emitting layer includes a main material and a guest material, use the multi-source co-evaporation method to adjust the evaporation rate of the main material RH to 0.1nm / s, the evaporation rate of the guest material RD to 10%, and the total evaporation film thickness is 30nm; vacuum evaporate Alq3 as the first electron transport layer on the light-emitting layer, the evaporation rate is 0.1nm / s, and the total evaporation film thickness is 30nm; vacuum evaporate the n-type charge generation layer on the electron transport layer, use the multi-source co-evaporation method to adjust the evaporation rate of compound 1 to 0.1nm / s, the evaporation rate of Yb to 5% For example, the total film thickness of the vapor deposition is set to 15nm; a p-type charge generation layer is vacuum evaporated thereon, and the evaporation rate of the compound HT is adjusted to 0.1nm / s by a multi-source co-evaporation method, and the evaporation rate of the compound NPD-9 is set to 3%, and the total film thickness of the vapor deposition is 15nm; then, the compound HT is evaporated as a second hole transport layer, and the evaporation rate is 0.1nm / s, and the thickness is 60nm; a second light-emitting layer is evaporated on the above-mentioned hole transport layer, and the light-emitting layer includes a main material and a guest material. The multi-source co-evaporation method is used to adjust the evaporation rate of the main material RH to 0.1nm / s, and the evaporation rate of the guest material RD is set to 10%, and the total film thickness of the vapor deposition is 30nm; Alq3 is vacuum evaporated on the light-emitting layer as a second electron transport layer, and the evaporation rate is 0.1nm / s, and the total film thickness of the vapor deposition is 30nm; LiF with a thickness of 1nm is vacuum evaporated on the electron transport layer as an electron injection layer, and an Al layer with a thickness of 100nm is used as the cathode of the device.

[0189]

[0190] Device Examples 2 to 13

[0191] The organic electroluminescent devices of Device Examples 2 to 13 were prepared by a method similar to that of Device Example 1, except that Compound 1 in Device Example 1 was replaced by the compounds shown in Table 1.

[0192] Device Comparison Examples 1 to 3

[0193] Organic electroluminescent devices of Comparative Examples 1 to 3 were prepared by a method similar to that of Device Example 1, except that Compound 1 in Device Example 1 was replaced by the following compounds Ref-1, Ref-2 and Ref-3, respectively.

[0194]

[0195] Test Example 1

[0196] At brightness 2000cd / m 2 The driving voltage and current efficiency of the organic electroluminescent device obtained by the device example in Table 1 below were measured. The results are shown in Table 1.

[0197] Table 1

[0198]

[0199] The above results show that, compared with the comparative example, the organic compound of the present invention has a lower driving voltage and a higher device luminous efficiency when used as an electron blocking material in an organic electroluminescent device.

[0200] Device Example 14

[0201] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent (volume ratio 1:1), baked in a clean environment to completely remove water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0202] The glass substrate with the anode is placed in a vacuum chamber and evacuated to 1×10 -5Pa, vacuum evaporate Ag on the above anode layer as a reflective electrode layer, the evaporation rate is 0.1nm / s, and the total evaporation film thickness is 100nm. Vacuum evaporate the first hole injection layer on the above reflective electrode layer, using the multi-source co-evaporation method, adjust the evaporation rate of compound HT to 0.1nm / s, the evaporation rate of compound NPD-9 to 3%, and the total evaporation film thickness is 10nm; then evaporate the compound HT as the first hole transport layer, the evaporation rate is 0.1nm / s, and the thickness is 60nm; evaporate the first light-emitting layer on the above hole transport layer, the light-emitting layer includes a main material and a guest material, and use the multi-source co-evaporation method to adjust the evaporation rate of the main material BH to 0.1nm / s, and the evaporation rate of the guest material BD to 5% For example, the total film thickness of the evaporation is 30nm; Alq3 is vacuum evaporated on the light-emitting layer as the first electron transport layer, the evaporation rate is 0.1nm / s, and the total film thickness of the evaporation is 30nm; the n-type charge generation layer is vacuum evaporated on the electron transport layer, and the evaporation rate of compound 1 is adjusted to 0.1nm / s by a multi-source co-evaporation method, and the Yb evaporation rate is set at 5%, and the total film thickness of the evaporation is 15nm; on this, a p-type charge generation layer is vacuum evaporated, and the evaporation rate of compound HT is adjusted to 0.1nm / s by a multi-source co-evaporation method, and the evaporation rate of compound NPD-9 is set at 3%. The total film thickness of the evaporation is 15nm; then, the compound HT is evaporated as the second hole transport layer, the evaporation rate is 0.1nm / s, and the thickness is 60nm; the second light-emitting layer is evaporated on the above hole transport layer, the light-emitting layer includes a main material and a guest material, and the evaporation rate of the main material GH is adjusted to 0.1nm / s by a multi-source co-evaporation method, and the evaporation rate of the guest material GD is set at 10%, and the total film thickness of the evaporation is 30nm; the third light-emitting layer is evaporated on the above hole transport layer, the light-emitting layer includes a main material and a guest material, and the evaporation rate of the main material RH is adjusted by a multi-source co-evaporation method. The plating rate is 0.1nm / s, the evaporation rate of the guest material RD is set at 10%, and the total evaporation film thickness is 30nm; Alq3 is vacuum evaporated on the light-emitting layer as the second electron transport layer, the evaporation rate is 0.1nm / s, and the total evaporation film thickness is 30nm; the cathode material is vacuum evaporated on the electron transport layer, and the Mg evaporation rate is adjusted to 0.1nm / s by a multi-source co-evaporation method, and the Ag evaporation rate is set to 20% of the Mg evaporation rate, and the total evaporation film thickness is 2nm; then Ag is evaporated on it, the evaporation rate is 0.1nm / s, and the total evaporation film thickness is 15nm.

[0203]

[0204] Device Examples 15 to 26

[0205] Organic electroluminescent devices of device examples 15 to 26 were prepared by a method similar to that of device example 14, except that compound 1 in device example 14 was replaced by the compounds shown in Table 2.

[0206] Device Comparison Examples 4 to 6

[0207] Organic electroluminescent devices of device comparison examples 4 to 6 were prepared by a method similar to that of device example 14, except that compound 1 in device example 14 was replaced by compounds Ref-1, Ref-2 and Ref-3, respectively.

[0208] Test Example 2

[0209] At a current density of 20 mA / cm 2 The driving voltage and current efficiency of the organic electroluminescent device obtained by the device example in Table 2 below were measured. The results are shown in Table 2.

[0210] Table 2

[0211]

[0212] The above results show that, compared with the comparative example, the organic compound of the present invention has a lower driving voltage and a higher device luminous efficiency when used as an electron blocking material in an organic electroluminescent device.

[0213] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. Use of at least one of the amine derivatives represented by formula (I) in an effective amount for charge generation as a charge generating material in a light-emitting unit, in, In formula (I), R 11 , R 12 are each independently selected from substituted or unsubstituted C 6-30 substituted or unsubstituted C containing at least one hetero atom selected from O, S 6-30 Heteroaryl; R 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains C 1-12 Alkyl, C 1-12 Alkoxy, C 3-8 of a cycloalkyl group; L1 is a C 6-30 The aromatic compound of at least one connecting group provided; Optionally, L1 has a selected from C 1-10 At least one substituent of an alkyl group or a phenyl group.

2. The use according to claim 1, wherein: In formula (I), R 11 , R 12 R is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl; 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains C 1-10 Alkyl, C 1-10 Alkoxy, C 3-6 of a cycloalkyl group; L1 is a C 6-24 The aromatic compound of at least one connecting group provided; Optionally, L1 has a selected from C 1-10 At least one substituent of an alkyl group or a phenyl group; Preferably, in formula (I), R 11 , R 12 R is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl; 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains C 1-8 Alkyl, C 1-8 Alkoxy, C 4-6 of a cycloalkyl group; L1 is a C 6-24 The aromatic compound of at least one connecting group provided; Optionally, L1 has a selected from C 1-8 At least one substituent of an alkyl group or a phenyl group; Preferably, in formula (I), R 11 , R 12 R is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl; 11 and R 12 The optional substituents are selected from at least one group in the W combination, wherein the W combination contains methyl, ethyl, n-propyl, isopropyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl; L1 is a connecting group provided by at least one compound selected from benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, dibenzofuran, and pyridine; optionally, L1 has at least one substituent selected from methyl, ethyl, n-propyl, isopropyl, C4 alkyl, C5 alkyl, C6 alkyl, and phenyl.

3. The use according to claim 1 or 2, wherein: The amine derivative represented by formula (I) is selected from any one of the following:

4. The use according to any one of claims 1 to 3, wherein: The light-emitting unit is a light-emitting unit in an organic electroluminescent device.

5. An organic electroluminescent device, characterized in that: The organic electroluminescent device is provided with a first electrode, a second electrode and a light-emitting unit located between the first electrode and the second electrode, and the light-emitting unit includes a first light-emitting portion, a second light-emitting portion and a first charge generation layer located between the first light-emitting portion and the second light-emitting portion. The first charge generation layer comprises at least one of the amine derivatives represented by formula (I) in the application described in any one of claims 1 to 4 as a charge generation material.

6. The organic electroluminescent device according to claim 5, wherein: The first light-emitting portion includes a hole injection layer, a first hole transport layer, a first light-emitting layer, and a first electron transport layer; and The second light-emitting portion includes a second hole transport layer, a second light-emitting layer, and a second electron transport layer.

7. The organic electroluminescent device according to claim 5 or 6, wherein: The charge generating material contains an n-type charge generating material and a p-type charge generating material, and the n-type charge generating material contains an amine derivative represented by the formula (I); Preferably, in the charge generating material, the weight ratio of the n-type charge generating material to the p-type charge generating material is 1:0.1-2.

8. The organic electroluminescent device according to claim 7, wherein: The charge generating material further contains at least one doping metal selected from Yb, Li, Ca and Mg; Preferably, based on the total amount of the n-type charge generating material, the content ratio of the doping metal is 1-10 wt %.

9. The organic electroluminescent device according to claim 8, wherein: The doping metal is located in a layer of the charge generating material where the n-type charge generating material is located.

10. The organic electroluminescent device according to claim 8, wherein: The doping metal is located on the upper surface and / or the lower surface of the layer where the n-type charge generating material of the charge generating material is located.

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