WO2023241569A1 - Aza-adamantane compound and organic electroluminescent element - Google Patents

Aza-adamantane compound and organic electroluminescent element Download PDF

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WO2023241569A1
WO2023241569A1 PCT/CN2023/099910 CN2023099910W WO2023241569A1 WO 2023241569 A1 WO2023241569 A1 WO 2023241569A1 CN 2023099910 W CN2023099910 W CN 2023099910W WO 2023241569 A1 WO2023241569 A1 WO 2023241569A1
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substituted
unsubstituted
aryl
aryl group
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曹建华
姜卫东
张九敏
王志杰
谢佩
张海威
边坤
戴雄
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上海八亿时空先进材料有限公司
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Definitions

  • the present invention relates to the technical field of organic electroluminescent materials, and in particular to an azaadamantane compound and its application in organic electroluminescent elements.
  • organic luminescence refers to the phenomenon of emitting light when electric energy is applied to an organic substance; that is, when an organic layer is arranged between an anode and a cathode, if a voltage is applied between the two electrodes, holes will be injected from the anode. To the organic layer, electrons are injected from the cathode to the organic layer; when the injected holes and electrons meet, excitons are formed. When the excitons transition to the ground state, they emit light and heat.
  • the object of the present invention is to provide an azaadamantane compound.
  • the organic electroluminescent element prepared by using the azaadamantane compound can significantly reduce the driving voltage, improve the luminous efficiency and life; another object of the present invention is to provide the azaadamantane compound. Applications of heteroadamantane compounds.
  • the present invention provides the following technical solutions:
  • the invention provides an azaadamantane compound, the structural formula of which is shown in formula (I):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from hydrogen, deuterium, halogen, nitrile, C 1 -C 40 alkyl, C 3 -C 40 cycloalkyl or branched alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 fused ring aryl, substituted or unsubstituted C 6 - A group consisting of a C 60 arylamine group, a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, or a group represented by formula (II). Any two or more adjacent substituents are optional. join or fuse to form substituted or unsubstituted rings;
  • Ar 1 and Ar 2 are each independently selected from a C 1 -C 40 alkyl group, a C 3 -C 40 cycloalkyl group or a branched alkyl group, a substituted or unsubstituted C 6 -C 60 aryl group, A group consisting of a substituted or unsubstituted C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, Ar 1.
  • Ar 2 can be arbitrarily joined or fused to form a substituted or unsubstituted ring;
  • n is selected from an integer from 0 to 5;
  • L 1 is selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, tert-butyl base, phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, dibenzothiophene, substituted or unsubstituted C 6 -C 60 Arylamine group, substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, or a group represented by formula (II), and in R 1 , R 2 , R 3 , R 4 , R 5 , At least one of R 6 , R 7 , and R 8 is a group represented by formula (II), or any two or more adjacent substituents may be optionally joined or fused to form a substituted or
  • Ar 1 and Ar 2 are each independently selected from the group consisting of a substituted or unsubstituted C 6 -C 60 aryl group and a substituted or unsubstituted C 6 -C 60 arylamine group.
  • said m is selected from 0, 1 or 2.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, deuterium, fluorine, nitrile group, substituted or unsubstituted C 6 -
  • the aryl group and heterocyclic aryl group are selected from the group consisting of the following groups: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, aiphenyl, terphenyl, tetraphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydrogen Pyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, trimeric indene, isotrimeric indene, spirotrimeric indene, spiroisotrimeric Indene, furan, benzofuran, isobenzofuran, dibenz
  • the L 1 is selected from a single bond or a group consisting of the following groups III-1 to III-15:
  • Z 11 and Z 12 are each independently selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidine group, hydrazine group, hydrazone group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonic acid Salt, phosphate group or its phosphate, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 3 -C 60 cycloalkyl group, C 3 -C 60 cycloalkenyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a group consisting of substituted or unsubstituted C 2
  • Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a substituted or unsubstituted C 6 -C 60 aryl sulfide group.
  • T 2 is selected from O, S, CR'R" or NAr';
  • R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl group, C 1 -C 60 heteroalkyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted A group consisting of C 6 -C 60 arylamine groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can optionally be joined or fused to form another one or more Substituted or unsubstituted rings, containing or not containing one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R', R" is methyl, phenyl or fluorenyl ;
  • Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of a C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
  • the Ar 1 and Ar 2 are selected from the group consisting of the following groups:
  • the hydrogen atom on each substituent may be substituted by a substituent selected from hydrogen deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or its carboxylic acid Salt, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkyl, C 3 -C 60 cycloalkenyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or A group consisting of an unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a substituted or unsubstituted C 2
  • G is selected from O, S, CR’R” or NAr’;
  • R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl group, C 1 -C 60 heteroalkyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted A group consisting of C 6 -C 60 arylamine groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can optionally be joined or fused to form another one or more Substituted or unsubstituted rings, containing or not containing one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R', R" is methyl, phenyl or fluorenyl ;
  • Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of a C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
  • the aryl group, condensed ring aryl group or heterocyclic aryl group of the present invention particularly refers to groups derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, aiphenyl, terphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis Or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, trimer indene, isotrimeric indene, spiro trimer indene, spiro isotrimeric indene, furan, Benzofuran, isobenz
  • substituted or unsubstituted means one selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group or its carboxyl group.
  • the aryl sulfide group and the C 2 -C 60 heterocyclic aryl group are substituted or unsubstituted by one or more substituents, or are connected by two or more substituents among the above-exemplified substituents. Superseded or not superseded.
  • the *-NAr 1 Ar 2 is selected from the group consisting of the following formulas B1 to B15:
  • *—G—* is selected from single bond, *—O—*, *—S—* or one of the following structures:
  • Each R 7 in the structure B1 to B15 is independently selected from hydrogen, deuterium, halogen, nitrile group, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group or branched chain alkyl group.
  • the plurality of substituents may be the same or different from each other.
  • the azaadamantane compound is selected from the group consisting of the following D253 to D525:
  • *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
  • the present invention also provides a method for preparing the above-mentioned azaadamantane compound, as shown in Scheme 1 to Scheme 2:
  • X 1 , X 2 , and X 3 are H, Cl, Br, I or OTf; R is H, alkyl or aryl; other symbols used are as defined in formula (I),
  • the raw materials for synthesizing the compound represented by formula (I) can be purchased through commercial channels.
  • the principle, operation process, conventional post-treatment, column purification, recrystallization purification and other means are well known to synthetic practitioners in the field and can be Implement the synthesis process and obtain the target product.
  • the compound of formula (I) is prepared from X1- substituted biphenyl through substitution reaction, condensation reaction, SUZUKI coupling and other reactions.
  • the intermediate Ar 1 Ar 2 N-(L) m B(OH) 2 or Ar 1 Ar 2 NH is prepared by palladium-catalyzed or base-catalyzed coupling reaction.
  • a palladium catalyst that can be used for palladium-catalyzed coupling reaction, it can be selected from: Pd(P- t Bu 3 ) 2 , Pd(PPh 3 ) 4 , Pd 2 (dba) 3 , Pd 2 (dba) 3 CHCl 3 , PdCl 2 (PPh 3 ) 2 , PdCl 2 (CH 3 CN) 2 , Pd(OAc) 2 , Pd(acac) 2 , Pd/C, PdCl 2 , [Pd(allyl)Cl] 2, etc., or use two mixture of one or more species.
  • the base used in the palladium-catalyzed coupling reaction or the base-catalyzed coupling reaction can be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amyloxide, sodium ethoxide, sodium methoxide, carbonic acid Sodium, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, etc., as well as one or a mixture of two or more thereof.
  • the coupling reaction can be carried out in an organic solvent, wherein the organic solvent can be selected from: diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol Ether solvents such as methyl ether, diglyme, or anisole, aromatic hydrocarbon agents such as benzene, toluene, and xylene, chlorobenzene, dichlorobenzene, N,N-dimethylformamide, N,N- One type or a mixture of two or more types of dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, etc. can be used.
  • the organic solvent can be selected from: diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethylene glycol
  • the present invention also provides an organic electroluminescent material, the raw material of which includes the above-mentioned azaadamantane compound; the organic electroluminescent material including the azaadamantane compound of the present invention has the ability of carrier transport.
  • the organic electroluminescent material is a hole injection layer material, a hole transport layer material, a hole blocking layer material, a light emitting layer material, an electron transport layer material, an electron injection layer material, a capping layer (referred to as a CPL layer) ) material or electron blocking layer material.
  • the present invention also provides the application of the above-mentioned azaadamantane compound in preparing organic electroluminescent elements.
  • the present invention also provides an organic electroluminescent element, which includes: a first electrode, a second electrode, a CPL layer, and one or more organic layers placed between the first electrode and the second electrode; At least one of the organic layer and the CPL layer includes the above-mentioned azaadamantane compound.
  • the organic electroluminescent element includes a cathode, an anode, CPL and at least one light-emitting layer. In addition to these layers, it may contain further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, excitation layers, etc. sub-blocking layer, electron blocking layer and/or charge generating layer. An intermediate layer having, for example, an exciton blocking function can also be introduced between the two luminescent layers. However, it should be noted that each of these layers does not necessarily have to be present.
  • the organic electroluminescent element described here may include one light-emitting layer, or it may include a plurality of light-emitting layers.
  • a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer.
  • Particularly preferred are systems with three luminescent layers, wherein the three layers can exhibit blue, green and red luminescence. If more than one luminescent layer is present, according to the invention at least one of these layers contains a compound of the invention.
  • the organic electroluminescent element according to the present invention does not include a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, that is, the light emitting layer and the hole injection layer or The anode is directly adjacent, and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or the cathode.
  • OLEDs comprise at least one organic layer disposed between and electrically connected to an anode and a cathode.
  • FIG. 1 shows a schematic diagram of an organic light-emitting device 100. Illustrations are not necessarily to scale.
  • the device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, an electron transport layer 107, an electron injection layer 108, a cathode 109, and a capping layer (CPL). )110.
  • Device 100 may be fabricated by sequentially depositing the described layers.
  • FIG. 2 shows a schematic diagram of an organic light-emitting device 200 including two light-emitting layers.
  • the device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, and a hole transport layer 209 , the second light-emitting layer 210, the electron transport layer 211, the electron injection layer 212 and the cathode 213.
  • Device 200 may be prepared by sequentially depositing the described layers.
  • the device 200 has two light-emitting layers of the same light color.
  • materials similar to those described with respect to device 100 may be used.
  • Figure 2 provides an example of how some layers may be added from the structure of device 100.
  • hole transport layer 204 transports holes and injects holes into light emitting layer 205, and may be described as a hole transport layer or an electron blocking layer.
  • an OLED may be described as having an organic layer disposed between a cathode and an anode. This organic layer may comprise a single layer or may further comprise multiple layers of different organic materials as described for example in Figures 1 and 2.
  • OLEDs containing polymeric materials may also be used, such as PLEDs containing polymeric materials.
  • an OLED with a single organic layer or multiple stacks may be used.
  • OLED structures can depart from the simple layered structure illustrated in Figures 1 and 2.
  • the substrate may include angled reflective surfaces to improve light coupling.
  • the organic electroluminescent element of the present invention in addition to one or more of the above-mentioned organic layers containing the above-described indene derivative, the organic layer and the electrode can be formed using materials and methods known in the art. manufacture.
  • the substance that can be used as an anode included in the organic electroluminescent element according to the present invention is not particularly limited.
  • metals such as vanadium, chromium, copper, zinc, gold, aluminum, or alloys thereof can be used. ;
  • Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; polythiophene, poly(3-methyl) Conductive polymers such as thiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole and polyaniline; and carbon black, etc.
  • the material that can be used as the cathode included in the organic electroluminescent element according to the present invention is not particularly limited.
  • magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum can be used.
  • silver, tin or lead and other metals or their alloys; and multi-layer structure materials such as LiF/Al or Li 2 O/Al.
  • the substance that can be used as the substrate included in the organic electroluminescent element according to the present invention is not particularly limited.
  • silicon wafers, quartz, glass plates, metal plates or plastic films and sheets can be used.
  • organic electroluminescent components are preferred in which one or more layers can be applied by means of a sublimation method, wherein the layers are deposited by vapor deposition in a vacuum sublimation device at an initial pressure of less than 10 -5 Pa, preferably less than 10 -6 Pa. to apply the material.
  • the initial pressure may also be even lower, for example below 10 -7 Pa.
  • organic electroluminescent components in which one or more layers can also be applied by means of an organic vapor deposition method or by means of carrier gas sublimation, wherein the material is applied at a pressure of between 10 -5 Pa and 1 Pa .
  • a particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
  • organic electroluminescent elements produced from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithography, photothermography, thermal transfer printing, spray printing, etc. Ink printing or nozzle printing to produce one or more layers.
  • Soluble compounds can be obtained, for example, by appropriately substituting compounds represented by formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers.
  • hybrid methods are possible, in which one or more layers are applied, for example, from solution and one or more further layers are applied by vapor deposition.
  • the invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, comprising applying at least one layer by means of a sublimation method and/or applying at least one layer by means of an organic vapor deposition method or by means of carrier gas sublimation , and/or at least one layer is applied from solution by spin coating or by means of printing methods.
  • the present invention relates to compounds comprising at least one compound of the invention indicated above.
  • the compounds may preferably also comprise other compounds.
  • Processing the compounds of the invention from the liquid phase requires processing of formulations of the compounds of the invention, which may be, for example, solutions, dispersions or emulsions.
  • formulations of the compounds of the invention which may be, for example, solutions, dispersions or emulsions.
  • mixtures of two or more solvents may preferably be used.
  • Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, Tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenone, 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, ⁇ -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohe
  • the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a CPL layer or an electron blocking layer.
  • the raw materials used in the present invention can be purchased from commercial stores. Any range recorded in the present invention includes the end value and any value between the end value and the end value or any value between the end value. Any subrange formed by.
  • the invention also relates to mixtures comprising at least one compound of formula (I) or the preferred embodiments described above and at least one further compound. If the compounds according to the invention are used as matrix materials, the other compounds can be fluorescent or phosphorescent emitters. The mixture may then additionally contain other materials as additional matrix materials.
  • the invention also relates to the use of the compounds of the invention in electronic components. Preferably, as mentioned above and below, the compounds according to the invention are used in the hole transport layer or as matrix material in the emissive layer.
  • the compounds according to the invention and the electronic components obtainable therefrom, in particular organic electroluminescent components differ from the prior art by one or more of the following surprising advantages:
  • the electronic components obtainable using the compounds of the present invention exhibit high efficiency, especially high luminous efficiency and high external quantum efficiency.
  • the compounds of the present invention provide low operating voltage.
  • the compounds according to the invention can be processed using conventional methods, so that cost advantages can also be achieved.
  • the films obtainable using the compounds of the present invention exhibit excellent qualities, especially in terms of film uniformity.
  • the compounds of the invention can be produced in a very fast and easy manner using conventional methods, so that cost advantages can also be achieved.
  • FIG. 1 shows a schematic diagram of an organic light-emitting device 100. Illustrations are not necessarily to scale.
  • the device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, an electron transport layer 107, an electron injection layer 108, a cathode 109, and a capping layer (CPL). )110.
  • Device 100 may be fabricated by sequentially depositing the described layers.
  • FIG. 2 shows a schematic diagram of an organic light-emitting device 200 with two light-emitting layers.
  • the device includes a substrate 201, an anode 202, hole injection 203, hole transport layer 204, first light-emitting layer 205, electron transport layer 206, charge generation layer 207, hole injection layer 208, hole transport layer 209, The second light-emitting layer 210, the electron transport layer 211, the electron injection layer 212 and the cathode 213.
  • Device 200 may be prepared by sequentially depositing the described layers.
  • the luminescence peak shapes of the first luminescent layer and the second luminescent layer may be overlapping or cross-overlapping or non-overlapping.
  • materials similar to those described with respect to device 100 may be used.
  • Figure 2 provides an example of how some layers may be added from the structure of device 100.
  • test instruments and methods for performance testing of OLED materials and components in the following examples are as follows:
  • Luminance and chromaticity coordinates tested using spectral scanner PhotoResearch PR-715;
  • the preparation method of compound D275 includes the following steps:
  • Int-1 12.0mmol of Int-1 was dissolved in 60mL of xylene, and under nitrogen protection, 10.0mmol of N-biphenyl-4'-(9-carbazolyl)-biphenyl-4-amine and 15.0mmol of Sodium tert-butoxide, 0.1 mmol copper iodide, 0.1 mmol Pd 2 (dba) 3 catalyst, then add 0.2 mmol Xantphos, raise the temperature to 110°C and stir for 16 hours, then cool to room temperature, add 20 mL of water to dilute, Extract with toluene, collect the organic phase, dry, filter, and concentrate the filtrate to dryness under reduced pressure.
  • *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
  • *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
  • *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
  • the preparation method of compound D483 includes the following steps:
  • *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
  • An organic electroluminescent element 100 has a structure as shown in Figure 1, including a substrate 101, an anode layer 102 provided on the substrate 101, a hole injection layer 103 provided on the anode layer 102, and a hole injection layer 103 provided on the anode layer 102.
  • the preparation method of the cathode layer 109 and the CPL layer 110 disposed on the cathode layer 109 includes the following steps:
  • Example 6 Following the same steps as in Example 6, replace RH12 in step 5) with the compound represented by formula (I) of the present invention, and obtain the OLED component of the present invention.
  • the performance test comparison results of the component are shown in Table 8.
  • a digital source meter and a luminance meter were used to measure the driving voltage and current efficiency of the organic electroluminescent elements prepared in Examples 6 to 10, as well as the lifetime of the elements. Specifically, increase the voltage at a rate of 0.1V per second, measure the voltage when the current density of the organic electroluminescent element reaches 10mA/ cm2 , which is the driving voltage, and measure the brightness at this time; the ratio of brightness to current density That is the current efficiency; the LT95% life test is as follows: use a luminance meter to maintain a constant current at a brightness of 1000cd/ m2 , and measure the time for the brightness of the organic electroluminescent element to decay to 950cd/ m2 , in hours, all data All are normalized results of comparison components.
  • the light-emitting element prepared by using the azaadamantane compound of the present invention as a hole transport layer material also has a reduced driving voltage, a significant improvement in luminous efficiency, and a LT95% lifespan under the condition of a current density of 10 mA/cm 2 It has obvious advantages and is a hole transport layer material with good performance.
  • azaadamantane contains nitrogen atoms of lone electron pairs, which has less impact on molecular film formation. Compared with adamantane, the hole mobility is increased, so its hole mobility is improved. It is superior to the comparative compound HT08 in terms of molecular film formation and carrier transport properties, and has more advantages in component performance and lifespan.
  • the light-emitting element prepared by using the azaadamantane compound of the present invention as an electron blocking layer material also has a lower driving voltage and a significantly improved luminous efficiency under the condition of a current density of 10 mA/ cm2 , and the LT95% lifespan has a great The amplitude is improved and it is an electronic material with excellent performance.
  • azaadamantane contains nitrogen atoms with lone electron pairs, which is more conducive to transporting holes and blocking electrons, reducing the probability of exciton formation in the non-emitting layer. Therefore, its performance in light-emitting components is even better.
  • the light-emitting element prepared by using the azaadamantane compound of the present invention as the host material of the light-emitting layer also has a reduced driving voltage and a significant improvement in luminous efficiency under the condition of a current density of 10 mA/ cm2 , and the LT95% life span is It has been greatly improved and is a light-emitting layer material with excellent performance.
  • the difference is that the steric hindrance of dimethyl fluorene is small.
  • Replacing the dimethyl group with azaadamantane not only increases the steric hindrance, but also helps to block the transport of holes. Therefore, the molecules constitute D-A bipolarity, and the carrier transmission in the light-emitting layer is more balanced, which is more conducive to the formation of excitons in the light-emitting layer, so its performance in light-emitting elements is better.
  • Me is methyl; Ph is phenyl; PhPh is biphenyl; Nap is naphthyl; FR is fluorenyl.
  • the light-emitting element prepared by using the azaadamantane compound of the present invention as an electron transport layer material also has a lower driving voltage and a significantly improved luminous efficiency under the condition of a current density of 10 mA/ cm2 , and the LT95% lifespan has a great The amplitude is improved and it is an electronic material with excellent performance.
  • azaadamantane contains nitrogen atoms with lone electron pairs.
  • the introduction of nitrogen atoms enhances the three-dimensional rigidity of adamantane, which is more conducive to the transmission of electrons and excitons. formed, so it performs better in light-emitting components.

Abstract

The present invention relates to the technical field of organic electroluminescent materials, in particular to an aza-adamantane compound and an organic electroluminescent element. The structural formula of the aza-adamantane compound is as shown in formula (I). The aza-adamantane compound as shown in formula (I) provided in the present invention is applied to an organic electroluminescent element, whereby the driving voltage can be significantly reduced, and the luminous efficiency and the service life can be improved.

Description

一种氮杂金刚烷化合物、有机电致发光元件An azaadamantane compound and an organic electroluminescent element
交叉引用cross reference
本申请要求2022年6月16日提交的专利名称为“一种氮杂金刚烷化合物、有机电致发光元件”的第202210684296.8号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。This application claims priority to Chinese patent application No. 202210684296.8, which was filed on June 16, 2022 and is titled "Azaadamantane compound, organic electroluminescent element", the entire disclosure of which is incorporated herein by reference in its entirety. .
技术领域Technical field
本发明涉及有机电致发光材料技术领域，尤其涉及一种氮杂金刚烷化合物及其在有机电致发光元件中的应用。The present invention relates to the technical field of organic electroluminescent materials, and in particular to an azaadamantane compound and its application in organic electroluminescent elements.
背景技术Background technique
一般而言，有机发光现象是指在对有机物质施加电能时发出光的现象；即在阳极与阴极之间配置有机层时，如果在两个电极之间施加电压，则空穴会从阳极注入至有机层，电子会从阴极注入至有机层；当所注入的空穴和电子相遇时，会形成激子，当该激子跃迁至基态时，会发出光和热。Generally speaking, organic luminescence refers to the phenomenon of emitting light when electric energy is applied to an organic substance; that is, when an organic layer is arranged between an anode and a cathode, if a voltage is applied between the two electrodes, holes will be injected from the anode. To the organic layer, electrons are injected from the cathode to the organic layer; when the injected holes and electrons meet, excitons are formed. When the excitons transition to the ground state, they emit light and heat.
最近几年有机电致发光显示技术已趋于成熟，一些产品已进入市场，但在产业化过程中，仍有许多问题亟待解决。特别是用于制作元件的各种有机材料，其载流子注入和传输性能、材料电发光性能、使用寿命、色纯度、各种材料之间及与各电极之间的匹配等，尚有许多问题还未解决；尤其是发光元件的发光效率和使用寿命还达不到实用化要求，这大大限制了OLED技术的发展。而利用三线态发光的金属配合物磷光材料具有高的发光效率，其绿光和红光材料已经达到使用要求，但是金属配合物磷光材料要求具有高三线态能级的磷光材料或空穴材料与之匹配。因此，开发具有高三线态能级的磷光材料或空穴材料是当前OLED发展的迫切需求。In recent years, organic electroluminescent display technology has matured, and some products have entered the market. However, there are still many problems that need to be solved during the industrialization process. In particular, there are many problems in the various organic materials used to make components, including their carrier injection and transmission properties, material electroluminescence properties, service life, color purity, matching between various materials and between various electrodes, etc. The problem has not yet been solved; in particular, the luminous efficiency and service life of light-emitting components have not met practical requirements, which has greatly restricted the development of OLED technology. Metal complex phosphorescent materials that utilize triplet luminescence have high luminous efficiency, and their green and red light materials have met the requirements for use. However, metal complex phosphorescent materials require phosphorescent materials or hole materials with high triplet energy levels and match. Therefore, the development of phosphorescent materials or hole materials with high triplet energy levels is an urgent need for the current development of OLEDs.
在目前的技术发展下，无论是对于荧光材料还是对于磷光材料，特别是在用于有机电致发光元件中的工作电压、效率和寿命方面和在升华期间的热稳定性方面，都还需要改进。Under the current technological development, both fluorescent materials and phosphorescent materials still need to be improved, especially in terms of operating voltage, efficiency and lifetime used in organic electroluminescent components and thermal stability during sublimation. .
由此，为了克服如上所述的以往技术问题而进一步提高有机电致发光元件的特性，继续要求对于在有机电致发光元件中可用作磷光材料或空穴材料的更加稳定且有效的物质的开发。Therefore, in order to overcome the conventional technical problems described above and further improve the characteristics of organic electroluminescent elements, there is a continuing demand for more stable and effective substances that can be used as phosphorescent materials or hole materials in organic electroluminescent elements. development.
鉴于此，特提出本发明。In view of this, the present invention is proposed.
发明内容Contents of the invention
本发明的目的在于提供一种氮杂金刚烷化合物，利用该氮杂金刚烷化合物制备的有机电致发光元件可显著降低驱动电压、提高发光效率和寿命；本发明的另一目的在于提供该氮杂金刚烷化合物的应用。The object of the present invention is to provide an azaadamantane compound. The organic electroluminescent element prepared by using the azaadamantane compound can significantly reduce the driving voltage, improve the luminous efficiency and life; another object of the present invention is to provide the azaadamantane compound. Applications of heteroadamantane compounds.
具体地，本发明提供以下技术方案：Specifically, the present invention provides the following technical solutions:
本发明提供一种氮杂金刚烷化合物，其结构式如式(I)所示：
The invention provides an azaadamantane compound, the structural formula of which is shown in formula (I):
R1、R2、R3、R4、R5、R6、R7、R8各自独立地选自由氢、氘、卤素、腈基、C1-C40的烷基、C3-C40的环烷基或带有支链的烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、取代或未取代的C2-C60杂环芳基、或者式(II)所示基团组成的群组，任意相邻的两个或多个取代基可任选的接合或稠合形成取代或未取代的环；
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from hydrogen, deuterium, halogen, nitrile, C 1 -C 40 alkyl, C 3 -C 40 cycloalkyl or branched alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 fused ring aryl, substituted or unsubstituted C 6 - A group consisting of a C 60 arylamine group, a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, or a group represented by formula (II). Any two or more adjacent substituents are optional. join or fuse to form substituted or unsubstituted rings;
Ar1、Ar2各自独立地选自由C1-C40的烷基、C3-C40的环烷基或带有支链的烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组，Ar1、Ar2可以任意的接合或稠合形成取代或未取代的环；Ar 1 and Ar 2 are each independently selected from a C 1 -C 40 alkyl group, a C 3 -C 40 cycloalkyl group or a branched alkyl group, a substituted or unsubstituted C 6 -C 60 aryl group, A group consisting of a substituted or unsubstituted C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, Ar 1. Ar 2 can be arbitrarily joined or fused to form a substituted or unsubstituted ring;
m选自0～5的整数；m is selected from an integer from 0 to 5;
L1选自单键、取代或未取代的C6-C60的亚芳基、或者取代或未取代的C2-C60亚杂芳基；L 1 is selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
*—表示R1、R2、R3、R4、R5、R6、R7或R8与L1的连接键。*—Indicates the connection key between R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 and L 1 .
进一步地，所述R1、R2、R3、R4、R5、R6、R7、R8各自独立地选自由氢、氘、氟、腈基、甲基、乙基、叔丁基、苯基、联苯基、三联苯基、萘基、菲基、三亚苯基、咔唑基、芴基、二苯并呋喃、二苯并噻吩、取代或未取代的C6-C60芳胺基、取代或未取代的C2-C60杂环芳基、或者式(II)所示基团组成的群组，并且在R1、R2、R3、R4、R5、R6、R7、R8中至少有一者为式(II)所示基团，或者任意相邻的两个或多个取代基可任选的接合或稠合形成取代或未取代的环。Further, the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, tert-butyl base, phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, dibenzothiophene, substituted or unsubstituted C 6 -C 60 Arylamine group, substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, or a group represented by formula (II), and in R 1 , R 2 , R 3 , R 4 , R 5 , At least one of R 6 , R 7 , and R 8 is a group represented by formula (II), or any two or more adjacent substituents may be optionally joined or fused to form a substituted or unsubstituted ring.
进一步地，所述Ar1、Ar2各自独立地选自由取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳胺基组成的群组。Further, the Ar 1 and Ar 2 are each independently selected from the group consisting of a substituted or unsubstituted C 6 -C 60 aryl group and a substituted or unsubstituted C 6 -C 60 arylamine group.
进一步地，所述m选自0、1或2。Further, said m is selected from 0, 1 or 2.
进一步地，所述R1、R2、R3、R4、R5、R6、R7、R8各自独立地选自由氢、氘、氟、腈基、取代或未取代的C6-C60芳基、取代或未取代的C2-C60杂环芳基组成的群组，并且在R1、R2、R3、R4、R5、R6、R7、R8中至少有一者为取代或未取代的C6-C60芳基或取代或未取代的C2-C60杂环芳基，或任意相邻的两个或多个取代基可任选的接合或稠合形成取代或未取代的环。Further, the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, deuterium, fluorine, nitrile group, substituted or unsubstituted C 6 - The group consisting of C 60 aryl, substituted or unsubstituted C 2 -C 60 heterocyclic aryl, and in R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 At least one of them is a substituted or unsubstituted C 6 -C 60 aryl group or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, or any two or more adjacent substituents may be optionally combined or Fused to form substituted or unsubstituted rings.
作为优选，所述芳基、杂环芳基选自由以下基团组成的群组：苯、萘、蒽、苯并蒽、菲、芘、苝、荧蒽、并四苯、并五苯、苯并芘、联苯、偶苯、三联苯、四联苯、三聚苯、芴、螺二芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、顺式或反式茚并咔唑、顺式或反式吲哚并咔唑、三聚茚、异三聚茚、螺三聚茚、螺异三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并[5,6]喹啉、苯并[6,7]喹啉、苯并[7,8]喹啉、吩噻嗪、吩噁嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、噁唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、异噁唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、六氮杂苯并菲、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1,5-二氮杂蒽、2,7-二氮杂芘、2,3-二氮杂芘、1,6-二氮杂芘、1,8-二氮杂芘、4,5-二氮杂芘，4,5,9,10-四氮杂苝、吡嗪、吩嗪、吩噁嗪、吩噻嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-噁二唑、1,2,4-噁二唑、1,2,5-噁二唑、1,3,4-噁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑、1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、吲嗪、喹唑啉和苯并噻二唑或者衍生自这些体系的组合的基团。Preferably, the aryl group and heterocyclic aryl group are selected from the group consisting of the following groups: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, aiphenyl, terphenyl, tetraphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydrogen Pyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, trimeric indene, isotrimeric indene, spirotrimeric indene, spiroisotrimeric Indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline , isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyridine Azole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanzimidazole, pyridimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthraceneoxazole Azole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazabenzophenanthrene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline Phenoline, 1,5-diazapyrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5 -Diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorine ring, naphthyridine, azacarbazole, benzocarboline, Carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine , 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole or groups derived from combinations of these systems .
作为优选，所述L1选自单键或由以下III-1～III-15所示基团组成的群组：

Preferably, the L 1 is selected from a single bond or a group consisting of the following groups III-1 to III-15:

其中，in,
Z11、Z12各自独立地选自由氢、氘、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60的烷基、C2-C60的烯基、C2-C60的炔基、C1-C60的烷氧基、C3-C60的环烷烃基、C3-C60的环烯烃基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基组成的群组；Z 11 and Z 12 are each independently selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidine group, hydrazine group, hydrazone group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonic acid Salt, phosphate group or its phosphate, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 3 -C 60 cycloalkyl group, C 3 -C 60 cycloalkenyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
Z13表示取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基中的一种或多种；Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a substituted or unsubstituted C 6 -C 60 aryl sulfide group. One or more C 2 -C 60 heterocyclic aryl groups;
y1表示1-4的整数；y2表示1-6的整数；y3表示1-3的整数；y4表示1-5的整数；y1 represents an integer from 1 to 4; y2 represents an integer from 1 to 6; y3 represents an integer from 1 to 3; y4 represents an integer from 1 to 5;
T2选自O、S、CR’R”或NAr’；T 2 is selected from O, S, CR'R" or NAr';
R’、R”各自独立地选自由氢、氘、C1-C60的烷基、C1-C60的杂烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基；R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl group, C 1 -C 60 heteroalkyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted A group consisting of C 6 -C 60 arylamine groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can optionally be joined or fused to form another one or more Substituted or unsubstituted rings, containing or not containing one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R', R" is methyl, phenyl or fluorenyl ;
Ar’选自由C1-C60的烷基、C1-C60的杂烷基、C3-C60的环烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基或萘基；Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of a C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
表示取代基与主体结构的连接键。 Indicates the bond between the substituent and the main structure.
作为优选，所述Ar1、Ar2选自由以下所示基团组成的群组：
Preferably, the Ar 1 and Ar 2 are selected from the group consisting of the following groups:
其中，in,
每个取代基上的氢原子均可被取代基取代，所述取代基选自由氢氘、卤素、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60烷基、C2-C60烯基、 C2-C60炔基、C1-C60烷氧基、C3-C60环烷烃基、C3-C60环烯烃基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基组成的群组；The hydrogen atom on each substituent may be substituted by a substituent selected from hydrogen deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or its carboxylic acid Salt, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkyl, C 3 -C 60 cycloalkenyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or A group consisting of an unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group;
G选自O、S、CR’R”或NAr’；G is selected from O, S, CR’R” or NAr’;
R’、R”各自独立地选自由氢、氘、C1-C60的烷基、C1-C60的杂烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基；R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl group, C 1 -C 60 heteroalkyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted A group consisting of C 6 -C 60 arylamine groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can optionally be joined or fused to form another one or more Substituted or unsubstituted rings, containing or not containing one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R', R" is methyl, phenyl or fluorenyl ;
Ar’选自由C1-C60的烷基、C1-C60的杂烷基、C3-C60的环烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基或萘基；Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of a C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
*—表示Ar1、Ar2与N的连接键。*—Indicates the connecting bond between Ar 1 , Ar 2 and N.
本发明的芳基、稠环芳基或杂环芳基，特别是指衍生自如下物质的基团：苯、萘、蒽、苯并蒽、菲、芘、苝、荧蒽、并四苯、并五苯、苯并芘、联苯、偶苯、三联苯、三聚苯、芴、螺二芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、顺式或反式茚并咔唑、顺式或反式吲哚并咔唑、三聚茚、异三聚茚、螺三聚茚、螺异三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并[5,6]喹啉、苯并[6,7]喹啉、苯并[7,8]喹啉、吩噻嗪、吩噁嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、噁唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、异噁唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、六氮杂苯并菲、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1,5-二氮杂蒽、2,7-二氮杂芘、2,3-二氮杂芘、1,6-二氮杂芘、1,8-二氮杂芘、4,5-二氮杂芘，4,5,9,10-四氮杂苝、吡嗪、吩嗪、吩噁嗪、吩噻嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-噁二唑、1,2,4-噁二唑、1,2,5-噁二唑、1,3,4-噁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑、1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、吲嗪、喹唑啉和苯并噻二唑或者衍生自这些体系的组合的基团。The aryl group, condensed ring aryl group or heterocyclic aryl group of the present invention particularly refers to groups derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, aiphenyl, terphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis Or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, trimer indene, isotrimeric indene, spiro trimer indene, spiro isotrimeric indene, furan, Benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline , acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyrazole, indazole , imidazole, benzimidazole, naphthoimidazole, phenanzimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthrazooxazole, phenanthro Oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazabenzophenanthrene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene Pyrene, 4,5,9,10-tetraazoperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorine ring, naphthyridine, azacarbazole, benzocarboline, carboline, phenanthrene Roroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2, 5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3, 4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2 , 3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole or groups derived from combinations of these systems.
本发明中，“取代或未取代的”这一用语是指，被选自氢、氘、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60的烷基、C2-C60的烯基、C2-C60的炔基、C1-C60的烷氧基、C3-C60的环烷基、C3-C60的环烯基、C6-C60的芳基、C6-C60的芳氧基、C6-C60的芳硫醚基和C2-C60的杂环芳基中的1个以上的取代基取代或未取代，或者被上述示例的取代基中的2个以上的取代基连接而成的取代基取代或未取代。In the present invention, the term "substituted or unsubstituted" means one selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group or its carboxyl group. Acid salt, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 3 -C 60 cycloalkyl group, C 3 -C 60 cycloalkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryloxy group, C 6 -C 60 The aryl sulfide group and the C 2 -C 60 heterocyclic aryl group are substituted or unsubstituted by one or more substituents, or are connected by two or more substituents among the above-exemplified substituents. Superseded or not superseded.
根据本发明的实施例，所述*—NAr1Ar2选自由下述式B1～B15组成的群组：

According to an embodiment of the present invention, the *-NAr 1 Ar 2 is selected from the group consisting of the following formulas B1 to B15:

其中，*—G—*选自单键、*—O—*、*—S—*或下述结构中的一种：
Among them, *—G—* is selected from single bond, *—O—*, *—S—* or one of the following structures:
*—和—*表示与两个苯环的连接键；*—and—* represent the connecting bonds with two benzene rings;
所述B1～B15结构中的每个R7各自独立地选自由氢、氘、卤素、腈基、C1-C40的烷基、C3-C40的环烷基或带有支链的烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、取代或未取代的C2-C60杂环芳基组成的群组，此时，当取代基为一种以上时，多个取代基彼此相同或不同。Each R 7 in the structure B1 to B15 is independently selected from hydrogen, deuterium, halogen, nitrile group, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group or branched chain alkyl group. Alkyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 fused ring aryl group, substituted or unsubstituted C 6 -C 60 arylamine group, substituted or unsubstituted A group consisting of C 2 -C 60 heterocyclic aryl groups. In this case, when there are more than one substituents, the plurality of substituents may be the same or different from each other.
作为优选，所述氮杂金刚烷化合物选自由以下D253至D525组成的群组：










Preferably, the azaadamantane compound is selected from the group consisting of the following D253 to D525:










其中，*—T3—*选自*—O—*、*—S—*或下述结构中的一种：
Among them, *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
*—和—*表示连接键。 *—and—* represent connection keys.
本发明还提供以上所述的氮杂金刚烷化合物的制备方法，如方案1～方案2所示：The present invention also provides a method for preparing the above-mentioned azaadamantane compound, as shown in Scheme 1 to Scheme 2:
方案1，
plan 1,
方案2，
Scenario 2,
在方案1、2中，X1、X2、X3为H、Cl、Br、I或OTf；R为H、烷基或芳基；其它所用符号如式(I)中所定义，In schemes 1 and 2, X 1 , X 2 , and X 3 are H, Cl, Br, I or OTf; R is H, alkyl or aryl; other symbols used are as defined in formula (I),
合成式(I)所示化合物的原料可通过商业途径购买而得，此方法原理、操作过程、常规后处理、过柱纯化、重结晶提纯等手段是本领域合成从员所熟知的，完全可以实现合成过程，得到目标产物。The raw materials for synthesizing the compound represented by formula (I) can be purchased through commercial channels. The principle, operation process, conventional post-treatment, column purification, recrystallization purification and other means are well known to synthetic practitioners in the field and can be Implement the synthesis process and obtain the target product.
具体地，式(I)的化合物是由X1取代的联苯经过取代反应、缩合反应、SUZUKI偶联等反应制备化合物式(I)。中间体Ar1Ar2N-(L)mB(OH)2或Ar1Ar2NH通过钯催化或碱催化偶联反应制备。Specifically, the compound of formula (I) is prepared from X1- substituted biphenyl through substitution reaction, condensation reaction, SUZUKI coupling and other reactions. The intermediate Ar 1 Ar 2 N-(L) m B(OH) 2 or Ar 1 Ar 2 NH is prepared by palladium-catalyzed or base-catalyzed coupling reaction.
作为可用于钯催化偶联反应的钯催化剂可选自：Pd(P-tBu3)2、Pd(PPh3)4、Pd2(dba)3、Pd2(dba)3CHCl3、PdCl2(PPh3)2、PdCl2(CH3CN)2、Pd(OAc)2、Pd(acac)2、Pd/C、PdCl2、[Pd(allyl)Cl]2等任意一种，或使用两种或更多种的混合物。As a palladium catalyst that can be used for palladium-catalyzed coupling reaction, it can be selected from: Pd(P- t Bu 3 ) 2 , Pd(PPh 3 ) 4 , Pd 2 (dba) 3 , Pd 2 (dba) 3 CHCl 3 , PdCl 2 (PPh 3 ) 2 , PdCl 2 (CH 3 CN) 2 , Pd(OAc) 2 , Pd(acac) 2 , Pd/C, PdCl 2 , [Pd(allyl)Cl] 2, etc., or use two mixture of one or more species.
此外，钯催化的偶联反应或碱催化的偶联反应使用的碱可选自：叔丁醇钠、叔丁醇钾、氢化钠、氢化锂、叔戊醇钠、乙醇钠、甲醇钠、碳酸钠、碳酸钾、碳酸铯、锂、氢化钾、三乙胺、氟化铯等，以及其中一种或两种或更多种的混合物。In addition, the base used in the palladium-catalyzed coupling reaction or the base-catalyzed coupling reaction can be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amyloxide, sodium ethoxide, sodium methoxide, carbonic acid Sodium, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, etc., as well as one or a mixture of two or more thereof.
偶联反应可以在有机溶剂中进行，其中有机溶剂可选自：乙醚、四氢呋喃、2-甲基四氢呋喃、1,4-二氧六环、乙二醇乙醚、乙二醇二乙醚、乙二醇甲醚、二甘醇二乙醚、或苯甲醚等醚类溶剂、苯、甲苯、二甲苯等芳烃类剂、氯苯、二氯苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、环丁砜等，可以使用一种或两种以上的混合物。The coupling reaction can be carried out in an organic solvent, wherein the organic solvent can be selected from: diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol Ether solvents such as methyl ether, diglyme, or anisole, aromatic hydrocarbon agents such as benzene, toluene, and xylene, chlorobenzene, dichlorobenzene, N,N-dimethylformamide, N,N- One type or a mixture of two or more types of dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, etc. can be used.
本发明还提供一种有机电致发光材料，其原料包括以上所述的氮杂金刚烷化合物；包括本发明的氮杂金刚烷化合物的有机电致发光材料具有载流子传输的能力。The present invention also provides an organic electroluminescent material, the raw material of which includes the above-mentioned azaadamantane compound; the organic electroluminescent material including the azaadamantane compound of the present invention has the ability of carrier transport.
作为优选，所述有机电致发光材料为空穴注入层材料、空穴传输层材料、空穴阻挡层材料、发光层材料、电子传输层材料、电子注入层材料、封盖层(简称CPL层)材料或电子阻挡层材料。Preferably, the organic electroluminescent material is a hole injection layer material, a hole transport layer material, a hole blocking layer material, a light emitting layer material, an electron transport layer material, an electron injection layer material, a capping layer (referred to as a CPL layer) ) material or electron blocking layer material.
本发明同时提供以上所述的氮杂金刚烷化合物在制备有机电致发光元件中的应用。 The present invention also provides the application of the above-mentioned azaadamantane compound in preparing organic electroluminescent elements.
本发明还提供一种有机电致发光元件，其包括：第一电极、第二电极、CPL层和置于所述第一电极、所述第二电极之间的一层以上的有机层；所述有机层、CPL层中的至少一层包括以上所述的氮杂金刚烷化合物。The present invention also provides an organic electroluminescent element, which includes: a first electrode, a second electrode, a CPL layer, and one or more organic layers placed between the first electrode and the second electrode; At least one of the organic layer and the CPL layer includes the above-mentioned azaadamantane compound.
所述有机电致发光元件包含阴极、阳极、CPL和至少一个发光层。除了这些层之外，它还可以包含其它的层，例如在每种情况下，包含一个或多个空穴注入层、空穴传输层、空穴阻挡层、电子传输层、电子注入层、激子阻挡层、电子阻挡层和/或电荷产生层。具有例如激子阻挡功能的中间层同样可引入两个发光层之间。然而，应当指出，这些层中的每个并非必须都存在。此处所述有机电致发光元件可包含一个发光层，或者它可包含多个发光层。即，将能够发光的多种发光化合物用于所述发光层中。特别优选具有三个发光层的体系，其中所述三个层可显示蓝色、绿色和红色发光。如果存在多于一个的发光层，则根据本发明，这些层中的至少一个层包含本发明的化合物。The organic electroluminescent element includes a cathode, an anode, CPL and at least one light-emitting layer. In addition to these layers, it may contain further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, excitation layers, etc. sub-blocking layer, electron blocking layer and/or charge generating layer. An intermediate layer having, for example, an exciton blocking function can also be introduced between the two luminescent layers. However, it should be noted that each of these layers does not necessarily have to be present. The organic electroluminescent element described here may include one light-emitting layer, or it may include a plurality of light-emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three luminescent layers, wherein the three layers can exhibit blue, green and red luminescence. If more than one luminescent layer is present, according to the invention at least one of these layers contains a compound of the invention.
进一步地，根据本发明的有机电致发光元件不包含单独的空穴注入层和/或空穴传输层和/或空穴阻挡层和/或电子传输层，即发光层与空穴注入层或阳极直接相邻，和/或发光层与电子传输层或电子注入层或阴极直接相邻。Further, the organic electroluminescent element according to the present invention does not include a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, that is, the light emitting layer and the hole injection layer or The anode is directly adjacent, and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or the cathode.
在根据本发明的有机电致发光元件的其它层中，特别是在空穴传输层中和发光层中以及在CPL中，所有材料可以按照根据现有技术通常所使用的方式来使用。本领域普通技术人员因此将能够在不付出创造性劳动的情况下与根据本发明的发光层组合使用关于有机电致发光元件所知的所有材料。In the other layers of the organic electroluminescent element according to the invention, in particular in the hole transport layer and in the light-emitting layer and in the CPL, all materials can be used in the manner generally used according to the prior art. A person skilled in the art will therefore be able to use, without inventive effort, all materials known for organic electroluminescent components in combination with the luminescent layer according to the invention.
一般来说，OLED包含至少一个有机层，其安置在阳极与阴极之间且与阳极和阴极电连接。图1展示有机发光装置100示意图。图示不一定按比例绘制。装置100可包含衬底101、阳极102、空穴注入层103、空穴传输层104、电子阻挡层105、发光层106、电子传输层107、电子注入层108、阴极109以及封盖层(CPL)110。装置100可通过依序沉积所描述的层来制造。Generally, OLEDs comprise at least one organic layer disposed between and electrically connected to an anode and a cathode. FIG. 1 shows a schematic diagram of an organic light-emitting device 100. Illustrations are not necessarily to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, an electron transport layer 107, an electron injection layer 108, a cathode 109, and a capping layer (CPL). )110. Device 100 may be fabricated by sequentially depositing the described layers.
图2展示含有两个发光层的有机发光装置200示意图。所述装置包含衬底201、阳极202、空穴注入层203、空穴传输层204、第一发光层205、电子传输层206、电荷产生层207、空穴注入层208、空穴传输层209、第二发光层210、电子传输层211、电子注入层212以及阴极213。可通过依序沉积所描述的层来制备装置200。因为最常见的OLED装置具有一个单色发光层或具有三个三原色的发光层，而装置200具有两个相同光色的发光层。在装置200的对应层中，可使用与关于装置100所描述的材料类似的材料。图2提供可如何从装置100的结构增加一些层的一个实例。FIG. 2 shows a schematic diagram of an organic light-emitting device 200 including two light-emitting layers. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, and a hole transport layer 209 , the second light-emitting layer 210, the electron transport layer 211, the electron injection layer 212 and the cathode 213. Device 200 may be prepared by sequentially depositing the described layers. Because the most common OLED devices have one single-color light-emitting layer or three primary color light-emitting layers, the device 200 has two light-emitting layers of the same light color. In corresponding layers of device 200, materials similar to those described with respect to device 100 may be used. Figure 2 provides an example of how some layers may be added from the structure of device 100.
图1和图2中所说明的简单分层结构是作为非限制实例而提供，且应当理解，可结合各种各样的其它结构使用本发明的实施例。所描述的特定材料和结构本质上是示范性的，且可使用其它材料和结构。可基于设计、性能和成本因素，通过以不同方式组合所描述的各个层来实现功能性OLED，或可完全省略若干层。还可包含未具体描述的其它层。可使用不同于具体描述的材料。尽管本文所提供的实例中的许多实例将各种层描述为包括单一材料，但将理解，可使用材料的组合，例如基质与掺杂剂的混合物，或更一般来说，混合物。并且，所述层可具有各种子层。本文中给予各个层的名称不意欲为严格限制性的。举例来说，在装置200中，空穴传输层204传输空穴并将空穴注入到发光层205中，且可被描述为空穴传输层或电子阻挡层。在一个实施例中，可将OLED描述为具有安置在阴极与阳极之间的有机层。此有机层可包括单个层或可进一步包括如例图1和图2所描述的不同有机材料的多个层。The simple layered structure illustrated in Figures 1 and 2 is provided as a non-limiting example, and it should be understood that embodiments of the present invention may be used in conjunction with a wide variety of other structures. The specific materials and structures described are exemplary in nature and other materials and structures may be used. Functional OLEDs can be achieved by combining the various layers described in different ways, or several layers can be omitted entirely, based on design, performance and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it will be understood that combinations of materials may be used, such as mixtures of hosts and dopants, or more generally, mixtures. Also, the layers may have various sub-layers. The names given to various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 204 transports holes and injects holes into light emitting layer 205, and may be described as a hole transport layer or an electron blocking layer. In one embodiment, an OLED may be described as having an organic layer disposed between a cathode and an anode. This organic layer may comprise a single layer or may further comprise multiple layers of different organic materials as described for example in Figures 1 and 2.
还可使用未具体描述的结构和材料，例如包含聚合物材料的PLED。作为另一实例，可使用具有单个有机层的OLED或多个堆叠。OLED结构可脱离图1和图2中所说明的简单分层结构。举例来说，衬底可包含有角度的反射表面以改进光耦合。Structures and materials not specifically described may also be used, such as PLEDs containing polymeric materials. As another example, an OLED with a single organic layer or multiple stacks may be used. OLED structures can depart from the simple layered structure illustrated in Figures 1 and 2. For example, the substrate may include angled reflective surfaces to improve light coupling.
另一方面，关于本发明的有机电致发光元件，除了上述有机物层中的一层以上包含以上所述的茚衍生物之外，可以利用本领域中公知的材料和方法来形成有机物层和电极制造。On the other hand, regarding the organic electroluminescent element of the present invention, in addition to one or more of the above-mentioned organic layers containing the above-described indene derivative, the organic layer and the electrode can be formed using materials and methods known in the art. manufacture.
此外，可用作根据本发明的有机电致发光元件中所包含的阳极的物质没有特别限定，作为非限制性例子，可以使用钒、铬、铜、锌、金、铝等金属或它们的合金；氧化锌、氧化铟、氧化铟锡(ITO)、氧化铟锌(IZO)等金属氧化物；ZnO:Al或SnO2:Sb等金属与氧化物的组合；聚噻吩、聚(3-甲基噻吩)、聚[3,4-(亚乙基-1,2-二氧)噻吩](PEDT)、聚吡咯和聚苯胺等导电性高分子；以及炭黑等。 In addition, the substance that can be used as an anode included in the organic electroluminescent element according to the present invention is not particularly limited. As non-limiting examples, metals such as vanadium, chromium, copper, zinc, gold, aluminum, or alloys thereof can be used. ; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; polythiophene, poly(3-methyl) Conductive polymers such as thiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole and polyaniline; and carbon black, etc.
可用作根据本发明的有机电致发光元件中所包含的阴极的物质没有特别限定，作为非限制性例子，可以使用镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡或铅等金属或它们的合金；及LiF/Al或Li2O/Al等多层结构物质等。The material that can be used as the cathode included in the organic electroluminescent element according to the present invention is not particularly limited. As non-limiting examples, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum can be used. , silver, tin or lead and other metals or their alloys; and multi-layer structure materials such as LiF/Al or Li 2 O/Al.
可用作根据本发明的有机电致发光元件中所包含的基板的物质没有特别限定，作为非限制性例子，可以使用硅片、石英、玻璃板、金属板或塑料膜和片等。The substance that can be used as the substrate included in the organic electroluminescent element according to the present invention is not particularly limited. As non-limiting examples, silicon wafers, quartz, glass plates, metal plates or plastic films and sheets can be used.
此外优选如下的有机电致发光元件，可以借助于升华方法施加一个或多个层，其中在真空升华装置中在低于10-5Pa、优选低于10-6Pa的初压下通过气相沉积来施加所述材料。然而，所述初压还可能甚至更低，例如低于10-7Pa。Furthermore, organic electroluminescent components are preferred in which one or more layers can be applied by means of a sublimation method, wherein the layers are deposited by vapor deposition in a vacuum sublimation device at an initial pressure of less than 10 -5 Pa, preferably less than 10 -6 Pa. to apply the material. However, the initial pressure may also be even lower, for example below 10 -7 Pa.
同样优选如下的有机电致发光元件，也可以借助于有机气相沉积方法或借助于载气升华来施加一个或多个层，其中，在10-5Pa至1Pa之间的压力下施加所述材料。该方法的特别的例子是有机蒸气喷印方法，其中所述材料通过喷嘴直接施加，并且因此是结构化的。Also preferred are organic electroluminescent components in which one or more layers can also be applied by means of an organic vapor deposition method or by means of carrier gas sublimation, wherein the material is applied at a pressure of between 10 -5 Pa and 1 Pa . A particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
此外优选如下的有机电致发光元件，从溶液中，例如通过旋涂，或借助于任何所希望的印刷方法例如丝网印刷、柔性版印刷、平版印刷、光引发热成像、热转印、喷墨印刷或喷嘴印刷，来产生一个或多个层。可溶性化合物，例如通过适当的取代式(I)所示的化合物获得可溶性化合物。这些方法也特别适于低聚物、树枝状大分子和聚合物。此外可行的是混合方法，其中例如从溶液中施加一个或多个层并且通过气相沉积施加一个或多个另外的层。Furthermore, preference is given to organic electroluminescent elements produced from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithography, photothermography, thermal transfer printing, spray printing, etc. Ink printing or nozzle printing to produce one or more layers. Soluble compounds can be obtained, for example, by appropriately substituting compounds represented by formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which one or more layers are applied, for example, from solution and one or more further layers are applied by vapor deposition.
这些方法是本领域普通技术人员通常已知的，并且他们可以在不付出创造性劳动的情况下将其应用于包含根据本发明的化合物的有机电致发光元件。These methods are generally known to those skilled in the art, and they can apply them to organic electroluminescent elements containing the compounds according to the invention without exerting creative effort.
因此，本发明还涉及制造根据本发明的有机电致发光元件的方法，包括借助于升华方法来施加至少一个层，和/或借助于有机气相沉积方法或借助于载气升华来施加至少一个层，和/或从溶液中通过旋涂或借助于印刷方法来施加至少一个层。The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, comprising applying at least one layer by means of a sublimation method and/or applying at least one layer by means of an organic vapor deposition method or by means of carrier gas sublimation , and/or at least one layer is applied from solution by spin coating or by means of printing methods.
此外，本发明涉及包含至少一种上文指出的本发明的化合物。如上文关于有机电致发光元件指出的相同优选情况适用于所述本发明的化合物。特别是，所述化合物此外还可优选包含其它化合物。从液相处理本发明的化合物，例如通过旋涂或通过印刷方法进行处理，需要处理本发明的化合物的制剂，这些制剂可以例如是溶液、分散体或乳液。出于这个目的、可优选使用两种或更多种溶剂的混合物。合适并且优选的溶剂例如是甲苯、苯甲醚、邻二甲苯、间二甲苯或对二甲苯、苯甲酸甲酯、均三甲苯、萘满、邻二甲氧基苯、四氢呋喃、甲基四氢呋喃、四氢吡喃、氯苯、二噁烷、苯氧基甲苯，特别是3-苯氧基甲苯、(-)-葑酮、1,2,3,5-四甲基苯、1,2,4,5-四甲基苯、1-甲基萘、2-甲基苯并噻唑、2-苯氧基乙醇、2-吡咯烷酮、3-甲基苯甲醚、4-甲基苯甲醚、3,4-二甲基苯甲醚、3,5-二甲基苯甲醚、苯乙酮、α-萜品醇、苯并噻唑、苯甲酸丁酯、异丙苯、环己醇、环己酮、环己基苯、十氢化萘、十二烷基苯、苯甲酸乙酯、茚满、苯甲酸甲酯、1-甲基吡咯烷酮、对甲基异丙基苯、苯乙醚、1,4-二异丙基苯、二苄醚、二乙二醇丁基甲基醚、三乙二醇丁基甲基醚、二乙二醇二丁基醚、三乙二醇二甲基醚、二乙二醇单丁基醚、三丙二醇二甲基醚、四乙二醇二甲基醚、2-异丙基萘、戊苯、己苯、庚苯、辛苯、1,1-双(3,4-二甲基苯基)乙烷，或这些溶剂的混合物。Furthermore, the present invention relates to compounds comprising at least one compound of the invention indicated above. The same preferences as noted above with respect to organic electroluminescent elements apply to the compounds of the invention. In particular, the compounds may preferably also comprise other compounds. Processing the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, requires processing of formulations of the compounds of the invention, which may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, Tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenone, 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, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanol, Hexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indan, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenethyl ether, 1,4 -Diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol mono Butyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-di methylphenyl)ethane, or mixtures of these solvents.
作为优选，所述有机层包括空穴注入层、空穴传输层、空穴阻挡层、发光层、电子传输层、电子注入层、CPL层或电子阻挡层。Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a CPL layer or an electron blocking layer.
另外，如无特殊说明，本发明中所用原料均可通过市售商购获得，本发明所记载的任何范围包括端值以及端值之间的任何数值以及端值或者端值之间的任意数值所构成的任意子范围。In addition, unless otherwise specified, the raw materials used in the present invention can be purchased from commercial stores. Any range recorded in the present invention includes the end value and any value between the end value and the end value or any value between the end value. Any subrange formed by.
本发明还涉及包含至少一种式(I)化合物或上述优选实施方式和至少一种其它化合物的混合物。如果将根据本发明的化合物用作基质材料，则其它化合物可以是荧光或磷光发光体。于是该混合物还可以另外包含其它材料作为附加基质材料。本发明还涉及本发明的化合物在电子元件中的用途。优选地，如上下文提及的，将根据本发明的化合物用于空穴传输层中或用作发光层中的基质材料。根据本发明的化合物和可由此获得的电子元件、特别是有机电致发光元件与现有技术的区别在于以下令人惊讶的优势中的一种或多种：The invention also relates to mixtures comprising at least one compound of formula (I) or the preferred embodiments described above and at least one further compound. If the compounds according to the invention are used as matrix materials, the other compounds can be fluorescent or phosphorescent emitters. The mixture may then additionally contain other materials as additional matrix materials. The invention also relates to the use of the compounds of the invention in electronic components. Preferably, as mentioned above and below, the compounds according to the invention are used in the hole transport layer or as matrix material in the emissive layer. The compounds according to the invention and the electronic components obtainable therefrom, in particular organic electroluminescent components, differ from the prior art by one or more of the following surprising advantages:
1.与使用常规化合物获得的电子元件相比，使用本发明的化合物可获得的电子元件表现出非常高的 稳定性和非常长的寿命。1. Electronic components obtainable using the compounds of the present invention exhibit very high Stability and very long life.
2.使用本发明的化合物可获得的电子元件表现出高的效率，特别是高的发光效率和高的外量子效率。2. The electronic components obtainable using the compounds of the present invention exhibit high efficiency, especially high luminous efficiency and high external quantum efficiency.
3.本发明的化合物提供低工作电压。3. The compounds of the present invention provide low operating voltage.
4.可以使用常规方法处理根据本发明的化合物，从而也能够实现成本优势。4. The compounds according to the invention can be processed using conventional methods, so that cost advantages can also be achieved.
5.使用本发明的化合物可获得的薄膜表现出优异的品质，特别是在薄膜的均匀性方面更是如此。5. The films obtainable using the compounds of the present invention exhibit excellent qualities, especially in terms of film uniformity.
6.可以使用常规方法以非常快速且容易的方式生产本发明的化合物，从而也能够实现成本优势。6. The compounds of the invention can be produced in a very fast and easy manner using conventional methods, so that cost advantages can also be achieved.
上文提及的这些优势并未伴随其它电子性质的削弱。These advantages mentioned above are not accompanied by a decrease in other electronic properties.
应该指出，本发明中所述的实施方式的变化落入本发明的范围内。本发明中公开的每个特征除非被明确排除，否则可被具有相同、等效或类似目的的替代特征代替。因此，除非另外说明，否则本发明中公开的每个特征均应被视为类属系列的实例或者等效或类似特征。It should be noted that variations of the embodiments described in this invention fall within the scope of this invention. Each feature disclosed in this invention, unless expressly excluded, may be replaced by alternative features serving the same, equivalent or similar purpose. Therefore, unless stated otherwise, each feature disclosed in this invention should be considered an example of a generic series or an equivalent or similar feature.
本发明的所有特征可以以任何方式彼此组合，除非特定特征和/或步骤是互斥的。这特别适用于本发明的优选特征。同样，非必须组合的特征可以单独(且不组合)使用。此外应该指出，许多特征，特别是本发明的优选实施方式的特征本身是创造性的，并且不应仅视为本发明实施方式的一部分。对于这些特征，除当前要求保护的每个发明以外或作为其替代，可以寻求独立的保护。All features of the invention may be combined with each other in any way, unless specific features and/or steps are mutually exclusive. This applies particularly to preferred features of the invention. Likewise, features that do not necessarily need to be combined can be used individually (and not in combination). Furthermore, it should be pointed out that many features, in particular features of the preferred embodiments of the invention, are inventive in themselves and should not be regarded as merely part of the embodiments of the invention. For these features, independent protection may be sought in addition to or as an alternative to each invention currently claimed.
对本发明中公开的技术动作的教导可以被提取出并且与其它实施例组合。本发明通过以下实施例更加详细地解释，但不希望由此限制本发明。基于所述描述，本领域技术人员将能够在所公开的整个范围内执行本发明，并且不付出创造性劳动就能够制备本发明的其它化合物并将其用于电子元件中，或使用本发明的方法。The teachings of the technical acts disclosed in the present invention can be extracted and combined with other embodiments. The invention is explained in more detail by the following examples, without wishing to limit the invention thereby. Based on the description, a person skilled in the art will be able to carry out the invention within the entire scope disclosed and to prepare other compounds of the invention and use them in electronic components or to use the method of the invention without exerting creative effort .
附图说明Description of the drawings
图1展示有机发光装置100示意图。图示不一定按比例绘制。装置100可包含衬底101、阳极102、空穴注入层103、空穴传输层104、电子阻挡层105、发光层106、电子传输层107、电子注入层108、阴极109以及封盖层(CPL)110。装置100可通过依序沉积所描述的层来制造。FIG. 1 shows a schematic diagram of an organic light-emitting device 100. Illustrations are not necessarily to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, an electron transport layer 107, an electron injection layer 108, a cathode 109, and a capping layer (CPL). )110. Device 100 may be fabricated by sequentially depositing the described layers.
图2展示两个发光层的有机发光装置200示意图。所述装置包含衬底201、阳极202、空穴注入203、空穴传输层204、第一发光层205、电子传输层206、电荷产生层207、空穴注入层208、空穴传输层209、第二发光层210、电子传输层211、电子注入层212以及阴极213。可通过依序沉积所描述的层来制备装置200。因为最常见的OLED装置具有一个发光层，而装置200具有第一发光层和第二发光层，第一发光层和第二发光层的发光峰形可以是重叠的或交叉重叠的或非重叠的。在装置200的对应层中，可使用与关于装置100所描述的材料类似的材料。图2提供可如何从装置100的结构增加一些层的一个实例。FIG. 2 shows a schematic diagram of an organic light-emitting device 200 with two light-emitting layers. The device includes a substrate 201, an anode 202, hole injection 203, hole transport layer 204, first light-emitting layer 205, electron transport layer 206, charge generation layer 207, hole injection layer 208, hole transport layer 209, The second light-emitting layer 210, the electron transport layer 211, the electron injection layer 212 and the cathode 213. Device 200 may be prepared by sequentially depositing the described layers. Because the most common OLED device has one luminescent layer, and the device 200 has a first luminescent layer and a second luminescent layer, the luminescence peak shapes of the first luminescent layer and the second luminescent layer may be overlapping or cross-overlapping or non-overlapping. . In corresponding layers of device 200, materials similar to those described with respect to device 100 may be used. Figure 2 provides an example of how some layers may be added from the structure of device 100.
具体实施方式Detailed ways
以下实施例用于说明本发明，但不用来限制本发明的范围。The following examples are used to illustrate the invention but are not intended to limit the scope of the invention.
在本发明的描述中，除非另有说明，“多个”的含义是两个或两个以上；术语“上”、“下”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。In the description of the present invention, unless otherwise stated, the meaning of "plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower", etc. is based on the orientation or position shown in the drawings. The positional relationship is only for the convenience of describing the present invention and simplifying the description. It does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention.
以下实施例中所使用的实验方法如无特殊说明，均为常规方法。以下实施例中所用的实验原料和相关设备等，如无特殊说明，均可从商业途径得到，所述百分比如无特殊说明，均为质量百分比。The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental raw materials and related equipment used in the following examples can all be obtained from commercial sources unless otherwise specified. The percentages mentioned are all mass percentages unless otherwise specified.
下述实施例对OLED材料及元件进行性能测试的测试仪器及方法如下：The test instruments and methods for performance testing of OLED materials and components in the following examples are as follows:
OLED元件性能检测条件：OLED component performance testing conditions:
亮度和色度坐标：使用光谱扫描仪PhotoResearch PR-715测试；Luminance and chromaticity coordinates: tested using spectral scanner PhotoResearch PR-715;
电流密度和起亮电压：使用数字源表Keithley 2420测试；Current density and lighting voltage: tested using digital source meter Keithley 2420;
功率效率：使用NEWPORT 1931-C测试。Power efficiency: tested using NEWPORT 1931-C.
实施例1Example 1
化合物D275的制备方法，包括如下步骤：The preparation method of compound D275 includes the following steps:
第一步：中间体Int-1的制备
Step 1: Preparation of intermediate Int-1
在氮气保护下，20.0mmol的2-溴-4'-氯-1,1'-联苯解于50mL干燥的THF中，液氮降温至-78℃，滴加入22.0mmol的2.5M正丁基锂正己烷溶液，搅拌反应30分钟，再滴加入24.0mmol的5-氮杂金刚烷-2-酮，升至室温搅拌反应1小时，加入20mL的饱和氯化铵水溶液，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，加入50mL的二氯甲烷溶解，再加入60.0mmol的三氟乙酸，搅拌反应12小时，用10％的氢氧化钠水溶液洗至碱性，收集有机相，干燥，过滤，滤液减压浓缩干，过硅胶短柱，正己烷洗脱，减压浓缩干，得到Int-1，白色固体，收率65％。Under nitrogen protection, 20.0 mmol of 2-bromo-4'-chloro-1,1'-biphenyl was decomposed into 50 mL of dry THF. The liquid nitrogen was cooled to -78°C, and 22.0 mmol of 2.5 M n-butyl was added dropwise. Lithium n-hexane solution, stir and react for 30 minutes, then add 24.0 mmol of 5-azaadamantan-2-one dropwise, raise to room temperature and stir for 1 hour, add 20 mL of saturated aqueous ammonium chloride solution, and extract with ethyl acetate. Collect the organic phase, dry, filter, and concentrate the filtrate to dryness under reduced pressure. Add 50 mL of dichloromethane to dissolve, then add 60.0 mmol of trifluoroacetic acid, stir for 12 hours, wash with 10% sodium hydroxide aqueous solution until alkaline, and collect The organic phase was dried and filtered. The filtrate was concentrated to dryness under reduced pressure, passed through a short silica gel column, eluted with n-hexane, and concentrated to dryness under reduced pressure to obtain Int-1, a white solid, with a yield of 65%.
第二步：化合物D275的制备
Step 2: Preparation of Compound D275
12.0mmol的Int-1溶解于60mL的二甲苯中，在氮气保护下，加入10.0mmol的N-联苯基-4'-(9-咔唑基)-联苯-4-胺、15.0mmol的叔丁醇钠、0.1mmol的碘化亚铜、0.1mmol的Pd2(dba)3催化剂，再加入0.2mmol的Xantphos，升温至110℃搅拌反应16小时，降到室温，加入20mL的水稀释，用甲苯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物D275，收率85％，MS(MALDI-TOF)：m/z＝772.3705[M+H]+；1HNMR(δ、CDCl3)：8.18(2H,s)；8.12(1H,s)；7.94～7.85(6H,m)；7.72～7.69(2H,m)；7.57～7.52(6H,m)；7.50～7.45(3H,m)；7.41～7.32(7H,m)；7.29～7.25(2H,m)；7.21～7.14(3H,m)；3.11～3.04(2H,m)；2.72～2.55(3H,m)；2.24～2.15(3H,m)；1.86～1.79(1H,m)；1.77～1.68(2H,m)；1.65～1.56(2H,m)。12.0mmol of Int-1 was dissolved in 60mL of xylene, and under nitrogen protection, 10.0mmol of N-biphenyl-4'-(9-carbazolyl)-biphenyl-4-amine and 15.0mmol of Sodium tert-butoxide, 0.1 mmol copper iodide, 0.1 mmol Pd 2 (dba) 3 catalyst, then add 0.2 mmol Xantphos, raise the temperature to 110°C and stir for 16 hours, then cool to room temperature, add 20 mL of water to dilute, Extract with toluene, collect the organic phase, dry, filter, and concentrate the filtrate to dryness under reduced pressure. Separate and purify with a silica gel column to obtain compound D275, yield 85%, MS (MALDI-TOF): m/z=772.3705[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.18(2H,s); 8.12(1H,s); 7.94～7.85(6H,m); 7.72～7.69(2H,m); 7.57～7.52(6H,m ); 7.50～7.45(3H,m); 7.41～7.32(7H,m); 7.29～7.25(2H,m); 7.21～7.14(3H,m); 3.11～3.04(2H,m); 2.72～2.55 (3H,m); 2.24～2.15(3H,m); 1.86～1.79(1H,m); 1.77～1.68(2H,m); 1.65～1.56(2H,m).
参照上述实施例1类似的合成方法，制备如表1所示产物。Referring to the similar synthetic method of Example 1 above, the products shown in Table 1 were prepared.
表1反应物与合成产物及收率对应表








Table 1 Correspondence table between reactants, synthetic products and yields








其中，*—T3—*选自*—O—*、*—S—*或下述结构中的一种：
Among them, *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
*—和—*表示连接键。*—and—* represent connection keys.
实施例2Example 2
化合物D413的制备，以T3为C(CH3)2为例：
Preparation of compound D413, taking T 3 as C(CH 3 ) 2 as an example:
在氮气保护下，35.0mmol的(4-([1,1'-联苯]-2-基(9,9-二甲基-9H-芴-2-基)胺)苯基)硼酸频哪醇酯混于80mL的甲苯中，加入25.0mmol的Int-1、75.0mmol的无水碳酸钾、0.01mmol的Pd0132催化剂，再加入40mL的乙醇和40mL的水，升温至回流搅拌反应12小时，降到室温，加入50mL的水稀释，用甲苯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，过硅胶短柱，甲苯洗脱，减压浓缩干，再用甲苯-THF重结晶，得到化合物D413，白色固体，收率78％，MS(MALDI-TOF)：m/z＝723.3747[M+H]+；1HNMR(δ、CDCl3)：8.27～8.25(1H,m)；8.08～8.06(1H,m)；7.90～7.84(4H,m)；7.78～7.76(1H,d)；7.53～7.48(4H,m)；7.45～7.34(9H,m)；7.32～7.27(3H,m)；7.16～7.12(2H,m)；7.09～7.05(2H,m)；3.08～3.02(2H,m)；2.69～2.55(3H,m)；2.24～2.16(3H,m)；1.85～1.79(1H,m)；1.74～1.65(8H,m)；1.62～1.54(2H,m)。Under nitrogen protection, 35.0 mmol of (4-([1,1'-biphenyl]-2-yl(9,9-dimethyl-9H-fluoren-2-yl)amine)phenyl)boronic acid pinacol The alcohol ester was mixed in 80 mL of toluene, 25.0 mmol of Int-1, 75.0 mmol of anhydrous potassium carbonate, and 0.01 mmol of Pd0132 catalyst were added, and then 40 mL of ethanol and 40 mL of water were added, and the temperature was heated to reflux and the reaction was stirred for 12 hours. to room temperature, add 50 mL of water to dilute, extract with toluene, collect the organic phase, dry, filter, and concentrate the filtrate to dryness under reduced pressure, pass through a short silica gel column, elute with toluene, concentrate to dryness under reduced pressure, and then recrystallize with toluene-THF to obtain Compound D413, white solid, yield 78%, MS (MALDI-TOF): m/z=723.3747[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.27～8.25 (1H,m); 8.08～ 8.06(1H,m); 7.90～7.84(4H,m); 7.78～7.76(1H,d); 7.53～7.48(4H,m); 7.45～7.34(9H,m); 7.32～7.27(3H,m ); 7.16～7.12(2H,m); 7.09～7.05(2H,m); 3.08～3.02(2H,m); 2.69～2.55(3H,m); 2.24～2.16(3H,m); 1.85～1.79 (1H,m); 1.74～1.65(8H,m); 1.62～1.54(2H,m).
参照上述实施例2类似的合成方法，制备如表2所示产物。Referring to the similar synthesis method of Example 2 above, the products shown in Table 2 were prepared.
表2反应物与合成产物及收率对应表






Table 2 Correspondence table between reactants, synthetic products and yields






其中，*—T3—*选自*—O—*、*—S—*或下述结构中的一种：
Among them, *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
*—和—*表示连接键。*—and—* represent connection keys.
实施例3Example 3
化合物D457的制备方法，以T3＝O为例，包括以下步骤：The preparation method of compound D457, taking T 3 =O as an example, includes the following steps:
第一步：化合物Int-2的制备
Step One: Preparation of Compound Int-2
在氮气保护下，20.0mmol的Int-1溶解于40mL的DMF中，加入24.0mmol的联硼酸频哪醇酯、2.0mmol的碘化亚铜、30.0mmol的无不醋酸钾和0.2mmol的PdCl2(dppf)催化剂，升温至110℃，搅拌反应12小时，降至室温，将反应液倒入100mL的水中，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-2，收率81％。Under nitrogen protection, 20.0 mmol of Int-1 was dissolved in 40 mL of DMF, and 24.0 mmol of pinacol diborate, 2.0 mmol of copper iodide, 30.0 mmol of potassium acetate and 0.2 mmol of PdCl 2 ( dppf) catalyst, raise the temperature to 110°C, stir the reaction for 12 hours, lower to room temperature, pour the reaction solution into 100 mL of water, extract with ethyl acetate, collect the organic phase, dry, filter, and concentrate the filtrate to dryness under reduced pressure, and use a silica gel column After separation and purification, compound Int-2 was obtained with a yield of 81%.
第二步：化合物D457的制备
Step 2: Preparation of Compound D457
在氮气保护下，12.0mmol的Int-2溶解于50mL的甲苯中，加入10.0mmol的2-氯-4-(二苯并[b,d]呋喃-1-基)-6-苯基-1,3,5-三嗪、24.0mmol的六水合磷酸钾、0.01mmol的Pd0132，再加入30mL的乙醇和20mL的水，升温回流搅拌反应15小时，降至室温，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物D457，白色固体，收率83％，MS(MALDI-TOF)：m/z＝609.2672[M+H]+；1HNMR(δ、CDCl3)：8.35～8.32(3H,m)；8.08～8.06(1H,d)；8.01～7.99(1H,m)；7.90～7.82(4H,m)；7.66～7.63(1H,m)；7.55～7.48(5H,m)；7.39～7.35(2H,m)；7.33～7.27(2H,m)；3.08～3.02(2H,m)；2.69～2.55(3H,m)；2.33～2.16(3H,m)；1.86～1.79(1H,m)；1.74～1.65(2H,m)；1.62～1.53(2H,m)。Under nitrogen protection, 12.0 mmol of Int-2 was dissolved in 50 mL of toluene, and 10.0 mmol of 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1 was added. , 3,5-triazine, 24.0 mmol of potassium phosphate hexahydrate, 0.01 mmol of Pd0132, then add 30 mL of ethanol and 20 mL of water, heat and reflux and stir for 15 hours, lower to room temperature, extract with ethyl acetate, and collect the organic matter phase, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure, and separated and purified with a silica gel column to obtain compound D457, a white solid, yield 83%, MS (MALDI-TOF): m/z=609.2672[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.35～8.32(3H,m); 8.08～8.06(1H,d); 8.01～7.99(1H,m); 7.90～7.82(4H,m); 7.66～7.63(1H, m); 7.55～7.48(5H,m); 7.39～7.35(2H,m); 7.33～7.27(2H,m); 3.08～3.02(2H,m); 2.69～2.55(3H,m); 2.33～ 2.16(3H,m); 1.86～1.79(1H,m); 1.74～1.65(2H,m); 1.62～1.53(2H,m).
参照上述实施例3类似的合成方法，制备如表3所示产物。Referring to a similar synthetic method in Example 3 above, the products shown in Table 3 were prepared.
表3反应物与合成产物及收率对应表


Table 3 Correspondence table between reactants, synthetic products and yields


其中，*—T3—*选自*—O—*、*—S—*或下述结构中的一种：
Among them, *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
*—和—*表示连接键。*—and—* represent connection keys.
实施例4Example 4
化合物D483的制备方法，包括以下步骤：The preparation method of compound D483 includes the following steps:
第一步：化合物Int-3的制备
Step One: Preparation of Compound Int-3
在氮气保护下，22.0mmol的Int-2’溶解于60mL的甲苯中，加入20.0mmol的邻溴硝基苯、66.0mmol的无不碳酸钠和0.1mmol的Pd(PPh3)4催化剂，再加入30mL的乙醇和30mL的水，升温至回流搅拌反应12小时，降至室温，加入50mL的水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-3，黄色固体，收率87％。Under nitrogen protection, 22.0 mmol of Int-2' was dissolved in 60 mL of toluene, 20.0 mmol of o-bronitrobenzene, 66.0 mmol of sodium carbonate and 0.1 mmol of Pd(PPh 3 ) 4 catalyst were added, and then 30 mL was added of ethanol and 30 mL of water, heated to reflux and stirred for 12 hours, then cooled to room temperature, diluted with 50 mL of water, extracted with ethyl acetate, collected the organic phase, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure, separated and purified with a silica gel column , compound Int-3 was obtained as a yellow solid with a yield of 87%.
第二步：化合物Int-4的制备
Step 2: Preparation of compound Int-4
在氮气保护下，20.0mmol的Int-3溶解于20mL的邻二氯苯中，加入60.0mmol的三苯基磷，升温至回流搅拌反应12小时，降至室温，加入50mL的二氯甲烷溶解，冲短硅胶柱，用二氯甲烷洗脱，减压浓缩干，用二氯甲烷-乙醇重结晶，得到化合物Int-4，白色固体，收率64％。Under nitrogen protection, 20.0 mmol of Int-3 was dissolved in 20 mL of o-dichlorobenzene, 60.0 mmol of triphenylphosphorus was added, the temperature was raised to reflux and the reaction was stirred for 12 hours, then dropped to room temperature, and 50 mL of dichloromethane was added to dissolve. Shorten the silica gel column, elute with dichloromethane, concentrate to dryness under reduced pressure, and recrystallize with dichloromethane-ethanol to obtain compound Int-4 as a white solid with a yield of 64%.
第三步：化合物D483的制备
Step 3: Preparation of Compound D483
在氮气保护下，20.0mmol的Int-4溶解于60mL的二甲苯中，加入24.0mmol的2-(3-溴苯基)-4,6-二苯基-1,3,5-三嗪、2.0mmol的碘化亚铜、30.0mmol的叔丁醇钠和0.2mmol的Pd2(dba)3催化剂以及0.2mL的10％三叔丁基磷甲苯溶液，升温至110℃，搅拌反应12小时，降至室温，加入50mL的水，用二氯甲烷萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物D483，收率86％，MS(MALDI-TOF)：m/z＝684.3135[M+H]+；1HNMR(δ、CDCl3)：8.35～8.32(4H,m)；8.28(1H,s)；8.21～8.15(4H,m)；7.86(1H,s)；7.74～7.68(2H,m)；7.63～7.54(3H,m)；7.52～7.40(7H,m)；7.37～7.34(1H,m)；7.19～7.16(1H,m)；3.13～3.07(2H,m)；2.74～2.55(3H,m)；2.24～2.13(3H,m)；1.86～1.70(3H,m)；1.67～1.58(2H,m)。Under nitrogen protection, 20.0 mmol of Int-4 was dissolved in 60 mL of xylene, and 24.0 mmol of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine was added. 2.0 mmol of copper iodide, 30.0 mmol of sodium tert-butoxide, 0.2 mmol of Pd 2 (dba) 3 catalyst and 0.2 mL of 10% tri-tert-butylphosphorus toluene solution were heated to 110°C and stirred for 12 hours. Cool to room temperature, add 50 mL of water, extract with dichloromethane, collect the organic phase, dry, filter, and concentrate the filtrate to dryness under reduced pressure. Separate and purify with a silica gel column to obtain compound D483, yield 86%, MS (MALDI-TOF) : m/z=684.3135[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.35～8.32(4H,m); 8.28(1H,s); 8.21～8.15(4H,m); 7.86(1H ,s); 7.74～7.68(2H,m); 7.63～7.54(3H,m); 7.52～7.40(7H,m); 7.37～7.34(1H,m); 7.19～7.16(1H,m); 3.13 ~3.07(2H,m); 2.74~2.55(3H,m); 2.24~2.13(3H,m); 1.86~1.70(3H,m); 1.67~1.58(2H,m).
实施例5Example 5
化合物D488的制备：
Preparation of compound D488:
在氮气保护下，20.0mmol的Int-4’溶解于60mL的DMSO中，降温至-10℃，分批加入22.0mmol的65％氢化钠固体，搅拌反应1小时，再加入22.0mmol的2-联苯基-4-氯-6-苯基-1,3,5-三嗪，升至室温拌反应12小时，加入150mL的冰水，用乙酸乙酯萃取，收集有机相，用饱和盐水洗，有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物D488，黄色固体，收率83％，MS(MALDI-TOF)：m/z＝684.3143[M+H]+；1HNMR(δ、CDCl3)：8.54(1H,s)；8.35～8.30(2H,m)；8.23～8.21(1H,m)；7.98～7.92(4H,m)；7.82～7.77(3H,m)；7.65～7.63(1H,d)；7.57～7.54(1H,m)；7.52～7.44(5H,m)；7.42～7.33(3H,m)；7.25～7.21(2H,m)；7.18～7.15(1H,m)；3.18～3.12(2H,m)；2.81～2.74(2H,m)；2.63～2.55(1H,m)；2.44～2.37(2H,m)；2.24～2.16(1H,m)；1.86～1.64(5H,m)。Under nitrogen protection, 20.0 mmol of Int-4' was dissolved in 60 mL of DMSO, cooled to -10°C, 22.0 mmol of 65% sodium hydride solid was added in batches, and the reaction was stirred for 1 hour, and then 22.0 mmol of 2-linked sodium hydride was added. Phenyl-4-chloro-6-phenyl-1,3,5-triazine, raise to room temperature and stir for 12 hours, add 150 mL of ice water, extract with ethyl acetate, collect the organic phase, and wash with saturated brine. The organic phase was dried and filtered, and the filtrate was concentrated to dryness under reduced pressure and separated and purified using a silica gel column to obtain compound D488, a yellow solid, yield 83%, MS (MALDI-TOF): m/z=684.3143[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.54(1H,s); 8.35～8.30(2H,m); 8.23～8.21(1H,m); 7.98～7.92(4H,m); 7.82～7.77(3H,m) ;7.65～7.63(1H,d);7.57～7.54(1H,m);7.52～7.44(5H,m);7.42～7.33(3H,m);7.25～7.21(2H,m);7.18～7.15( 1H,m); 3.18～3.12(2H,m); 2.81～2.74(2H,m); 2.63～2.55(1H,m); 2.44～2.37(2H,m); 2.24～2.16(1H,m); 1.86～1.64(5H,m).
参照上述实施例4和实施例5类似的合成方法，制备如表4所示产物。Referring to the synthetic methods similar to Example 4 and Example 5 above, the products shown in Table 4 were prepared.
表4反应物与合成产物及收率对应表



Table 4 Correspondence table between reactants, synthetic products and yields



其中，*—T3—*选自*—O—*、*—S—*或下述结构中的一种：
Among them, *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
*—和—*表示连接键。*—and—* represent connection keys.
实施例6Example 6
一种有机电致发光元件100，其结构如图1所示，包括基板101、设于基板101上的阳极层102、设于阳极层102上的空穴注入层103、设于空穴注入层103上的空穴传输层104、设于空穴传输层104上的电子阻挡层105、设于电子阻挡层105上的发光层106、设于发光层106上的电子传输层107、电子注入层108、阴极层109，以及设于阴极层109之上的CPL层110，其制备方法包括如下步骤：An organic electroluminescent element 100 has a structure as shown in Figure 1, including a substrate 101, an anode layer 102 provided on the substrate 101, a hole injection layer 103 provided on the anode layer 102, and a hole injection layer 103 provided on the anode layer 102. The hole transport layer 104 on the hole transport layer 103, the electron blocking layer 105 on the hole transport layer 104, the light emitting layer 106 on the electron blocking layer 105, the electron transport layer 107 on the light emitting layer 106, and the electron injection layer 108. The preparation method of the cathode layer 109 and the CPL layer 110 disposed on the cathode layer 109 includes the following steps:
1)将涂布了ITO导电层的玻璃基片在清洗剂中超声处理30分钟，在去离子水中冲洗，在丙酮/乙醇混合溶剂中超声30分钟，在洁净的环境下烘烤至完全干燥，用紫外光清洗机照射10分钟，并用低能阳离子束轰击表面。1) Ultrasonicate the glass substrate coated with the ITO conductive layer in a cleaning agent for 30 minutes, rinse in deionized water, ultrasonicate in an acetone/ethanol mixed solvent for 30 minutes, and bake in a clean environment until completely dry. Use a UV cleaner for 10 minutes and bombard the surface with a low-energy cation beam.
2)把上述处理好的ITO玻璃基片置于真空腔内，抽真空至1×10-5～9×10-3Pa，在上述ITO膜上蒸镀金属银作为阳极层，蒸镀膜厚为蒸镀化合物HI01和F4TCNQ作为空穴注入层，F4TCNQ为HI01质量的3％，蒸镀膜厚为 2) Place the above-processed ITO glass substrate in a vacuum chamber, evacuate to 1×10 -5 ~ 9×10 -3 Pa, evaporate metallic silver on the above-mentioned ITO film as an anode layer, and the thickness of the evaporated film is The evaporated compounds HI01 and F4TCNQ are used as hole injection layers. F4TCNQ is 3% of the mass of HI01. The evaporated film thickness is
3)在上述空穴注入层上继续蒸镀HT08为空穴传输层，蒸镀膜厚为 3) Continue to evaporate HT08 as a hole transport layer on the above hole injection layer, and the evaporated film thickness is
4)在上述空穴传输层上继续蒸镀化合物HT10为电子阻挡层，蒸镀膜厚为 4) Continue to evaporate compound HT10 as an electron blocking layer on the above hole transport layer, and the evaporated film thickness is
5)在电子阻挡层上继续蒸镀RH12为主体材料和RD016为掺杂材料，RD016为RH12质量的3％，作为有机发光层，蒸镀膜厚为 5) Continue to evaporate RH12 as the main material and RD016 as the doping material on the electron blocking layer. RD016 is 3% of the mass of RH12. As the organic light-emitting layer, the evaporated film thickness is
6)在有机发光层上继续蒸镀一层LiQ和ET14作为电子传输层，LiQ和ET14的质量比为50:50，蒸镀膜厚为 6) Continue to evaporate a layer of LiQ and ET14 on the organic light-emitting layer as the electron transport layer. The mass ratio of LiQ and ET14 is 50:50, and the evaporated film thickness is
7)在电子传输层之上继续蒸镀一层LiF为电子注入层，蒸镀膜厚为 7) Continue to evaporate a layer of LiF on top of the electron transport layer as the electron injection layer. The evaporated film thickness is
8)在电子注入层之上蒸镀金属镁和银作为透明阴极层，镁和银的质量比为1:2，蒸镀膜厚为 8) Evaporate metal magnesium and silver as a transparent cathode layer on the electron injection layer. The mass ratio of magnesium and silver is 1:2, and the thickness of the evaporated film is
9)在透明阴极层之上再蒸镀一层NPB作为元件的CPL层，蒸镀膜厚为得到本发明提供的OLED元件。9) Evaporate another layer of NPB on the transparent cathode layer as the CPL layer of the component. The evaporated film thickness is The OLED element provided by the invention is obtained.
实施例6中使用的化合物HI01、HT08、HT10、RH12、RD016、ET14和F4TCNQ的结构如下：
The structures of the compounds HI01, HT08, HT10, RH12, RD016, ET14 and F4TCNQ used in Example 6 are as follows:
实施例7Example 7
按照与实施例6相同的步骤，将步骤3)中的HT08替换为本发明的式(I)所示化合物，得到本发明的OLED元件，元件的性能测试比对结果见表6。Following the same steps as in Example 6, HT08 in step 3) is replaced with the compound represented by formula (I) of the present invention to obtain the OLED component of the present invention. The performance test comparison results of the component are shown in Table 6.
实施例8Example 8
按照与实施例6相同的步骤，将步骤4)中的HT10替换为本发明的式(I)所示化合物，得到本发明的OLED元件，元件的性能测试比对结果见表7。Follow the same steps as in Example 6, replace HT10 in step 4) with the compound represented by formula (I) of the present invention, and obtain the OLED component of the present invention. The performance test comparison results of the component are shown in Table 7.
实施例9Example 9
按照与实施例6相同的步骤，将步骤5)中的RH12替换为本发明的式(I)所示化合物，得到本发明的OLED元件，元件的性能测试比对结果见表8。Follow the same steps as in Example 6, replace RH12 in step 5) with the compound represented by formula (I) of the present invention, and obtain the OLED component of the present invention. The performance test comparison results of the component are shown in Table 8.
实施例10Example 10
按照与实施例6相同的步骤，将步骤6)中的ET14替换为本发明的式(I)所示化合物，得到本发明的OLED元件，元件的性能测试比对结果见表8。Follow the same steps as in Example 6, replace ET14 in step 6) with the compound represented by formula (I) of the present invention, and obtain the OLED component of the present invention. The performance test comparison results of the component are shown in Table 8.
对上述过程制备的有机电致发光元件进行如下性能测试：The organic electroluminescent elements prepared by the above process were subjected to the following performance tests:
使用数字源表及亮度计测定实施例6～实施例10中制备得到的有机电致发光元件的驱动电压和电流效率以及元件的寿命。具体而言，以每秒0.1V的速率提升电压，测定当有机电致发光元件的电流密度达到10mA/cm2时的电压即驱动电压，同时测出此时的亮度；亮度与电流密度的比值即为电流效率；LT95％寿命测试如下：使用亮度计在1000cd/m2亮度下，保持恒定的电流，测量有机电致发光元件的亮度衰减为950cd/m2的时间，单位为小时，所有数据均为对比元件的归一化结果。A digital source meter and a luminance meter were used to measure the driving voltage and current efficiency of the organic electroluminescent elements prepared in Examples 6 to 10, as well as the lifetime of the elements. Specifically, increase the voltage at a rate of 0.1V per second, measure the voltage when the current density of the organic electroluminescent element reaches 10mA/ cm2 , which is the driving voltage, and measure the brightness at this time; the ratio of brightness to current density That is the current efficiency; the LT95% life test is as follows: use a luminance meter to maintain a constant current at a brightness of 1000cd/ m2 , and measure the time for the brightness of the organic electroluminescent element to decay to 950cd/ m2 , in hours, all data All are normalized results of comparison components.
表5各元件性能检测结果





Table 5 Performance test results of each component





由表5可知，本发明的氮杂金刚烷化合物作为空穴传输层材料制备成的发光元件同样在电流密度为10mA/cm2条件下，驱动电压降低，发光效率有提高显著，而且LT95％寿命有明显优势，是性能良好的空穴传输层材料。As can be seen from Table 5, the light-emitting element prepared by using the azaadamantane compound of the present invention as a hole transport layer material also has a reduced driving voltage, a significant improvement in luminous efficiency, and a LT95% lifespan under the condition of a current density of 10 mA/cm 2 It has obvious advantages and is a hole transport layer material with good performance.
实施例6的化合物HT08与本发明的化合物相比，区别在于氮杂金刚烷含有孤电子对的氮原子，对分子成膜的影响较小，与金刚烷相比空穴迁移率提高，所以其在分子成膜及载流子的传输性能上均较对比的化合物HT08优异，在元件性能和寿命上表现更有优势。Comparing the compound HT08 of Example 6 with the compound of the present invention, the difference is that azaadamantane contains nitrogen atoms of lone electron pairs, which has less impact on molecular film formation. Compared with adamantane, the hole mobility is increased, so its hole mobility is improved. It is superior to the comparative compound HT08 in terms of molecular film formation and carrier transport properties, and has more advantages in component performance and lifespan.
表6各元件性能检测结果





Table 6 Performance test results of each component





由表6可知，本发明的氮杂金刚烷化合物作为电子阻挡层材料制备成的发光元件同样在电流密度为10mA/cm2条件下，驱动电压降低，发光效率提高明显，而且LT95％寿命有大幅度提升，是性能优异的电子材料。As can be seen from Table 6, the light-emitting element prepared by using the azaadamantane compound of the present invention as an electron blocking layer material also has a lower driving voltage and a significantly improved luminous efficiency under the condition of a current density of 10 mA/ cm2 , and the LT95% lifespan has a great The amplitude is improved and it is an electronic material with excellent performance.
实施例6中的化合物HT10与本发明的化合物相比，区别在于氮杂金刚烷含有孤电子对的氮原子，更有利于输送空穴而阻挡电子，降低激子在非发光层形成的概率，所以其在发光元件的表现上更加优异。Comparing the compound HT10 in Example 6 with the compound of the present invention, the difference is that azaadamantane contains nitrogen atoms with lone electron pairs, which is more conducive to transporting holes and blocking electrons, reducing the probability of exciton formation in the non-emitting layer. Therefore, its performance in light-emitting components is even better.
表7各元件性能检测结果

Table 7 Performance test results of each component

由表7可知，本发明的氮杂金刚烷化合物作为发光层的主体材料制备成的发光元件同样在电流密度为10mA/cm2条件下，驱动电压降低，发光效率提高明显，而且LT95％寿命有大幅度提升，是性能优异的发光层材料。As can be seen from Table 7, the light-emitting element prepared by using the azaadamantane compound of the present invention as the host material of the light-emitting layer also has a reduced driving voltage and a significant improvement in luminous efficiency under the condition of a current density of 10 mA/ cm2 , and the LT95% life span is It has been greatly improved and is a light-emitting layer material with excellent performance.
实施例6中的化合物RH12与本发明的化合物相比，区别在于二甲基芴的位阻小，将二甲基替换为氮杂金刚烷后不仅位增大，而且利于阻挡空穴的输送，因此分子构成D-A双极性，发光层内的载流子传输更加平衡，更有利于激子在发光层内形成，所以其在发光元件的表现上更加优异。Comparing the compound RH12 in Example 6 with the compound of the present invention, the difference is that the steric hindrance of dimethyl fluorene is small. Replacing the dimethyl group with azaadamantane not only increases the steric hindrance, but also helps to block the transport of holes. Therefore, the molecules constitute D-A bipolarity, and the carrier transmission in the light-emitting layer is more balanced, which is more conducive to the formation of excitons in the light-emitting layer, so its performance in light-emitting elements is better.
表8各元件性能检测结果

Table 8 Performance test results of each component

上述表5至表8中，Me为甲基；Ph为苯基；PhPh为联苯基；Nap为萘基；FR为芴基。In the above Tables 5 to 8, Me is methyl; Ph is phenyl; PhPh is biphenyl; Nap is naphthyl; FR is fluorenyl.
由表8可知，本发明的氮杂金刚烷化合物作为电子传输层材料制备成的发光元件同样在电流密度为10mA/cm2条件下，驱动电压降低，发光效率提高明显，而且LT95％寿命有大幅度提升，是性能优异的电子材料。As can be seen from Table 8, the light-emitting element prepared by using the azaadamantane compound of the present invention as an electron transport layer material also has a lower driving voltage and a significantly improved luminous efficiency under the condition of a current density of 10 mA/ cm2 , and the LT95% lifespan has a great The amplitude is improved and it is an electronic material with excellent performance.
实施例6中的化合物ET14与本发明的化合物相比，区别在于氮杂金刚烷含有孤电子对的氮原子，氮原子的引入使金刚烷的立体刚性增强，更利于电子的传输和激子的形成，所以其在发光元件的表现上更加优异。Comparing the compound ET14 in Example 6 with the compound of the present invention, the difference is that azaadamantane contains nitrogen atoms with lone electron pairs. The introduction of nitrogen atoms enhances the three-dimensional rigidity of adamantane, which is more conducive to the transmission of electrons and excitons. formed, so it performs better in light-emitting components.
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。 Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims (10)

  1. 一种氮杂金刚烷化合物，其特征在于，其结构式如式(I)所示：
    An azaadamantane compound is characterized in that its structural formula is as shown in formula (I):
    R1、R2、R3、R4、R5、R6、R7、R8各自独立地选自由氢、氘、卤素、腈基、C1-C40的烷基、C3-C40的环烷基或带有支链的烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、取代或未取代的C2-C60杂环芳基、或者式(II)所示基团组成的群组，任意相邻的两个或多个取代基可任选的接合或稠合形成取代或未取代的环；
    R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from hydrogen, deuterium, halogen, nitrile, C 1 -C 40 alkyl, C 3 -C 40 cycloalkyl or branched alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 fused ring aryl, substituted or unsubstituted C 6 - A group consisting of a C 60 arylamine group, a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, or a group represented by formula (II). Any two or more adjacent substituents are optional. join or fuse to form substituted or unsubstituted rings;
    Ar1、Ar2各自独立地选自由C1-C40的烷基、C3-C40的环烷基或带有支链的烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组，Ar1、Ar2可以任意的接合或稠合形成取代或未取代的环；Ar 1 and Ar 2 are each independently selected from a C 1 -C 40 alkyl group, a C 3 -C 40 cycloalkyl group or a branched alkyl group, a substituted or unsubstituted C 6 -C 60 aryl group, A group consisting of a substituted or unsubstituted C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, Ar 1. Ar 2 can be arbitrarily joined or fused to form a substituted or unsubstituted ring;
    m选自0～5的整数；m is selected from an integer from 0 to 5;
    L1选自单键、取代或未取代的C6-C60的亚芳基、或者取代或未取代的C2-C60亚杂芳基；L 1 is selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
    *—表示R1、R2、R3、R4、R5、R6、R7或R8与L1的连接键。*—Indicates the connection key between R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 and L 1 .
  2. 根据权利要求1所述的氮杂金刚烷化合物，其特征在于，所述R1、R2、R3、R4、R5、R6、R7、R8各自独立地选自由氢、氘、氟、腈基、甲基、乙基、叔丁基、苯基、联苯基、三联苯基、萘基、菲基、三亚苯基、咔唑基、芴基、二苯并呋喃、二苯并噻吩、取代或未取代的C6-C60芳胺基、取代或未取代的C2-C60杂环芳基、或者式(II)所示基团组成的群组，并且在R1、R2、R3、R4、R5、R6、R7、R8中至少有一者为式(II)所示基团，或者任意相邻的两个或多个取代基可任选的接合或稠合形成取代或未取代的环；The azaadamantane compound according to claim 1, characterized in that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, deuterium , fluorine, nitrile, methyl, ethyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, dibenzofuran A group consisting of benzothiophene, a substituted or unsubstituted C 6 -C 60 arylamine group, a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, or a group represented by formula (II), and in R 1. At least one of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a group represented by formula (II), or any two or more adjacent substituents may be any Optional joining or fusion to form a substituted or unsubstituted ring;
    Ar1、Ar2各自独立地选自由取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳胺基组成的群组；Ar 1 and Ar 2 are each independently selected from the group consisting of a substituted or unsubstituted C 6 -C 60 aryl group and a substituted or unsubstituted C 6 -C 60 arylamine group;
    m选自0、1或2。m is selected from 0, 1 or 2.
  3. 根据权利要求1或2任一项所述的氮杂金刚烷化合物，其特征在于，所述L1选自单键或由以下III-1～III-15所示基团组成的群组：

    The azaadamantane compound according to any one of claims 1 or 2, characterized in that said L 1 is selected from a single bond or a group consisting of the following groups represented by III-1 to III-15:

    其中，in,
    Z11、Z12各自独立地选自由氢、氘、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60的烷基、C2-C60的烯基、C2-C60的炔基、C1-C60的烷氧基、C3-C60的环烷烃基、C3-C60的环烯烃基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基组成的群组；Z 11 and Z 12 are each independently selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidine group, hydrazine group, hydrazone group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonic acid Salt, phosphate group or its phosphate, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 3 -C 60 cycloalkyl group, C 3 -C 60 cycloalkenyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
    Z13表示取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基中的一种或多种；Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a substituted or unsubstituted C 6 -C 60 aryl sulfide group. One or more C 2 -C 60 heterocyclic aryl groups;
    y1表示1-4的整数；y2表示1-6的整数；y3表示1-3的整数；y4表示1-5的整数；y1 represents an integer from 1 to 4; y2 represents an integer from 1 to 6; y3 represents an integer from 1 to 3; y4 represents an integer from 1 to 5;
    T2选自O、S、CR’R”或NAr’；T 2 is selected from O, S, CR'R" or NAr';
    R’、R”各自独立地选自由氢、氘、C1-C60的烷基、C1-C60的杂烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基；R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl group, C 1 -C 60 heteroalkyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted A group consisting of C 6 -C 60 arylamine groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can optionally be joined or fused to form another one or more Substituted or unsubstituted rings, containing or not containing one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R', R" is methyl, phenyl or fluorenyl ;
    Ar’选自由C1-C60的烷基、C1-C60的杂烷基、C3-C60的环烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基或萘基；Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of a C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
    表示取代基与主体结构的连接键。 Indicates the bond between the substituent and the main structure.
  4. 根据权利要求1～3任一项所述的氮杂金刚烷化合物，其特征在于，所述Ar1、Ar2选自由以下所示基团组成的群组：
    The azaadamantane compound according to any one of claims 1 to 3, wherein Ar 1 and Ar 2 are selected from the group consisting of the following groups:
    其中，in,
    每个取代基上的氢原子均可被取代基取代，所述取代基选自由氢氘、卤素、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60烷基、C2-C60烯基、C2-C60炔基、C1-C60烷氧基、C3-C60环烷烃基、C3-C60环烯烃基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基组成的群组；The hydrogen atom on each substituent may be substituted by a substituent selected from hydrogen deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or its carboxylic acid Salt, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group , C 3 -C 60 cycloalkyl group, C 3 -C 60 cycloalkenyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted A group consisting of a C 6 -C 60 aryl sulfide group or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group;
    G选自O、S、CR’R”或NAr’；G is selected from O, S, CR’R” or NAr’;
    R’、R”各自独立地选自由氢、氘、C1-C60的烷基、C1-C60的杂烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基； R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl group, C 1 -C 60 heteroalkyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted A group consisting of C 6 -C 60 arylamine groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can optionally be joined or fused to form another one or more Substituted or unsubstituted rings, containing or not containing one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R', R" is methyl, phenyl or fluorenyl ;
    Ar’选自由C1-C60的烷基、C1-C60的杂烷基、C3-C60的环烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的C6-C60芳胺基、或者取代或未取代的C2-C60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基或萘基；Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of a C 6 -C 60 fused ring aryl group, a substituted or unsubstituted C 6 -C 60 arylamine group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
    *—表示Ar1、Ar2与N的连接键。*—Indicates the connecting bond between Ar 1 , Ar 2 and N.
  5. 根据权利要求1-4任一项所述的氮杂金刚烷化合物，其特征在于，所述*—NAr1Ar2选自由下述式B1～B15组成的群组：
    The azaadamantane compound according to any one of claims 1 to 4, wherein the *-NAr 1 Ar 2 is selected from the group consisting of the following formulas B1 to B15:
    其中，*—G—*选自连接键、*—O—*、*—S—*或下述结构中的一种：
    Among them, *—G—* is selected from connecting bonds, *—O—*, *—S—* or one of the following structures:
    *—和—*表示与两个环之间的连接键；*—and—* represent the connecting bonds between the two rings;
    所述B1～B15结构中的每个R7各自独立地选自由氢、氘、卤素、腈基、C1-C40的烷基、C3-C40的环烷基或带有支链的烷基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、取代或未取代的 C6-C60芳胺基、取代或未取代的C2-C60杂环芳基组成的群组，此时，当取代基为一种以上时，多个取代基彼此相同或不同。Each R 7 in the structure B1 to B15 is independently selected from hydrogen, deuterium, halogen, nitrile group, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group or branched chain alkyl group. Alkyl, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 fused ring aryl group, substituted or unsubstituted A group consisting of a C 6 -C 60 arylamine group and a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group. In this case, when there is more than one substituent, the plurality of substituents are the same or different from each other.
  6. 根据权利要求1所述的氮杂金刚烷化合物，其特征在于，所述R1、R2、R3、R4、R5、R6、R7、R8各自独立地选自由氢、氘、氟、腈基、取代或未取代的C6-C60芳基、取代或未取代的C2-C60杂环芳基组成的群组，并且在R1、R2、R3、R4、R5、R6、R7、R8中至少有一者为取代或未取代的C6-C60芳基或取代或未取代的C2-C60杂环芳基，或任意相邻的两个或多个取代基可任选的接合或稠合形成取代或未取代的环；The azaadamantane compound according to claim 1, characterized in that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, deuterium , fluorine, nitrile group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, and in R 1 , R 2 , R 3 , R 4. At least one of R 5 , R 6 , R 7 and R 8 is a substituted or unsubstituted C 6 -C 60 aryl group or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group, or any adjacent Two or more substituents of may optionally be joined or fused to form a substituted or unsubstituted ring;
    所述芳基、杂环芳基选自由以下基团组成的群组：苯、萘、蒽、苯并蒽、菲、芘、苝、荧蒽、并四苯、并五苯、苯并芘、联苯、偶苯、三联苯、四联苯、三聚苯、芴、螺二芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、顺式或反式茚并咔唑、顺式或反式吲哚并咔唑、三聚茚、异三聚茚、螺三聚茚、螺异三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并[5,6]喹啉、苯并[6,7]喹啉、苯并[7,8]喹啉、吩噻嗪、吩噁嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、噁唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、异噁唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、六氮杂苯并菲、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1,5-二氮杂蒽、2,7-二氮杂芘、2,3-二氮杂芘、1,6-二氮杂芘、1,8-二氮杂芘、4,5-二氮杂芘，4,5,9,10-四氮杂苝、吡嗪、吩嗪、吩噁嗪、吩噻嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-噁二唑、1,2,4-噁二唑、1,2,5-噁二唑、1,3,4-噁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑、1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、吲嗪、喹唑啉和苯并噻二唑或者衍生自这些体系的组合的基团。The aryl group and heterocyclic aryl group are selected from the group consisting of the following groups: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, aiphenyl, terphenyl, tetraphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydrogen Pyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, trimeric indene, isotrimeric indene, spirotrimeric indene, spiroisotrimeric Indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline , isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyridine Azole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanzimidazole, pyridimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthraceneoxazole Azole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazabenzophenanthrene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline Phenoline, 1,5-diazapyrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5 -Diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorine ring, naphthyridine, azacarbazole, benzocarboline, Carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine , 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole or groups derived from combinations of these systems .
  7. 根据权利要求1-6任一项所述的氮杂金刚烷化合物，其特征在于，所述氮杂金刚烷化合物选自由以下D253至D525组成的群组：










    The azaadamantane compound according to any one of claims 1 to 6, characterized in that the azaadamantane compound is selected from the group consisting of the following D253 to D525:










    其中，*—T3—*选自*—O—*、*—S—*或下述结构中的一种：
    Among them, *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
    *—和—*表示连接键。 *—and—* represent connection keys.
  8. 一种有机电致发光材料，其特征在于，其原料包括权利要求1-7任一项所述的氮杂金刚烷化合物。An organic electroluminescent material, characterized in that its raw materials include the azaadamantane compound according to any one of claims 1 to 7.
  9. 权利要求1-7任一项所述的氮杂金刚烷化合物在制备有机电致发光元件中的应用。Application of the azaadamantane compound according to any one of claims 1 to 7 in the preparation of organic electroluminescent elements.
  10. 一种有机电致发光元件，其特征在于，其包括：第一电极、第二电极、CPL层和置于所述第一电极、第二电极之间的至少一个有机层；所述有机层、CPL层中的至少一层包括权利要求1-7任一项所述的氮杂金刚烷化合物。 An organic electroluminescent element, characterized in that it includes: a first electrode, a second electrode, a CPL layer and at least one organic layer placed between the first electrode and the second electrode; the organic layer, At least one of the CPL layers includes the azaadamantane compound of any one of claims 1-7.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112209840A (en) * 2020-03-13 2021-01-12 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic component, and electronic device
CN113045434A (en) * 2021-03-03 2021-06-29 陕西莱特光电材料股份有限公司 Organic compound, and organic electroluminescent device and electronic device using same
CN113105420A (en) * 2021-04-13 2021-07-13 浙江虹舞科技有限公司 Fused ring arylamine compound, application thereof and organic electroluminescent device containing compound
CN114591183A (en) * 2022-01-28 2022-06-07 陕西莱特迈思光电材料有限公司 Organic compound, electronic element, and electronic device
CN115028630A (en) * 2022-06-16 2022-09-09 上海八亿时空先进材料有限公司 Azaadamantane compound and organic electroluminescent element

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11968883B2 (en) * 2017-07-26 2024-04-23 Universal Display Corporation Organic electroluminescent materials and devices
KR20210156921A (en) * 2020-06-18 2021-12-28 삼성디스플레이 주식회사 Heterocyclic compound and organic light-emitting device including the same
KR20220023864A (en) * 2020-08-20 2022-03-03 삼성디스플레이 주식회사 Amine compound and light emitting device including the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112209840A (en) * 2020-03-13 2021-01-12 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic component, and electronic device
CN113045434A (en) * 2021-03-03 2021-06-29 陕西莱特光电材料股份有限公司 Organic compound, and organic electroluminescent device and electronic device using same
CN113105420A (en) * 2021-04-13 2021-07-13 浙江虹舞科技有限公司 Fused ring arylamine compound, application thereof and organic electroluminescent device containing compound
CN114591183A (en) * 2022-01-28 2022-06-07 陕西莱特迈思光电材料有限公司 Organic compound, electronic element, and electronic device
CN115028630A (en) * 2022-06-16 2022-09-09 上海八亿时空先进材料有限公司 Azaadamantane compound and organic electroluminescent element

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