CN112250631A - Benzophenanthridine derivative, electroluminescent material and organic electroluminescent element - Google Patents

Benzophenanthridine derivative, electroluminescent material and organic electroluminescent element Download PDF

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CN112250631A
CN112250631A CN202011116525.3A CN202011116525A CN112250631A CN 112250631 A CN112250631 A CN 112250631A CN 202011116525 A CN202011116525 A CN 202011116525A CN 112250631 A CN112250631 A CN 112250631A
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benzophenanthridine
derivative
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姜卫东
戴雄
侯斌
刘殿君
李程辉
谢佩
边坤
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

The invention relates to a benzophenanthridine derivative, an electroluminescent material and an organic electroluminescent element, wherein the structural formula of the derivative is shown as a formula (I), the benzophenanthridine derivative can be applied to an organic layer of the organic electroluminescent element due to excellent electronic mobility, thermal stability and luminescent property, and has good film-forming property, and the benzophenanthridine derivative prepared by the invention is applied to an electronic transmission layer and an electric transmission layerWhen the sub-transport auxiliary layer is formed, an organic electroluminescent element having a lower driving voltage, a higher light extraction efficiency, and a longer life than those of the conventional electron transport materials can be manufactured, and thus a full-color display panel having improved performance and life can be manufactured.
Figure DDA0002730477630000011

Description

Benzophenanthridine derivative, electroluminescent material and organic electroluminescent element
Technical Field
The invention belongs to the technical field of materials for organic electroluminescent elements, and particularly relates to a benzophenanthridine derivative, an electroluminescent material and an organic electroluminescent element.
Background
In general, the organic light emitting phenomenon refers to a phenomenon in which light is emitted when electric energy is applied to an organic substance. That is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
As one method for efficiently manufacturing an organic electroluminescent element, studies have been made to replace an organic layer in a single-layer manufactured element with a multilayer structure, and in 1987, down proposed an organic electroluminescent element having a laminated structure of a hole layer and a functional layer of a light-emitting layer, and most of the organic electroluminescent elements currently used include: the light emitting device includes a substrate, an anode, a hole injection layer receiving holes from the anode, a hole transport layer transporting holes, a light emitting layer emitting light by recombination of holes and electrons, an electron transport layer transporting electrons, an electron injection layer receiving electrons from the cathode, and a cathode. The reason why the organic electroluminescent element is formed in a multilayer structure is that since the moving speeds of holes and electrons are different, if the hole injection layer and the transport layer, and the electron transport layer and the electron injection layer are appropriately formed, holes and electrons can be efficiently transported, and the balance between holes and electrons can be achieved in the element, thereby improving the exciton utilization rate.
As the earliest report on electron transport materials, oxadiazole derivatives were cited. Then, it was reported that triazole derivatives, phenanthroline derivatives, imidazole derivatives, and the like exhibit electron transport properties, and for example, chinese patents CN103833507B, CN107573328B, and CN107556310B are applicable to substances of an electron transport layer. As an organic monomolecular substance, an organic metal complex which is relatively excellent in electron stability and electron transfer rate is reported as a good candidate, and Liq which is excellent in stability and has a large electron affinity is the most excellent substance, and is also the most basically used substance at present.
Patents CN103896851B, CN103896852B and CN104193783B disclose structures of phenyl-substituted pyridazine, naphthyl-substituted pyridazine and benzisoquinoline, which are applied to near-infrared luminescent materials or ligands of near-infrared luminescent materials, and the diimine is decomposed under high temperature or ultraviolet irradiation to release nitrogen, resulting in poor thermal stability of molecules.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a benzophenanthridine derivative, an electroluminescent material and an organic electroluminescent element.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a benzophenanthridine derivative, wherein the structural formula of the derivative is shown as a formula (I):
Figure BDA0002730477610000021
wherein R is1～R11Each independently selected from hydrogen, deuterium, halogen, cyano, C1-C40Alkyl of (C)2-C40Alkenyl of, C2-C40Alkynyl of (A), C3-C40Cycloalkyl of (2), heterocycloalkyl of atomic number 3 to 40, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C1-C40Alkoxy group of (C)6-C60Aryloxy group of (A), C1-C40Alkylsilyl group of (C)6-C60Arylsilyl group of (C)1-C40Alkyl boron group of (2), C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Any two or more adjacent substituents may be optionally joined or fused, or bridging groups bonded to the same nitrogen atom, phosphorus atom, boron atom, oxygen atom, or sulfur atom may be bridged to each other to form a single ring or a fused ring.
Further, R2～R6、R8～R11Each independently selected from hydrogen, deuterium, halogen, cyano, C1-C40Alkyl of (C)2-C40Alkenyl of, C2-C40Alkynyl of (A), C3-C40Cycloalkyl group, heterocycloalkyl group having 3 to 40 atomic numbers, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C1-C40Alkoxy group of (C)6-C60Aryloxy group of (A), C1-C40Alkylsilyl group of (C)6-C60Arylsilyl group of (C)1-C40Alkyl boron group of (2), C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Any two or more adjacent substituents of the arylamine group of (a) may be optionally joined or condensed, or bonded to the same nitrogen atom, phosphorus atom, boron atom, oxygen atomBridging groups of atoms or sulfur atoms with each other to form a single or fused ring; r1、R7Each independently selected from hydrogen, deuterium, halogen, cyano, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60And R is selected from the group consisting of arylamine groups of (A), and R1And R2、R7And R6Or R7And R8Bridging groups which may be joined or fused, or bonded to the same nitrogen, phosphorus, boron, oxygen or sulfur atom, are bridged to each other to form a single or fused ring.
Further, R2～R6、R8～R11Each independently selected from hydrogen, deuterium, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Any two or more adjacent substituents may be optionally joined or condensed, or bridging groups bonded to the same nitrogen atom, phosphorus atom, boron atom, oxygen atom, or sulfur atom may be bridged with each other to form a single ring or a condensed ring, R1、R7Each independently selected from hydrogen, deuterium, halogen, cyano, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60And R is selected from the group consisting of arylamine groups of (A), and R1And R2、R7And R6Or R7And R8Bridging groups which may be joined or fused, or bonded to the same nitrogen, phosphorus, boron, oxygen or sulfur atom, are bridged to each other to form a single or fused ring.
Further, said R1～R11Each independently selected from hydrogen, deuterium, halogen, cyano, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Any two or more adjacent substituents of one of the arylamine groups of (a) may be optionally joined or fused, orBridging groups bonded to the same nitrogen, phosphorus, boron, oxygen or sulfur atom are bridged to each other to form a single or fused ring.
In the invention, a plurality of substituent groups R are introduced1To R11Particularly, aryl and/or heteroaryl, the molecular weight of the compound is significantly increased, and the glass transition temperature is increased, thereby enabling higher thermal stability than conventional light-emitting materials. Therefore, the performance and life characteristics of the organic electroluminescent element including the compound according to the present invention can be greatly improved. Therefore, the organic electroluminescent element with improved performance and life characteristics can ultimately maximize the performance of a full-color organic light-emitting panel.
Further, said C2-C60The heteroaryl is one of the following structural formulas II-1 to II-17:
Figure BDA0002730477610000041
wherein Z is1、Z2Each independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic group or a sulfonate thereof, a phosphoric group or a phosphate thereof, C1-C40Alkyl radical, C2-C40Alkenyl radical, C2-C40Alkynyl, C1-C40Alkoxy radical, C3-C40Cycloalkyl radical, C3-C40Cycloalkenyl radical, C6-C60Aryl radical, C6-C60Aryloxy radical, C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Arylamino or C of2-C60Heteroaryl of (a);
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T1represents oxygen, sulfur, CR12R13Or NCy1；
The R is12And R13Each independently selected from hydrogen, deuterium, C1-C40Alkyl of (C)2-C40Alkenyl of, C2-C40Alkynyl of (A), C3-C40Cycloalkyl of (2), heterocycloalkyl of atomic number 3 to 40, C6-C60Aryl of (C)2-C60Heteroaryl of (a);
the Cy is1Is selected from C6-C60Aryl radical, C2-C60One of heteroaryl;
Figure BDA0002730477610000052
represents a bond between a substituent and the main structure.
Further, the specific structural formula of the benzophenanthridine derivative is shown as CJHP 253-CJHP 488:
Figure BDA0002730477610000051
Figure BDA0002730477610000061
Figure BDA0002730477610000071
Figure BDA0002730477610000081
Figure BDA0002730477610000091
Figure BDA0002730477610000101
Figure BDA0002730477610000111
Figure BDA0002730477610000121
Figure BDA0002730477610000131
wherein, T3Is O-, S-or one of the following structures,
Figure BDA0002730477610000132
Figure BDA0002730477610000141
wherein, -and-represent a connecting bond.
Alkyl in the sense of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms, and includes, as non-limiting examples thereof, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl and the like.
An alkyloxy group, preferably having 1 to 40 carbon atoms, in the sense of the present invention is taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexoxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy, 2, 2-trifluoroethoxy and the like.
Heteroalkyl in the sense of the present invention is preferably one having 1 to 40 carbon atoms, such as, as non-limiting examples, alkoxy, alkylthio, fluorinated alkoxy, fluorinated alkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutoxy, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2,2, 2-trifluoroethoxy, 2,2, 2-trifluoroethylthio, vinyloxy, vinylthio, propenyloxy, propenylthio, butenylthio, butenyloxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexenyloxy, cyclohexenylthio, ethynyloxy, ethynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio. In general, cycloalkyl, cycloalkenyl according to the invention are preferably cycloalkyl, cycloalkenyl with a number of carbon atoms of 3 to 40, such as, as non-limiting examples thereof, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctenyl, wherein one or more-CH 2-groups may be replaced by the above-mentioned groups; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms, or nitrile groups.
The heterocycloalkyl group in the present invention refers to a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon having 3 to 40 carbon atoms. At this time, one or more carbons, preferably 1 to 3 carbons, in the ring are substituted with a hetero atom such as nitrogen, oxygen, or sulfur, and as non-limiting examples thereof, morpholine, pyran, piperazine, and the like.
The alkenyl group of the present invention may be a monovalent functional group obtained by removing a hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. As non-limiting examples thereof, there are vinyl, allyl, isopropenyl, 2-butenyl, heptenyl, octenyl and the like.
The alkynyl group in the present invention refers to a monovalent functional group obtained by removing a hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. As non-limiting examples thereof, there are ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl and the like.
The aryl group in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a single ring or an aromatic hydrocarbon having 6 to 60 carbon atoms in combination with two or more. In this case, two or more rings may be attached to each other or in a condensed form. As non-limiting examples thereof, there may be mentioned phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure BDA0002730477610000151
A phenyl group, a perylene group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, a phenanthrenyl group, a pyrenyl group, a tetrahydropyrenyl group, an indenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, a cis-or trans-indonocarbazolyl group, a triindenyl group, an isotridecyl group, a spiroisotridecyl group, a furyl group, a benzofuryl group, an isobenzofuryl group, a dibenzofuryl group, a thienyl group, a benzothienyl group, an isobenzothienyl group, a dibenzothienyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, a carbazolyl group, a pyridyl group, a quinolyl group, an]Quinolyl, benzo [6,7 ]]Quinolyl, benzo [7,8 ]]Quinolyl, phenothiazinyl, phenoxazine, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazenanthrayl, 2, 7-diazapyryl, 2, 3-diazapyl, 1, 6-diazapyl, 1, 8-diazapyl, 4, 5-diazapylAzapyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorerynyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, carbolinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl and benzothiadiazolyl or groups derived from combinations of these systems.
The aryloxy group, the arylboron group, the arylphosphorus group and the arylphosphorus oxide group in the present invention mean a monovalent functional group in which an aryl group having 6 to 60 carbon atoms is bonded to an oxygen atom, a boron atom, a phosphorus oxide and a nitrogen atom. As non-limiting examples, there are phenoxy, naphthoxy, diphenoxy, dibenzene-boron, diphenylphosphino oxide, diphenylamine and the like.
The alkylsilyl group in the present invention means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, the arylsilyl group means a silyl group substituted with an aryl group having 6 to 60 carbon atoms, and the arylamine means an amine substituted with an aryl group having 6 to 60 carbon atoms.
The arylene group and the heteroarylene group in the present invention mean a divalent functional group obtained by removing a hydrogen atom from the above-mentioned aryl group having 6 to 60 carbon atoms and heteroaryl group having 2 to 60 carbon atoms. In this case, as non-limiting examples thereof, phenylene, naphthylene, biphenylene, pyridylene and the like are given.
The invention provides an electroluminescent material which comprises the benzophenanthridine derivative.
The invention also provides an organic electroluminescent element which comprises a first electrode, a second electrode and a plurality of organic layers positioned between the first electrode and the second electrode, wherein at least one layer of the organic layers contains the benzophenanthridine derivative.
Further, the organic layer containing benzophenanthridine derivatives is a free light-emitting layer, an electron transport layer, an electron injection layer, an electron transport auxiliary layer or an electron blocking layer.
Further, the organic layer containing benzophenanthridine derivatives is a light-emitting layer, and the benzophenanthridine derivatives are host substances of the light-emitting layer. May comprise a compound of formula (I) as described above. When such a light-emitting layer contains the compound represented by the above formula (I), the hole transport ability increases, and the chance of combining holes and electrons in the light-emitting layer increases, so that an organic electroluminescent element excellent in efficiency, lifetime, luminance, and driving voltage can be provided. In addition, the light-emitting layer of the organic electroluminescent element of the present invention may contain a compound other than the compound represented by the above formula (I) as a host.
The organic electroluminescent element of the present invention comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. Among them, the organic layer containing the benzophenanthridine derivative represented by the above formula (I) is preferably a light-emitting layer, an electron transport layer, and an electron transport auxiliary layer further stacked on the electron transport layer. In this case, the compound represented by the above chemical formula (I) can be used as a host substance or an electron transport layer and an electron transport auxiliary layer substance of the above light-emitting layer. However, it should be noted that each of these layers need not be present. The organic electroluminescent element described herein may include one light-emitting layer, or it may include a plurality of light-emitting layers. I.e. a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, wherein the three layers can exhibit blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises according to the invention a benzophenanthridine derivative according to the invention.
Further, the organic electroluminescent element according to the invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer and/or electron injection layer, i.e. the light-emitting layer is directly adjacent to the hole injection layer or the anode and/or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode.
In the other layers of the organic electroluminescent device according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent arrangements which are characterized in that one or more layers are applied by means of a sublimation process, with a temperature of less than 10 ℃ in a vacuum sublimation apparatus-5Pa, preferably less than 10-6Pa is applied by vapor deposition. However, the initial pressure may also be even lower, e.g. below 10-7Pa。
Preference is likewise given to organic electroluminescent elements which are characterized in that one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10 is-5The material is applied under a pressure between Pa and 1 Pa. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
These methods are generally known to those skilled in the art, and they can be applied to an organic electroluminescent element comprising the compound according to the present invention without inventive labor.
The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, characterized in that at least one layer is applied by means of a sublimation method and/or in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the invention relates to compositions comprising at least one of the compounds according to the invention. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, the compounds may furthermore preferably comprise further compounds. The processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires the preparation of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchytone, 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, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 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 monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1, 1-bis (3, 4-dimethylphenyl) ethane, or a mixture of these solvents.
The electron transport layer of the organic electroluminescent element of the present invention may contain an electron transport material, and in this case, may contain a compound represented by the above formula (I). When the electron transport layer contains the compound represented by the formula (I), the electron transport ability is enhanced by the two electron-withdrawing groups, and the injected electrons can be smoothly transported to the light-emitting layer, so that an organic electroluminescent element having excellent efficiency, lifetime, luminance, driving voltage, and the like can be provided. Wherein an electron transport assisting layer may be further laminated on the electron transport layer. In the case where the compound represented by the above formula (I) is contained in the transport auxiliary layer, the efficiency, lifetime, driving voltage, and the like of the blue organic electroluminescent element can be improved particularly because the effect of preventing excitons from transitioning from the light-emitting layer and the electron transport layer is achieved due to the high triplet energy level.
The structure of the organic electroluminescent element of the present invention is not particularly limited, and as a non-limiting example, as shown in fig. 1 and 2, a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and a cathode may be sequentially stacked. An electron injection layer may be further stacked on the electron transport layer, and a hole blocking layer may be further stacked on the light emitting layer. In addition, the organic electroluminescent element of the present invention may have a structure in which an insulating layer or an adhesive layer is interposed between an electrode and an organic layer.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
In the present invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are, unless otherwise specified, available from published commercial sources, and the percentages are, unless otherwise specified, percentages by mass.
Compared with the prior art, the invention has the beneficial effects that:
the benzophenanthridine derivative provided by the invention can be applied to an organic layer of an organic electroluminescent element due to excellent electronic mobility, thermal stability and luminescent property, and has good film forming property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of a bottom emission example of an organic electroluminescent device of the present invention;
fig. 2 is a schematic view of one example of top emission of the organic electroluminescent device of the present invention.
Reference numerals
1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer/electron blocking layer, 5-luminescent layer, 6-hole blocking layer/electron transport layer, 7-electron injection layer and 8-cathode.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The following examples are provided for testing the performance of OLED materials and devices using the following test apparatus and method:
OLED device performance detection conditions:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C.
Example 1
The preparation method of the compound CJHP299 comprises the following steps:
the first step is as follows: preparation of intermediate Int-1
Figure BDA0002730477610000211
20.0mmol of 1-bromo-2-hydroxy-3-naphthoic acid methyl ester, 20.0mmol of pyridine and 2.0mmol of DMAP are mixed, 100mL of dichloromethane is added for stirring and dissolving, 21.0mmol of trifluoromethanesulfonic anhydride is dropwise added, stirring reaction is carried out at room temperature for 10 hours, 100mL of water is added, an organic phase is separated, washing is carried out by using saturated saline water, the organic phase is collected, drying and filtering are carried out, the filtrate is concentrated under reduced pressure and dried, and separation and purification are carried out by using a silica gel column, so that white solid Int-1 is obtained, and the yield is 92%.
The second step is that: preparation of intermediate Int-2
Figure BDA0002730477610000212
15.0mmol of intermediate Int-1 was dissolved in 250mL of anhydrous THF, cooled to below 0 ℃ with ice salt bath under nitrogen protection, 16.0mmol of THF solution of 4-phenylphenyllithium was added dropwise, stirred for 2 hours, warmed to room temperature, stirred for 2 hours, 50mL of 2N dilute hydrochloric acid aqueous solution was added, the organic phase was separated, extracted with ethyl acetate, collected, dried, filtered, concentrated to dryness under reduced pressure, and separated and purified with silica gel column to give a yellow solid with yield: 78 percent.
The third step: preparation of intermediate Int-3
Figure BDA0002730477610000213
10.0mmol of intermediate Int-2, 12.0mmol of pinacol 2-nitrophenylborate, 30.0mmol of sodium carbonate, 100mL of toluene, 50mL of ethanol and 30mL of water, and 23.0mg of Pd (PPh)3)4Heating the catalyst, refluxing, stirring and reacting for 6 hours, cooling to room temperature, adding 30mL of water for dilution, separating an organic phase, extracting a water phase by using ethyl acetate, collecting the organic phase, drying, filtering, concentrating under reduced pressure to dryness, and recrystallizing by using ethanol to obtain a yellow solid, wherein the yield is as follows: and 64 percent.
The fourth step: preparation of intermediate Int-4
Figure BDA0002730477610000221
Dissolving 10.0mmol of intermediate Int-3 in 150mL of acetic acid, heating to 100 ℃, adding 50.0mmol of iron powder in batches, stirring for reaction for 1 hour, heating for reflux reaction for 10 hours, cooling to room temperature, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a yellow solid, wherein the yield is as follows: 85 percent.
The fifth step: preparation of compound CJHP299
Figure BDA0002730477610000222
10.2mmol of (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid, 8.5mmol of the intermediate Int-4, 3.6g (34.0mmol) of sodium carbonate and 5mg of Pd (PPh)3)4Adding 40mL of toluene, 10mL of ethanol and 10mL of water into the catalyst, heating, refluxing and stirring for reaction for 12 hours, cooling to room temperature, extracting with dichloromethane, drying an organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, separating and purifying by using a silica gel column, heating the filtrate to boiling by using ethanol, and filtering while the filtrate is hot to obtain 4.8g of a product CJHP299 with the yield of 82%. MS (MALDI-TOF): m/z 689.2721[ M + H ]]+；1HNMR(δ、CDCl3)：8.78～8.75(5H,m)；8.59～8.57(2H,m)；8.48～8.46(2H,m)；8.37～8.34(2H,m)；8.21～8.18(3H,m)；7.90～7.85(4H,m)；7.57～7.38(12H,m)；7.14～7.11(2H,m)。
Example 2
Preparation of compounds CJHP281 to CJHP298, CJHP300 to CJHP328, CJHP371 to CJHP389, CJHP425 to CJHP436 and CJHP468 to CJHP480 referring to the preparation of compound CJHP299 in example 1, except that different compounds are used instead of (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid in the fifth step of example 1 according to actual needs according to the desired product, and the mass amount of the compound is changed according to molar amount, and other parameters are adjusted conventionally.
Example 3
Preparation of compound CJHP261, comprising the following steps:
the first step is as follows: preparation of intermediate Int-5
Figure BDA0002730477610000231
10.0mmol of intermediate Int-4 prepared in the fourth step of example 1 was dissolved in 80mL of dry THF, cooled to-80 ℃ with liquid nitrogen under nitrogen protection, 4.8mL of 2.5M N-butyllithium N-hexane solution was added dropwise, stirred for 1 hour, 15.0mmol of trimethyl borate was added dropwise, stirred for 1 hour, warmed to room temperature, 50mL of 2N dilute hydrochloric acid aqueous solution was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was collected, dried, filtered, the filtrate was concentrated under reduced pressure, dispersed with petroleum ether, and filtered to obtain Int-5 as a yellow solid with a yield of 76%.
The second step is that: preparation of compound CJHP261
9.5mmol of intermediate Int-5, 8.0mmol of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 24.0mmol of sodium carbonate and 5mg of Pd (PPh)3)4Adding catalyst, 40mL of toluene, 10mL of ethanol and 5mL of water, heating, refluxing, stirring, reacting for 12 hours, cooling to room temperature, extracting with ethyl acetate, drying organic phase, filtering, and concentrating the filtrate under reduced pressureAfter drying, the residue was separated and purified by a silica gel column to obtain 3.6g of CJHP261 with a yield of 74%. MS (MALDI-TOF): m/z 613.2410[ M + H ]]+；1HNMR(δ、CDCl3)：8.92(1H,s)；8.80～8.77(4H,m)；8.37～8.34(5H,m)；7.92～7.81(5H,m)；7.64～7.48(10H,m)；7.45～7.37(3H,m)。
Example 4
The preparation of the compounds CJHP253 to CJHP260, CJHP262 to CJHP280 and CJHP447 to CJHP449, referring to the synthesis method of example 3, is different only in that different compounds are used according to the difference of the desired products to replace 2-chloro-4, 6-diphenyl-1, 3, 5-triazine in the second step of example 3 according to actual needs, and the mass amount of the compounds is changed according to the molar amount, and other parameters are adjusted accordingly.
Example 5
The preparation of compound CJHP370 comprises the following steps:
the first step is as follows: preparation of intermediate Int-6
Figure BDA0002730477610000241
10.0mmol of intermediate Int-1 prepared in example 1, 12.0mmol of pinacol 2-nitrophenylborate, 30.0mmol of sodium carbonate, 100mL of THF and 40mL of water are mixed, and 23.0mg of Pd (PPh) are added3)4Heating the catalyst, refluxing and stirring for reacting for 6 hours, cooling to room temperature, adding 30mL of water for diluting, extracting the water phase by using ethyl acetate, collecting the organic phase, drying, filtering, concentrating under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a yellow solid, wherein the yield is as follows: 56 percent.
The second step is that: preparation of intermediate Int-7
Figure BDA0002730477610000242
Dispersing 10.0mmol of intermediate Int-6 in 120mL of ethanol, adding 50.0mmol of iron powder and 50.0mmol of ammonium chloride, adding 60mL of water, heating, refluxing, stirring, reacting for 10 hours, cooling to room temperature, filtering, washing a filter cake with dichloromethane, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain yellow solid Int-7 with the yield of 85%.
The third step: preparation of intermediate Int-8
Figure BDA0002730477610000243
Mixing 10.0mmol of intermediate Int-7 with 80mL of thionyl chloride, heating and refluxing, slowly dropwise adding 2mL of pyridine, stirring for reaction for 12 hours, cooling to room temperature, concentrating under reduced pressure to remove thionyl chloride, adding 100mL of ice water for dilution, extracting with ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a compound Int-8 with the yield of 82%.
The fourth step: preparation of intermediate Int-9
Figure BDA0002730477610000251
Dissolving 12.0mmol of carbazole in 60mL of dimethyl sulfoxide, cooling to 5 ℃ by using an ice water bath, adding 12.0mmol of sodium hydride (60% oil dispersion) solid in batches, stirring for reaction for 1 hour, adding 10.0mmol of intermediate Int-8, heating to room temperature, stirring for reaction for 8 hours, pouring the reaction solution into 200mL of ice water, filtering, washing a filter cake by using water, and separating and purifying by using a silica gel column to obtain a compound Int-9 with the yield of 88%.
The fifth step: preparation of compound CJHP370
Figure BDA0002730477610000252
9.6mmol of (3- (9H-carbazol-9-yl) phenyl) boronic acid, 8.0mmol of intermediate Int-9, 5.5g (16.0mmol) of potassium phosphate hydrate and 185.0mg of Pd (PPh)3)4Adding catalyst, adding 80mL of toluene, 40mL of ethanol and 40mL of water, heating, refluxing, stirring, reacting for 12 hours, cooling to room temperature, adding 20mL of water for dilution, extracting with dichloromethane, drying the organic phase, filtering, and filteringConcentrating the solution under reduced pressure, and separating and purifying with silica gel column to obtain CJHP370 with yield of 82%. MS (MALDI-TOF): m/z636.2456[ M + H ]]+；1HNMR(δ、CDCl3)：8.75(1H,s)；8.69～8.67(1H,m)；8.14～8.10(5H,m)；7.94～7.92(2H,m)；7.84～7.79(3H,m)；7.50～7.42(6H,m)；7.35～7.28(9H,m)；7.14～7.12(1H,m)；7.08～7.07(1H,m)。
Example 6
The preparation of the compounds CJHP 329-CJHP 339, CJHP 343-CJHP 369, CJHP390, CJHP 437-CJHP 446 refers to the synthesis method of example 5, except that different compounds are used to replace carbazole in the fourth step and (3- (9H-carbazole-9-yl) phenyl) boronic acid in the fifth step according to actual needs according to different required products, and the mass amount of the compounds is changed according to molar amount, and other parameters are adjusted adaptively.
Example 7
Preparation of compound CJHP392, comprising the following steps:
the first step is as follows: preparation of intermediate Int-11
Figure BDA0002730477610000261
Under the protection of nitrogen, 15.0mmol of intermediate Int-10 (prepared according to the synthesis method of the first to fourth steps in example 1) was dissolved in 80mL of N, N-dimethylformamide, 18.0mmol of NBS was added in portions at room temperature, the mixture was stirred for 2 hours, the reaction mixture was heated to 50 ℃ and stirred for 1 hour, the reaction mixture was poured into 200mL of water, the reaction mixture was stirred for 1 hour, the mixture was filtered, and the filter cake was recrystallized from ethanol to obtain intermediate Int-11 with a yield of 92%.
The second step is that: preparation of compound CJHP392
Figure BDA0002730477610000262
10.0mmol of intermediate Int-11, 24.0mmol of 2-naphthaleneboronic acid, 6.5g (60.0mmol) of sodium carbonate and 11.5mg of Pd (PPh)3)4Catalyst, addAdding 80mL of toluene, 40mL of ethanol and 40mL of water, heating, refluxing, stirring, reacting for 12 hours, cooling to room temperature, extracting with ethyl acetate, drying organic phase, filtering, concentrating the filtrate under reduced pressure, separating and purifying by using a silica gel column, and recrystallizing by using toluene-THF to obtain the product CJHP392 with the yield of 77%. MS (MALDI-TOF): m/z 608.2394[ M + H ]]+；1HNMR(δ、CDCl3)：8.79～8.77(2H,d)；8.60(1H,s)；8.46(1H,s)；8.41～8.39(1H,d)；8.09～7.81(16H,m)；7.57～7.52(6H,m)；7.43～7.37(2H,m)。
Example 8
Synthesis of CJHP391, CJHP393 to CJHP424, CJHP464, CJHP465 referring to the synthesis method of example 7,
except that 2-naphthalene boronic acid in the second step of example 7 was replaced with a different compound according to actual needs depending on the desired product, the amount of the compound used by mass was changed according to the molar amount, and other parameters were adjusted adaptively.
Example 9
Preparation of compound CJHP 453:
Figure BDA0002730477610000271
under the protection of nitrogen, 11.0mmol of intermediate Int-12 and 13.2mmol of 7H-dibenzo [ c, g%]Carbazole, 1.6g of sodium tert-butoxide and 0.21g of cuprous iodide, 20.7mg of Pd2(dba)3CHCl3And 0.1mL of 10% tri-tert-butylphosphine toluene solution, then 60mL of dry toluene is added, the temperature is raised to 100 ℃, the mixture is stirred and reacted for 12 hours, the mixture is cooled to room temperature, 20mL of water is added for dilution, the ethyl acetate is used for extraction, the organic phase is dried, the filtration is carried out, the filtrate is concentrated under reduced pressure and dried, the separation and purification are carried out by a silica gel column, and then the recrystallization is carried out by dichloromethane-tetrahydrofuran, so that the CJHP453 is obtained, and the yield is 66%. MS (MALDI-TOF): m/z 627.2171[ M + H ]]+；1HNMR(δ、CDCl3)：9.15(1H,s)；8.71～8.69(1H,m)；8.54～8.52(1H,m)；8.37～7.34(3H,m)；8.17～8.14(3H,m)；8.08～8.06(2H,d)；8.01～7.97(4H,m)；7.82～7.77(2H,m)；7.73～7.58(5H,m)；7.42～7.39(2H,m)；7.28～7.24(1H,m)。
Example 10
The synthesis of compounds CJHP 450-CJHP 452 and CJHP 454-CJHP 457, see the synthesis method of example 9, except that different compounds are used to replace Int-12 and 7H-dibenzo [ c, g ] carbazole as intermediates in example 9 according to actual needs, and the mass amount of the compounds is changed according to molar amount, and other parameters are adaptively adjusted according to the required product.
Example 11
Preparation of compound CJHP462, comprising the following steps:
the first step is as follows: preparation of intermediate Int-13
Figure BDA0002730477610000281
Under nitrogen protection, 10.0mmol of intermediate Int-10 was dissolved in 80mL of toluene, and 12.0mmol of p-bromophenylboronic acid, 25.0mmol of anhydrous sodium carbonate and 25mg of Pd (PPh) were added3)4And (3) heating, refluxing and stirring the catalyst for reaction for 8 hours under the protection of nitrogen, cooling to room temperature, extracting with dichloromethane, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by a silica gel column to obtain an intermediate Int-13 with the yield of 68%.
The second step is that: preparation of intermediate Int-14
Figure BDA0002730477610000282
Referring to the first step synthesis of example 7, intermediate Int-14 was prepared as a yellow solid in 88% yield by replacing intermediate Int-10 of the first step of example 7 with Int-13.
The third step: preparation of compound CJHP462
Figure BDA0002730477610000283
10.0mmol of intermediate Int-14,24.0mmol of diphenylamine, 2.9g (30.0mmol) of sodium tert-butoxide, 190.5mg of cuprous iodide, 20.7mg of Pd2(dba)3CHCl3And 0.1mL of 10% tri-tert-butylphosphine toluene solution, adding 80mL of dry toluene, heating, refluxing, stirring, reacting for 12 hours, cooling to room temperature, extracting with ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure, separating and purifying with a silica gel column, and recrystallizing with toluene-dichloromethane to obtain the product CJHP462 with a yield of 69%. MS (MALDI-TOF): m/z 766.3245[ M + H ]]+；1HNMR(δ、CDCl3)：8.78～8.76(2H,d)；8.24～8.22(2H,d)；7.96～7.83(6H,m)；7.67～7.54(6H,m)；7.35～7.24(11H,m)；7.05～7.02(4H,m)；6.97～6.94(8H,m)。
Example 12
The synthesis of compounds CJHP 340-CJHP 342, CJHP 458-CJHP 461, and CJHP 463-CJHP 467 is similar to that of example 11 except that the diphenylamine in the third step of example 11 is replaced with different compounds according to actual needs according to the desired products, the mass amount of the compounds is changed according to the molar amount, and other parameters are adaptively adjusted.
Example 13
Preparation of compound CJHP486, comprising the steps of:
the first step is as follows: preparation of intermediate Int-13
Figure BDA0002730477610000291
Under nitrogen, 10.0mmol of intermediate Int-15 (prepared according to the synthesis method of the first to fourth steps in example 1) was dissolved in 80mL of toluene, and 12.0mmol of p-bromophenylboronic acid, 25.0mmol of anhydrous sodium carbonate and 25mg of Pd (PPh)3)4And (3) heating, refluxing and stirring the catalyst for reaction for 8 hours under the protection of nitrogen, cooling to room temperature, extracting with dichloromethane, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by a silica gel column to obtain an intermediate Int-16 with the yield of 65%.
The second step is that: preparation of intermediate Int-17
Figure BDA0002730477610000292
Under the protection of nitrogen, 10.0mmol of intermediate Int-16 is dissolved in 100mL of dry THF, liquid nitrogen is used for cooling to-80 ℃, 4.8mL of 2.5M N-butyllithium N-hexane melt is dropwise added, stirring reaction is carried out for 30 minutes, 15.0mmol of trimethyl borate solution in THF is dropwise added, stirring reaction is carried out for 1 hour, the temperature is raised to room temperature, 50mL of 2N dilute hydrochloric acid aqueous solution is added, extraction is carried out by ethyl acetate, an organic phase is collected, drying and filtration are carried out, the filtrate is decompressed, concentrated and dried, petroleum ether is added for dispersion and filtration, and the intermediate Int-17 is obtained, wherein the yield is 72%.
The third step: preparation of compound CJHP486
Figure BDA0002730477610000301
9.6mmol of intermediate Int-17, 8.0mmol of intermediate Int-12, 2.2g (20.0mmol) of sodium carbonate and 92.4mg of Pd (PPh3)4 catalyst, 60mL of toluene, 30mL of ethanol and 20mL of water are added, the mixture is heated under reflux and stirred for 12 hours, the mixture is cooled to room temperature, 20mL of water is added for dilution, the mixture is extracted by dichloromethane, an organic phase is dried and filtered, a filtrate is concentrated under reduced pressure to dryness, and the filtrate is separated and purified by a silica gel column to obtain a compound CJHP486 with the yield of 82%. MS (MALDI-TOF): m/z 686.2614[ M + H ]]+；1HNMR(δ、CDCl3)：9.22(1H,s)；8.79～8.77(2H,d)；8.54～8.53(1H,m)；8.31(4H,s)；8.27～8.16(7H,m)；7.96～7.92(3H,m)；7.78～7.76(2H,m)；7.63～7.52(6H,m)；7.45～7.42(1H,m)；7.38～7.33(4H,m)。
Example 14
Synthesis of compounds CJHP 481-CJHP 485, CJHP487, CJHP488 referring to the method of example 13, except that different compounds were used according to actual needs to replace the intermediate Int-12 of the third step in example 13 according to the desired product, and the mass amount of the compound was changed according to the molar amount, and other parameters were adaptively adjusted.
Test example 1
After sublimation purification of each of the compounds prepared in examples 1 to 15, an organic electroluminescent element was produced by the following method:
1) the ITO-coated glass substrate is ultrasonically washed by distilled water, ultrasonically washed by mixed solvent of isopropanol and acetone/ethanol, baked in clean environment to be completely dried, irradiated by an ultraviolet light cleaning machine for 10 minutes, cleaned by UV for 5 minutes, and transferred to a vacuum evaporation machine.
2) HT002 (eight billion space-time) is laminated on the processed ITO electrode in sequence,
Figure BDA0002730477610000312
) HT022 (eight billion space-time,
Figure BDA0002730477610000313
) HT001 (space-time-of-billion,
Figure BDA0002730477610000314
) ADN + 5% DA021 (billionth space-time,
Figure BDA0002730477610000318
) cJHP 253-CJHP 488 Compound + 50% Liq
Figure BDA0002730477610000317
/LiF
Figure BDA0002730477610000316
/Al
Figure BDA0002730477610000315
An organic electroluminescent element was produced.
Comparative example 1
An organic electroluminescent element was prepared in the same manner as in test example 1 except that Alq3 (8-hydroxyquinoline aluminum) was used as the electron transport layer material instead of the benzophenanthridine derivative according to the present invention.
Comparative example 2
An organic electroluminescent element was produced in the same manner as in test example 1, except that the benzophenanthridine derivative of the present invention was not used as an electron transporting layer material.
Wherein the structural formulas of AND AND Alq3 are shown as follows:
Figure BDA0002730477610000311
for the organic electroluminescent elements prepared in test example 1 and comparative examples 1 and 2, a current density of 10mA/cm was measured2The driving voltage, current efficiency, light emission peak, part of the compounds and the test results of the organic electroluminescent elements prepared in comparative examples 1 and 2 are shown in table 1.
TABLE 1
Test compounds Drive voltage (V) Maximum peak (nm) Current efficiency (cd/A)
CJHP261 3.82 465 7.25
CJHP287 4.04 465 7.19
CJHP299 3.69 464 7.86
CJHP317 3.56 465 7.98
CJHP370 4.26 463 6.91
CJHP392 4.12 466 7.05
CJHP453 3.95 466 7.17
CJHP462 4.20 464 6.86
CJHP486 3.78 465 7.16
Comparative example 1 4.77 463 5.82
Comparative example 2 4.92 466 6.45
As can be seen from the above table, the organic electroluminescent element using the compound of the present invention for the electron transport layer showed superior performance in terms of driving voltage, current efficiency, and the maximum peak of light emission, compared to the organic electroluminescent element using Alq3 for the electron transport layer and the organic electroluminescent element without the electron transport layer.
The results of the testing of the other compounds are essentially consistent with the data in Table 1, and are not listed due to space limitations.
Test example 2
After sublimation purification of each of the compounds prepared in examples 1 to 15, an organic electroluminescent element was produced by the following method:
1) the ITO-coated glass substrate is ultrasonically washed by distilled water, ultrasonically washed by mixed solvent of isopropanol and acetone/ethanol, baked in clean environment to be completely dried, irradiated by an ultraviolet light cleaning machine for 10 minutes, cleaned by UV for 5 minutes, and transferred to a vacuum evaporation machine.
2) HT002 (eight billion space-time) is laminated on the processed ITO electrode in sequence,
Figure BDA0002730477610000321
) HT022 (eight billion space-time,
Figure BDA0002730477610000322
) HT001 (space-time-of-billion,
Figure BDA0002730477610000323
) CJHP253 to CJHP488 individual compounds + 6% RD018 (eight billion space-time,
Figure BDA0002730477610000324
)/CJHP317+50％Liq
Figure BDA0002730477610000325
/LiF
Figure BDA0002730477610000326
/Al
Figure BDA0002730477610000327
an organic electroluminescent element was produced.
Comparative example 3
An organic electroluminescent element was prepared in the same manner as in test example 2 except that RH03 was used as the host material of the light-emitting layer instead of the benzophenanthridine derivative according to the present invention.
The structure of RH03 is as follows:
Figure BDA0002730477610000331
for the organic electroluminescent elements prepared in test example 2 and comparative example 3, the current density was measured at 10mA/cm2The driving voltage, current efficiency, light emission peak, part of the compounds and the test results of the organic electroluminescent element prepared in comparative example 2 are shown in table 2.
TABLE 2
Figure BDA0002730477610000332
As can be seen from the above table, the organic electroluminescent element using the benzophenanthridine derivative of the present invention for the light-emitting layer host exhibits superior performance in terms of driving voltage, current efficiency, and the maximum peak of light emission, as compared to the organic electroluminescent element using RH03 for the light-emitting layer host.
The results of the testing of the other compounds are essentially consistent with the data in Table 2, and are not listed due to space limitations.
From the above, it is found that the organic electroluminescent element produced by using the benzophenanthridine derivative of the present invention can be applied to a flat light emitting body such as a mobile phone, a wall-mounted television, a flat panel display, and illumination, a light source such as a backlight source of a copying machine, a printer, and a liquid crystal display, a display panel, a marker lamp, and the like.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. A benzophenanthridine derivative is characterized in that the structural formula of the derivative is shown as a formula (I):
Figure FDA0002730477600000011
wherein R is1～R11Each independently selected from hydrogen, deuterium, halogen, cyano, C1-C40Alkyl of (C)2-C40Alkenyl of, C2-C40Alkynyl of (A), C3-C40Cycloalkyl of (2), heterocycloalkyl of atomic number 3 to 40, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C1-C40Alkoxy group of (C)6-C60Aryloxy group of (A), C1-C40Alkylsilyl group of (C)6-C60Arylsilyl group of (C)1-C40Alkyl boron group of (2), C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Any two or more adjacent substituents may be optionally joined or fused, or bridging groups bonded to the same nitrogen atom, phosphorus atom, boron atom, oxygen atom, or sulfur atom may be bridged to each other to form a single ring or a fused ring.
2. Benzophenanthridine derivatives according to claim 1, characterized in that R2～R6、R8～R11Each independently selected from hydrogen, deuterium, halogen, cyano, C1-C40Alkyl of (C)2-C40Alkenyl of, C2-C40Alkynyl of (A), C3-C40Cycloalkyl group, heterocycloalkyl group having 3 to 40 atomic numbers, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C1-C40Alkoxy group of (C)6-C60Aryloxy group of (A), C1-C40Alkylsilyl group of (C)6-C60Arylsilyl group of (C)1-C40Alkyl boron group of (2), C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Any two or more adjacent substituents of the group consisting of arylamine groups of (a) may be optionally joined or condensed, or bridged with each other by a bridging group bonded to the same nitrogen atom, phosphorus atom, boron atom, oxygen atom or sulfur atom, to form a single ring or a condensed ring; r1、R7Each independently selected from hydrogen, deuterium, halogen, cyano, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60And R is selected from the group consisting of arylamine groups of (A), and R1And R2、R7And R6Or R7And R8Bridging groups which may be joined or fused, or bonded to the same nitrogen, phosphorus, boron, oxygen or sulfur atom, are bridged to each other to form a single or fused ring.
3. Benzophenanthridine derivatives according to claim 1, characterized in that R2～R6、R8～R11Each independently selected from hydrogen, deuterium, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Any two or more adjacent substituents may be optionally joined or condensed, or bridging groups bonded to the same nitrogen atom, phosphorus atom, boron atom, oxygen atom, or sulfur atom are bridged to each other to form a single ring or a condensed ring, R1、R7Each independently selected from hydrogen, deuterium, halogen, cyano, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60And R is selected from the group consisting of arylamine groups of (A), and R1And R2、R7And R6Or R7And R8Bridging groups which may be joined or fused, or bonded to the same nitrogen, phosphorus, boron, oxygen or sulfur atom, are bridged to each other to form a single or fused ring.
4. The benzophenanthridine derivative of claim 1, wherein R is1～R11Each independently selected from hydrogen, deuterium, halogen, cyano, C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Any two or more adjacent substituents may be optionally joined or fused, or bridging groups bonded to the same nitrogen atom, phosphorus atom, boron atom, oxygen atom, or sulfur atom may be bridged to each other to form a single ring or a fused ring.
5. The benzophenanthridine derivative of any one of claims 1 to 4, wherein C is2-C60The heteroaryl is one of the following structural formulas II-1 to II-17:
Figure FDA0002730477600000021
wherein Z is1、Z2Each independently selected from hydrogen, deuterium, halogen atom, hydroxylA group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, C1-C40Alkyl radical, C2-C40Alkenyl radical, C2-C40Alkynyl, C1-C40Alkoxy radical, C3-C40Cycloalkyl radical, C3-C40Cycloalkenyl radical, C6-C60Aryl radical, C6-C60Aryloxy radical, C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60Arylamino or C of2-C60One of the heteroaryl groups of (a);
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T1represents oxygen, sulfur, CR12R13Or NCy1；
The R is12And R13Each independently selected from hydrogen, deuterium, C1-C40Alkyl of (C)2-C40Alkenyl of, C2-C40Alkynyl of (A), C3-C40Cycloalkyl of (2), heterocycloalkyl of atomic number 3 to 40, C6-C60Aryl of (C)2-C60Heteroaryl of (a);
the Cy is1C selection6-C60Aryl radical, C2-C60One of heteroaryl;
Figure FDA0002730477600000031
represents a bond between a substituent and the main structure.
6. The benzophenanthridine derivative of any one of claims 1-5, wherein the benzophenanthridine derivative has a specific structural formula of CJHP253 to CJHP 488:
Figure FDA0002730477600000032
Figure FDA0002730477600000041
Figure FDA0002730477600000051
Figure FDA0002730477600000061
Figure FDA0002730477600000071
Figure FDA0002730477600000081
Figure FDA0002730477600000091
Figure FDA0002730477600000101
Figure FDA0002730477600000111
wherein, T3Is O-, S-or one of the following structures,
Figure FDA0002730477600000121
wherein, -and-represent a connecting bond.
7. An electroluminescent material, characterized in that it comprises a benzophenanthridine derivative according to any one of claims 1 to 6.
8. An organic electroluminescent element comprising a first electrode, a second electrode, and a plurality of organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers contains the benzophenanthridine derivative according to any one of claims 1 to 6.
9. The organic electroluminescent element according to claim 8, wherein the organic layer containing a benzophenanthridine derivative is a free light-emitting layer, an electron-transporting layer, an electron-injecting layer, an electron-transporting auxiliary layer, or an electron-blocking layer.
10. The organic electroluminescent element according to claim 9, wherein the organic layer containing a benzophenanthridine derivative is a light-emitting layer, and the benzophenanthridine derivative is a host substance of the light-emitting layer.
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