CN113429406B - Benzonaphthyridine derivative, organic electroluminescent material, and organic electroluminescent element - Google Patents

Benzonaphthyridine derivative, organic electroluminescent material, and organic electroluminescent element Download PDF

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CN113429406B
CN113429406B CN202110704453.2A CN202110704453A CN113429406B CN 113429406 B CN113429406 B CN 113429406B CN 202110704453 A CN202110704453 A CN 202110704453A CN 113429406 B CN113429406 B CN 113429406B
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曹建华
戴雄
刘赛赛
邸庆童
郭文龙
赵佳
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

The invention relates to a benzonaphthyridine derivative, an organic electroluminescent material and an organic electroluminescent element, wherein the structural formula of the benzonaphthyridine derivative is shown as a formula (I). The benzonaphthyridine derivative has good film forming property, and can be used for manufacturing an organic electroluminescent element with lower driving voltage, higher light-emitting efficiency and longer service life compared with the conventional electronic transmission material when being applied to an electronic transmission layer and an electronic transmission auxiliary layer, thereby manufacturing a full-color display panel with improved performance and service life.
Figure DDA0003130595580000011

Description

Benzonaphthyridine derivative, organic electroluminescent material, and organic electroluminescent element
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to a benzonaphthyridine derivative, an organic 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.
Further, many organic monomolecular substances having an imidazole group, an oxazole group, a thiazole group, and a spirofluorene group have been disclosed as substances that can be applied to an electron injection layer and a transport layer in the past. For example, TPBI described in chinese patents CN103833507B, CN107573328B, CN107556310B and U.S. Pat. No. 5,645,948 issued by kodak in 1996 are substances for electron transport layers having an imidazole group, and in the structure thereof, three N-phenylbenzimidazole groups are contained at the 1,3,5 substitution position of benzene, and in terms of function, not only have the ability to transport electrons but also have the function of blocking holes crossing over from the light-emitting layer, but have a problem of low thermal stability when actually applied to elements.
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 benzonaphthyridine derivative, an organic electroluminescent material and an organic electroluminescent element.
The invention provides a benzonaphthyridine derivative, wherein the structural formula of the benzonaphthyridine derivative is shown as the formula (I):
Figure BDA0003130595560000021
wherein X1、X2Selected from N or CR6And X1And X2Not N at the same time;
R1～R6each independently selected from hydrogen, deuterium, cyano, nitro, C1-C40Alkyl of (C)2-C40Alkenyl of, C2-C40Alkynyl of, C3-C40Cycloalkyl of (2), heterocycloalkyl of atomic number 3 to 40, C6-C60Aryl of, C2-C60Heteroaryl of (A), C1-C40Alkoxy group of (1), C6-C60Aryloxy group of (1), 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 (1), 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, fused, or bonded to a bridging group of the same nitrogen atom, phosphorus atom, boron atom, oxygen, or sulfur to bridge with each other to form a single ring or a fused ring;
Ar1、Ar2is selected from C6-C60Aryl of (C)2-C60Heteroaryl of (1), C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (2) and C6-C60One or more of the arylamine groups of (a).
Further, said X1、X2Selected from N or CR6And X1And X2Not N at the same time;
R1～R6each independently selected from hydrogen, deuterium, C1-C40Alkyl of (C)6-C60Aryl of, C2-C60Heteroaryl of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1), C6-C60One of arylamine groups of (a);
Ar1、Ar2is selected from C6-C60Aryl of, C2-C60Heteroaryl of (A), C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of (1) and C6-C60One of arylamine groups of (a).
Further, said C2-C60The heteroaryl group of (a) is one of the following structures:
Figure BDA0003130595560000031
wherein Z is1、Z2Each independently selected from 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-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, CR15R16Or NAr3；
The R is15And R16Each 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-C60One of the heteroaryl groups of (a);
ar is3Is selected from C6-C60Aryl of (C)2-C60Heteroaryl of (A), C6-C60Aryl boron group of (1), C6-C60Aryl phosphorus radical of (1), C6-C60Aryl phosphorus oxide group of (2) and C6-C60One of the arylamine groups of (a);
Figure BDA0003130595560000041
represents the bond of the substituent to the host structure.
Further, the heteroaryl is selected from one of pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroimidazole, imidazopyridine, triazolopyridine and quinazoline;
according to the benzonaphthyridine derivative of the present invention, by introducing various substituents, particularly aryl and/or heteroaryl groups, the molecular weight of the compound is significantly increased, and the glass transition temperature is increased, thereby enabling higher thermal stability than that of conventional light-emitting materials. Therefore, the performance and lifetime characteristics of the organic electroluminescent element including the benzonaphthyridine derivative according to the present invention can be greatly improved. The organic electroluminescent element with such improved performance and life characteristics can eventually maximize the performance of a full-color organic light-emitting panel.
Further, the pyrimidineThe pyridine, pyrazine, triazine, imidazole, benzimidazole, phenanthroimidazole, imidazopyridine, triazolopyridine and quinazoline may each independently be deuterium, halogen atom, cyano group, nitro group, C1-C40Alkyl of (C)2-C40Alkenyl of, C2-C40Alkynyl of (A), C3-C40Cycloalkyl of (C)3-C40Heterocycloalkyl of (A), C6-C60Aryl of (C)2-C60Heteroaryl of (1), C1-C40Alkoxy group of (1), C6-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 (2) and C6-C60When the substituent is plural, plural substituents may be the same as or different from each other.
Further, the benzonaphthyridine derivative is one of CJHP 149-CJHP 322, and the specific structural formula is as follows:
Figure BDA0003130595560000042
Figure BDA0003130595560000051
Figure BDA0003130595560000061
Figure BDA0003130595560000071
Figure BDA0003130595560000081
Figure BDA0003130595560000091
Figure BDA0003130595560000101
Figure BDA0003130595560000111
Figure BDA0003130595560000121
wherein, T2is-O-, -S-, or one of the following structures:
Figure BDA0003130595560000122
Figure BDA0003130595560000131
* -and-represent a 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 in the sense of the present invention, preferably having 1 to 40 carbon atoms, is understood 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 and 2, 2-trifluoroethoxy and the like.
Heteroalkyl in the sense of the present invention is preferably heteroalkyl having from 1 to 40 carbon atoms, as non-limiting examples of which are 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, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2-trifluoroethoxy, 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, the cycloalkyl, cycloalkenyl groups of the present invention are preferably those having a number of carbon atoms of from 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 according to the present invention means 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 according to 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 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 according to 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 according to 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 of 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 are phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure BDA0003130595560000141
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 isotridendenyl group, a spiroisotridelenyl group, a furanyl group, a benzofuranyl group, an isobenzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, a carbazolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a benzo [5, 6.6 ] benzo]Quinolyl, benzo [6,7 ]]Quinolyl, benzo [7,8 ]]Quinolyl, phenothiazinyl, phenoxazine, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, quinoxalyl pyrazinoimidazolyl, quinoxalinimidazolyl, oxazolyl, benzoxazolyl naphthooxazolyl, anthraoxazolyl, phenanthrooxazyl,Isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, pyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazanthryl, 2, 7-diazapenyl, 2, 3-diazapenyl, 1, 6-diazapenyl, 1, 8-diazapenyl, 4, 5-diazapenyl, 4,5,9,10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluoreryl cyclic, 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 thiadiazolyl groups derived from combinations of these groups or groups derived from 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.
Further, the organic electroluminescent material comprises the benzonaphthyridine derivative.
A second object of the present invention is to provide an organic electroluminescent element comprising a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layers comprise the benzonaphthyridine derivative.
The organic electroluminescent element includes 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 compound represented by the above formula (I) is preferably a light-emitting layer, an electron transport layer, and an electron transport assisting 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. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particular preference is given to systems having three light-emitting layers, where the three layers can exhibit blue, green and red emission. If more than one light-emitting layer is present, at least one of these layers comprises the compounds of the invention according to the invention.
The present invention provides an organic electroluminescent element comprising the compound represented by the above formula (I). Specifically, the organic electroluminescent element according to the present invention comprises a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein at least one of the one or more organic layers comprises a compound represented by the formula (I). In this case, the above-mentioned compounds may be used alone or in combination of two or more. The one or more organic layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. Preferably, the organic layer including the compound of formula (I) may be a light emitting layer, an electron transport layer, and a hole transport layer, and more preferably, may be an electron transport layer or a light emitting layer.
The light-emitting layer of the organic electroluminescent element according to the present invention may contain a host material, and in this case, the compound of the formula (I) may be contained as the host material. When such a light-emitting layer contains the compound represented by the above formula (I), the carrier 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 dopant.
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 the 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 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 auxiliary 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 the transition of excitons from the light-emitting layer and the electron transport layer is obtained due to the high triplet level.
The structure of the organic electroluminescent element of the present invention is not particularly limited, and may be a structure in which 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 are sequentially stacked as shown in fig. 1 and 2, as a non-limiting example. 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 the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", and the like, indicate orientations or positional relationships that are based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and to simplify the description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
Further, the organic layer is a light-emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer or an optical refraction layer.
Furthermore, the benzonaphthyridine derivative is a material of an electron transport layer.
Further, the benzonaphthyridine derivative is a material of a light-emitting layer.
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 anode and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
In the other layers of the organic electroluminescent device according to the invention, in particular in the hole-injecting layer and the 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 below 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 in which 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, are obtained by appropriate substitution of a compound of formula (I). 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, at least one layer being applied by means of a sublimation method, and/or at least one layer being applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or at least one layer being applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to pharmaceutical compositions comprising at least one compound of the invention as indicated above. 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, α -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 dibutyl glycol, tripropyl glycol, 1, 2-dimethyl benzyl glycol, 1, 2-octylbenzene, 2-dimethyl benzene ether, 2, 1, octylbenzene, or mixtures of these solvents.
In addition, the starting materials used in the present invention are commercially available unless otherwise specified, and any range recited herein includes any value between the endpoints and any subrange between the endpoints or any value between the endpoints.
Compared with the prior art, the invention has the beneficial effects that:
the benzonaphthyridine derivative has good film forming property, and can be used for manufacturing an organic electroluminescent element with lower driving voltage, higher light-emitting efficiency and longer service life compared with the conventional electronic transmission material when being applied to an electronic transmission layer and an electronic transmission auxiliary layer, thereby manufacturing a full-color display panel with improved performance and service life.
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 embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art 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 barrier layer, 5-luminescent layer, 6-hole barrier/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 were used to test the performance of OLED materials and devices using the following instruments and methods:
OLED device performance detection conditions:
luminance and chromaticity coordinates: testing with a spectrum scanner PhotoResearchPR-715;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: NEWPORT1931-C was used for testing.
Example 1
The preparation method of the compound CJHP160 comprises the following steps:
the first step is as follows: preparation of Compound Int-1
Figure BDA0003130595560000201
Dissolving 50.0mmol of acetophenone, 50.0mmol of aniline and 50.0mmol of SM-3 (CAS: 849619-11-0) in 100mL of DMSO, adding 80.0mmol of iodine and 10.0mmol of concentrated hydrochloric acid, heating to 110 ℃, stirring for reaction for 24 hours, cooling to room temperature, pouring the reaction solution into 200mL of saturated aqueous sodium sulfite solution, extracting with ethyl acetate, washing the organic phase with saturated aqueous salt solution, collecting the organic phase, drying, filtering, concentrating the filtrate under reduced pressure, and separating and purifying with a silica gel column to obtain an intermediate compound Int-1 as a yellow solid with yield: 77 percent.
The second step: preparation of Compounds A and B
Figure BDA0003130595560000211
Dissolving 20.0mmol of Int-1 and 0.2mol of glycine ethyl ester hydrochloride in 150mL of n-butanol, heating, refluxing, stirring, reacting for 48 hours, cooling to room temperature, concentrating and drying under reduced pressure, separating and purifying with silica gel column, and recrystallizing with ethanol to obtain intermediate compound A, yellow solid, yield: 42% to yield compound B as intermediate, yellow solid, yield: and 43 percent.
The second step: preparation of Compound Int-2
Figure BDA0003130595560000212
10.0mmol of compound A and 20.0mol of sodium hydroxide are dissolved in 5mL of THF and 10mL of water, the mixture is heated and refluxed for 5 hours, the reaction is cooled to room temperature, THF is removed by concentration under reduced pressure, dilute hydrochloric acid is added dropwise to adjust the pH value, the mixture is filtered, and the filter cake is washed with water to obtain compound Int-2 as a yellow solid, yield: and 90 percent.
The third step: preparation of Compound Int-3
Figure BDA0003130595560000213
Mixing 20.0mmol of compound Int-2 with 50mL of quinoline, adding 10.0mmol of copper powder, heating, refluxing, stirring, reacting for 1 hour, cooling to room temperature, pouring the reaction solution into 200mL of water, filtering, washing a filter cake with water, and separating and purifying by using a silica gel column to obtain a compound Int-3, namely a white solid, and the yield is as follows: 75 percent.
The fourth step: preparation of Compound Int-4
Figure BDA0003130595560000221
Dissolving 20.0mmol of compound Int-3 in 50mL of dry THF, cooling to-78 ℃ with liquid nitrogen under the protection of nitrogen, dropwise adding 9.5mL of 2.5M N-butyllithium N-hexane solution, stirring for 10 minutes, dropwise adding 30.0mmol of trimethyl borate, stirring for 10 minutes, heating to room temperature, dropwise adding 50mL of 2N dilute hydrochloric acid aqueous solution, extracting with ethyl acetate, collecting the desired phase, drying, filtering, concentrating and drying the filtrate under reduced pressure, adding petroleum ether for dispersion, and filtering to obtain compound Int-4, a white solid, yield: 86 percent.
The fifth step: preparation of compound CJHP160
Figure BDA0003130595560000222
12.0mmol of Int-4, 10.0mmol of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (CAS: 3842-55-5), 30.0mmol of anhydrous potassium carbonate and 58.0mg of Pd (PPh)3)4Adding 40mL of toluene, 20mL of ethanol and 20mL of water into the catalyst, heating, refluxing, stirring, reacting for 12 hours, cooling to room temperature, filtering, washing a filter cake with water and ethanol, separating and purifying by using a silica gel column, and recrystallizing by using toluene-ethanol to obtain a product CJHP160 with the yield of 78%, wherein the mass ratio of MS (MALDI-TOF): m/z564.2204[ M + H ]]+。
Example 2
Preparation of compound CJHP 261:
Figure BDA0003130595560000223
20.0mmol of intermediate Int-5 (Panax ginseng C.A.)Prepared as in the synthetic method of example 1) was dissolved in 80mL of dry THF, the temperature was reduced to-78 deg.C under nitrogen protection, 10.0mL of a 2.5M n-butyllithium n-hexane solution was added dropwise, the mixture was stirred for 1 hour, the temperature was increased to-50 deg.C, 25.0mmol of a solution of diphenylphosphoryl chloride (CAS: 1079-66-9) in THF was added dropwise, the mixture was stirred for 1 hour, the mixture was heated to room temperature and stirred for 10 hours, 50mL of methanol was added, the mixture was concentrated and dried under reduced pressure, the residue was dissolved in 80mL of dichloromethane, 20mL of 35% hydrogen peroxide was added, the mixture was stirred for 12 hours, the organic phase was separated, washed with water, dried, filtered, concentrated and dried under reduced pressure, and purified by silica gel column to give a product, CJHP261, yield 52%, MS (MALDI-TOF): m/z533.1796[ M + H ]]+。
Example 3
Preparation of compound CJHP 184:
Figure BDA0003130595560000231
20.0mmol of intermediate Int-3 (prepared by the method of example 1) was dissolved in 80mL of dry toluene, and 18.0mmol of carbazole (CAS: 86-74-8), 24.0mmol of sodium tert-butoxide, 1.6mmol of cuprous iodide, and 0.2mmol of Pd were added under nitrogen protection2(dba)3Heating the catalyst and 0.2mL of 10% tri-tert-butylphosphine toluene solution to 100 ℃, stirring for reaction for 10 hours, cooling to room temperature, adding 50mL of water, stirring for reaction for 1 hour, filtering, washing the cake with water and ethanol, and separating and purifying the yellow solid by using a silica gel column to obtain the product CJHP184 with the yield of 86%, wherein MS (MALDI-TOF): m/z498.1954[ M + H]+。
Referring to a similar synthetic method to the above example 1 to example 3, the following compounds were prepared:
Figure BDA0003130595560000232
Figure BDA0003130595560000241
Figure BDA0003130595560000251
Figure BDA0003130595560000261
Figure BDA0003130595560000271
Figure BDA0003130595560000281
Figure BDA0003130595560000291
Figure BDA0003130595560000301
Figure BDA0003130595560000311
Figure BDA0003130595560000321
Figure BDA0003130595560000331
Figure BDA0003130595560000341
Figure BDA0003130595560000351
Figure BDA0003130595560000361
Figure BDA0003130595560000371
test example 1
The compounds prepared in examples 1 to 3 were purified by sublimation to prepare an organic electroluminescent element, and the specific preparation method was as follows:
(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) On the treated ITO electrode, HT002 (eight billionth space-time) is laminated in sequence,
Figure BDA0003130595560000372
) HT022 (eight billion space-time,
Figure BDA0003130595560000373
) the/HT 001 (space-time-in-billion,
Figure BDA0003130595560000374
) ADN +10% DA021 (billionth of spatio-temporal,
Figure BDA0003130595560000375
) CJHP 149-CJHP 322 compounds
Figure BDA0003130595560000376
/LiF
Figure BDA0003130595560000377
/Al
Figure BDA0003130595560000378
An organic electroluminescent element was produced.
Comparative example 1
As the electron transporting layer material, alq was used3An organic electroluminescent element was prepared in the same manner as in test example 1 except that (8-hydroxyquinolinylaluminum) was used instead of the compounds CJHP149 to CJHP 322.
Comparative example 2
An organic electroluminescent element was prepared in the same manner as in test example 1 except that the compounds CJHP149 to CJHP322 were not used as the electron transporting layer material.
Wherein ADN and Alq3The structural formula of (A) is as follows:
Figure BDA0003130595560000381
for the organic electroluminescent elements prepared in test example 1 and comparative examples 1 to 2, the current density was measured at 10mA/cm2The results of the normalized test of the driving voltage, the current efficiency, the external quantum efficiency, and the data of some of the compounds and the organic electroluminescent elements prepared in comparative examples 1 to 2 are shown in table 1.
TABLE 1
Figure BDA0003130595560000382
Figure BDA0003130595560000391
Figure BDA0003130595560000401
Figure BDA0003130595560000411
Figure BDA0003130595560000421
The results of the testing of the other compounds are in substantial agreement with the data in Table 1 and are not listed again for reasons of space limitation.
As can be seen from Table 1, the benzonaphthyridine derivatives prepared according to the present invention are used in organic electroluminescent elements and Alq for electron transport layers3The organic electroluminescent element for an electron transport layer shows excellent properties in terms of driving voltage, current efficiency, and external quantum efficiency, as compared with an organic electroluminescent element without an electron transport layer.
Schematic diagrams of bottom light emission and top light emission of an organic electroluminescent device prepared from the benzonaphthyridine derivative are shown in fig. 1 and fig. 2, wherein the organic electroluminescent device comprises a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer/electron blocking layer 4, a light emitting layer 5, a hole blocking/electron transport layer 6, an electron injection layer 7 and a cathode 8.
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 (8)

1. A benzonaphthyridine derivative is characterized in that the structural formula of the benzonaphthyridine derivative is shown as a formula (I):
Figure FDA0003773237560000011
wherein X1、X2Selected from N or CR6And X1And X2Not N at the same time;
R1～R6each independently selected from hydrogen, deuterium, cyano, nitro, C6-C60Aryl of, C2-C60Heteroaryl of (1), C6-C60Aryl phosphorus radical of (2), C6-C60One of the aryl phosphorus oxide groups of (a);
Ar1、Ar2is selected from C6-C60Aryl of (C)2-C60One or more of the heteroaryl groups of (a).
2. The benzonaphthyridine derivative according to claim 1, wherein C is2-C60The heteroaryl group of (a) is one of the following structures:
Figure FDA0003773237560000012
Figure FDA0003773237560000021
wherein Z is1、Z2Each independently selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group C6-C60Aryl radical, C6-C60Aryl phosphorus radical of (2), C6-C60Aryl phosphorus oxide group of, or C2-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, CR15R16Or NAr3；
Said R is15And R16Each independently selected from hydrogen, deuterium, C6-C60Aryl of (C)2-C60One of the heteroaryl groups of (a);
ar is3Is selected from C6-C60Aryl of, C2-C60Heteroaryl of (A), C6-C60Aryl phosphorus radical of (1), C6-C60One of the arylphosphorus oxide groups of (a);
Figure FDA0003773237560000022
represents a bond between a substituent and the main structure.
3. The benzonaphthyridine derivative according to claim 1 or 2, wherein the benzonaphthyridine derivative is one of CJHP149 to CJHP322, and the specific structural formula is as follows:
Figure FDA0003773237560000023
Figure FDA0003773237560000031
Figure FDA0003773237560000041
Figure FDA0003773237560000051
Figure FDA0003773237560000061
Figure FDA0003773237560000071
Figure FDA0003773237560000081
Figure FDA0003773237560000091
Figure FDA0003773237560000101
Figure FDA0003773237560000111
Figure FDA0003773237560000121
wherein, T2is-O-, -S-or one of the following structures:
Figure FDA0003773237560000122
Figure FDA0003773237560000131
* -and-represent a connecting bond.
4. An organic electroluminescent material, characterized in that the organic electroluminescent material comprises the benzonaphthyridine derivative according to any one of claims 1 to 3.
5. An organic electroluminescent element comprising a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises the benzonaphthyridine derivative according to any one of claims 1 to 3.
6. The organic electroluminescent element according to claim 5, wherein the organic layer is a light-emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer or an optical refraction layer.
7. The organic electroluminescent element as claimed in claim 5, wherein the benzonaphthyridine derivative is a material of an electron transport layer.
8. The organic electroluminescent element according to claim 5, wherein the benzonaphthyridine derivative is a material of a light-emitting layer.
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