CN112321598A - Carbazole derivative and application thereof - Google Patents
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Abstract
The invention relates to a carbazole derivative and application thereof, wherein the structural formula of the carbazole derivative is shown as a formula (I), the carbazole derivative has higher triplet state energy level, and is suitable for being used as a material for an organic electroluminescent elementThe carbazole derivative has good thermal stability and film-forming property, can be applied to materials for organic electroluminescent elements, display devices and lighting devices, and can prolong the service life, thereby reducing the manufacturing cost of the materials for organic electroluminescent elements, the display devices and the lighting devices.
Description
Technical Field
The invention belongs to the technical field of materials for organic electroluminescent elements, and particularly relates to a carbazole derivative and application thereof.
Background
In recent years, organic electroluminescent display technologies have become mature, and some products have entered the market, but in the process of industrialization, many problems still need to be solved, especially, many problems still remain unsolved, such as carrier injection and transport performance, electroluminescent performance of materials, service life, color purity, matching between various materials and between various electrodes, and the like, of various organic materials used for manufacturing elements. Especially, the light emitting element has not yet achieved practical requirements in terms of luminous efficiency and service life, which greatly limits the development of OLED technology.
Organic electroluminescence is largely divided into fluorescence and phosphorescence, but according to the spin quantum statistical theory, the probability of singlet excitons and triplet excitons is 1:3, i.e., the theoretical limit of fluorescence from radiative transition of singlet excitons is 25%, and the theoretical limit of fluorescence from radiative transition of triplet excitons is 75%. It is urgent to use 75% of the energy of triplet excitons. Forrest et al discovered in 1997 that the phosphorescence electroluminescence phenomenon breaks through the limit of 25% efficiency of the quantum efficiency of the organic electroluminescence material, and arouses people to pay extensive attention to the metal complex phosphorescence material. Since then, much research has been conducted on phosphorescent materials.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the above problems of the prior art, the present invention provides a carbazole derivative and use thereof, which is used as a raw material of a material for an organic electroluminescent element and can provide a material for an organic electroluminescent element and an organic electroluminescent element having a reduced starting voltage, improved luminous efficiency, and improved luminance.
The first object of the present invention is to provide a carbazole derivative, wherein the carbazole derivative has a structural formula shown in formula (I):
wherein R is1～R6Identical or different from hydrogen, deuterium, having C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Alkenyl or alkynyl group of (A), an aromatic ring system or a heteroaromatic ring system having 5 to 60 carbon atoms, R1～R6Each group may be substituted by one or more groups R, and wherein two or more adjacent substituent groups may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;
x is selected from O or S;
w is the same or different at each occurrence and is selected from CR or N, and any two adjacent groups W represent a group of formula (1) or (2):
wherein G is C (R)2NR, oxygen or sulfur; z is the same or different at each occurrence, Z is CR or N, and ^ represents an adjacent group W;
r is the same or different at each occurrence and is selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, a nitro group, and N (Ar)1)2、N(R7)2、C(＝O)Ar1、C(＝O)R7、P(＝O)(Ar1)2Having a structure of C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Alkenyl or alkynyl groups of (A), an aromatic or heteroaromatic ring system having 5 to 80, preferably 5 to 60, carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, each of the R groups being optionally substituted by one or more radicals R7Substituted, or combinations of these systems, wherein one or more non-adjacent-CH2The radicals may be substituted by R7C＝CR7、C≡C、Si(R7)2、Ge(R7)2、Sn(R7)2、C＝O、C＝S、C＝Se、C＝NR7、P(＝O)(R7)、SO、SO2、NR7O, S or CONR7And in which one or more hydrogen atoms are replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, where two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R7Substitution;
R7identical or different at each occurrence and selected from the group consisting of hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar)1)2、N(R8)2、C(＝O)Ar1、C(＝O)R8、P(＝O)(Ar1)2Having a structure of C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40One of alkenyl or alkynyl, aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, R7Each radical in (a) may be substituted by one or more radicals R8Substituted, or combinations of these systems, wherein one or more non-adjacent-CH2The radicals may be substituted by R8C＝CR8、C≡C、Si(R8)2、Ge(R8)2、Sn(R8)2、C＝O、C＝S、C＝Se、C＝NR8、P(＝O)(R8)、SO、SO2、NR8O, S or CONR8And wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, wherein two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R8Substitution;
Ar1identical or different at each occurrence and selected from aromatic or heteroaromatic ring systems having from 5 to 30 carbon atoms which may be substituted by one or more nonaromatic radicals R8Substitution; two groups Ar here bonded to the same nitrogen or phosphorus atom3Can also be selected from N (R) through a single bond8)、C(R8)2Oxygen or sulfur bridging groups;
R8selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, having C1～C20An aliphatic hydrocarbon group, an aromatic or heteroaromatic ring system having 5 to 30 carbon atoms, R8Wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R8They can form mono-or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.
Aromatic or heteroaromatic ring systems in the sense of the present invention are intended to be taken to mean systems which do not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be linked by non-aromatic units, for example C, N, O or an S atom. Thus, for example, as with systems in which two or more aryl groups are linked by, for example, a short alkyl group, systems such as fluorene, 9' -spirobifluorene, 9-diarylfluorene, triarylamine, diaryl ether, and the like are also considered to refer to aromatic ring systems in the sense of the present invention.
Aryl in the sense of the present invention contains 6 to 60 carbon atoms and heteroaryl in the sense of the present invention contains 2 to 60 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. Aryl or heteroaryl herein is considered to mean a simple aromatic ring, i.e. benzene, naphthalene, etc., or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatic rings, such as biphenyl, which are connected to one another by single bonds, are, in contrast, not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.
Containing 1 to 40 carbon atoms and in which the individual hydrogen atoms or-CH2The aliphatic hydrocarbon radicals or alkyl or alkenyl or alkynyl radicals which may also be substituted by the abovementioned radicals are preferably to be understood as meaning the following radicals: 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, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. The alkoxy group, preferably an alkoxy group having 1 to 40 carbon atoms, is considered to mean a methoxy group, a trifluoromethoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, a sec-pentyloxy group, a 2-methylbutyloxy group, a n-hexyloxy group, a cyclohexyloxy group, a n-heptyloxy group, a cycloheptyloxy group, a n-octyloxy group, a cyclooctyloxy group, a 2-ethylhexyloxy group, a pentafluoroethoxy group and a 2,2, 2-. The heteroalkyl group is preferably an alkyl group having 1 to 40 carbon atoms, meaning a hydrogen atom or-CH alone2Radicals which may be substituted by oxygen, sulfur, halogen atomsThe group, which is to be understood as meaning 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, 2,2, 2-trifluoroethoxy, 2,2, 2-trifluoroethylthio, vinyloxy, vinylthio, propenyloxy, propenylthio, butenylthio, butenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexenyloxy, cyclohexenylthio, ethynyloxy, ethynylthio, propynyloxy, propynylthio, butynyloxy, butenyloxy, pentenyloxy, pentenylthio, cyclopentenylthio, hexenyloxy, cyclohexenylthio, ethynylthio, ethynyl, Butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio.
In general, the cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, where one or more-CH may be present2The radicals may be replaced by the radicals mentioned above; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms, or nitrile groups.
The aromatic or heteroaromatic ring atoms according to the invention may in each case also be substituted by the abovementioned radicals R8Substituted aromatic or heteroaromatic ring systems, in particular radicals derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,
Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-indenocarbazole, cis-or trans-indolocarbazole, triindene, isotridendene, spirotriindene, spiroisotridendene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, and thiopheneIsoquinoline, acridine, phenanthridine, benzo [5,6 ]]Quinoline, benzo [6,7 ]]Quinoline, benzo [7,8 ]]Quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxaloimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroixazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diaza-thracene, 2, 7-diaza, 2, 3-diaza-pyrene, 1, 6-diaza-pyrene, 1, 8-diaza-pyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescent red ring, naphthyridine, azacarbazole, benzocarbazine, carboline, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, tetrazole, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole, or a group derived from a combination of these systems.
Further, said R1～R6The same or different, selected from hydrogen, deuterium, an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, R1～R6Each group may be substituted by one or more groups R, and wherein two or more adjacent substituent groups may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;
x is selected from O or S;
w is the same or different at each occurrence and is selected from CR or N, and any two adjacent groups W represent a group of formula (1) or (2):
x is selected from O or S;
w is the same or different at each occurrence and is selected from CR or N, and any two adjacent groups W represent a group of formula (1) or (2):
wherein G is C (R)2NR, oxygen or sulfur; z is the same or different at each occurrence, Z is CR or N, and ^ represents an adjacent group W;
r is the same or different at each occurrence and is selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, a nitro group, and N (Ar)1)2、N(R7)2、C(＝O)Ar1、C(＝O)R7、P(＝O)(Ar1)2Having a structure of C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Alkenyl or alkynyl groups of (A), an aromatic or heteroaromatic ring system having 5 to 80, preferably 5 to 60, carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, each of the R groups being optionally substituted by one or more radicals R7Substituted, or combinations of these systems, wherein one or more non-adjacent-CH2The radicals may be substituted by R7C＝CR7、C≡C、Si(R7)2、Ge(R7)2、Sn(R7)2、C＝O、C＝S、C＝Se、C＝NR7、P(＝O)(R7)、SO、SO2、NR7O, S or CONR7And in which one or more hydrogen atoms are replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, where two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R7Substitution;
R7identical or different at each occurrence and selected from the group consisting of hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar)1)2、N(R8)2、C(＝O)Ar1、C(＝O)R8、P(＝O)(Ar1)2Having a structure of C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40One of alkenyl or alkynyl, aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, R7Each radical in (a) may be substituted by one or more radicals R8Substituted, or combinations of these systems, wherein one or more non-adjacent-CH2The radicals may be substituted by R8C＝CR8、C≡C、Si(R8)2、Ge(R8)2、Sn(R8)2、C＝O、C＝S、C＝Se、C＝NR8、P(＝O)(R8)、SO、SO2、NR8O, S or CONR8And wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, wherein two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R8Substitution;
Ar1identical or different at each occurrence and selected from aromatic or heteroaromatic ring systems having from 5 to 30 carbon atoms which may be substituted by one or more nonaromatic radicals R8Substitution; two groups Ar here bonded to the same nitrogen or phosphorus atom3Can also be selected from N (R) through a single bond8)、C(R8)2Oxygen or sulfur bridging groups;
R8selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, having C1～C20An aliphatic hydrocarbon group, an aromatic or heteroaromatic ring system having 5 to 30 carbon atoms, R8Wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R8They can form mono-or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.
Further, the carbazole derivative has a specific structure as one of CJHK 486-CJHK 716:
wherein, X is selected from O or S independently.
The second object of the present invention is to provide a use of the carbazole derivative in a material for an organic element.
The organic device material of the present invention contains the compound of the present invention. The material for organic devices may be composed of the compound of the present invention alone or may contain other compounds.
The material for organic devices is a material for organic electroluminescent devices, a material for organic field effect transistors, or a material for organic thin film solar cells.
The compound of the present invention contained in the material for an organic electroluminescent element of the present invention can be used as a host material. In this case, the material for an organic electroluminescent element of the present invention may contain another compound as a dopant.
Further, the material for an organic electroluminescent element is a material for a light-emitting layer.
Furthermore, the material for the organic electroluminescent element is an electron transport layer material, a hole transport layer material or an encapsulation layer material.
A third object of the present invention is to provide an organic electroluminescent element comprising a first electrode, a second electrode and at least one organic layer interposed between the first electrode and the second electrode, the at least one organic layer comprising the carbazole 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. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent device 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. 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 compound 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, 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 element 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 elements which are characterized in that one or more layers are applied by means of a sublimation process, in which the temperature in a vacuum sublimation apparatus is below 10%-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 present invention relates to a carbazole derivative comprising at least one of the above-indicated carbazole derivatives of the present invention. The same preferences as indicated above for the organic electroluminescent element apply to the carbazole derivative of the present invention. In particular, the carbazole derivative may preferably contain other compounds in addition. The processing of the carbazole derivatives 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.
Further, the organic layer may further include one or more selected from an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer, a light emitting layer, and a light refraction layer.
The organic electroluminescent element of the present invention may be either a top emission light element or a bottom emission light element. The structure and the production method of the organic electroluminescent element of the present invention are not limited. The organic electroluminescent element prepared by the compound can reduce the starting voltage and improve the luminous efficiency and brightness.
In a fourth aspect of the present invention, there is provided a display device comprising the organic electroluminescent element.
In a fifth aspect of the present invention, there is provided a lighting device comprising the organic electroluminescent element.
Compared with the prior art, the invention has the beneficial effects that:
the carbazole derivative of the present invention has a high triplet level, is suitable for use as a material for an organic electroluminescent element, has a low activation voltage, and has high luminous efficiency and luminance.
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 transmission/electron blocking layer, 5-luminescent layer, 6-hole blocking/electron transmission 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 element 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;
and (3) life test: an LTS-1004AC life test apparatus was used.
Example 1
The preparation method of the compound CJHK684 comprises the following steps:
first step, preparation of Compound Int-1
0.10mol of 1-dibenzofuran boronic acid or 1-dibenzothiophene boronic acid was dispersed in 150mL of toluene under nitrogen protection, and 0.1mol of 1, 8-dibromonaphthalene, 0.20mol of anhydrous sodium carbonate, and 0.5g of Pd (PPh)3)4Adding 150mL of ethanol and 100mL of water into the catalyst, heating, refluxing, stirring and reacting for 8 hours, cooling to room temperature, adding 100mL of water for dilution, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a white solid with the yield of 83%.
The second step is that: preparation of Compound Int-2
25.0mmol of the intermediate Int-1 prepared in the first step, 7.5mmol of tricyclohexylphosphonium tetrafluoroborate, 5.0mmol of palladium acetate, 50.0mmol of anhydrous cesium carbonate and 80mL of dimethylacetamide, under the protection of nitrogen, heating, refluxing, stirring, reacting for 12 hours, cooling to room temperature, adding 200mL of water for dilution, extracting with ethyl acetate, collecting the organic phase, washing with saturated saline, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying with a silica gel column to obtain the compound Int-2 with the yield of 58%.
The third step: preparation of Compound Int-3
20.0mmol of the intermediate Int-2 prepared in the second step is dissolved in 100mL of dry tetrahydrofuran, the temperature is reduced to minus 80 ℃ by liquid nitrogen under the protection of nitrogen, 10.0mL of 2.5M butyl lithium n-hexane solution is dropwise added, the stirring reaction is carried out for 1 hour, 30.0mmol of trimethyl borate solution is dropwise added and dissolved in anhydrous tetrahydrofuran, the stirring reaction is carried out for 1 hour, the temperature is increased to minus 10 ℃, 50mL of 2M dilute hydrochloric acid aqueous solution is added, the stirring reaction is carried out for 30 minutes, the ethyl acetate is used for extraction, an organic phase is collected, drying and filtering are carried out, the filtrate is subjected to reduced pressure concentration and drying, petroleum ether is added for dispersion and filtering, and the compound Int-3 is obtained, wherein the yield is 65%.
The fourth step: preparation of Compound Int-4
Under nitrogen protection, 20.0mmol of intermediate Int-3 was dispersed in 60mL of toluene, and 17.0mmol of o-nitrobromobenzene, 40.0mmol of anhydrous sodium carbonate, and 0.2g of Pd (PPh) were added3)4Adding 30mL of ethanol and 30mL of water into the catalyst, heating, refluxing, stirring and reacting for 8 hours, cooling to room temperature, adding 100mL of water for dilution, extracting with ethyl acetate, collecting an 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 with the yield of 74%.
The fifth step: preparation of Compound Int-5
20.0mmol of the intermediate Int-4 prepared in the fourth step and 60.0mL of triethyl phosphite are mixed, heated, refluxed, stirred and reacted for 16 hours, cooled to room temperature, concentrated under reduced pressure to dryness, and separated and purified by a silica gel column to obtain the compound Int-5 as a yellow solid with the yield of 85%.
And a sixth step: preparation of compound CJHK684
10.0mmol of the intermediate Int-5 prepared in the fifth step is dissolved in 50mL of dry dimethyl sulfoxide, cooled to 5 ℃ in an ice water bath under the protection of nitrogen, 12.0mmol of 65% sodium hydride is added in batches, stirred and reacted for 1 hour, then 12.0mmol of 2- ([1,1' -biphenyl ] -4-yl) -4-chloro-6-phenyl-1, 3, 5-triazine is added, the temperature is raised to room temperature, stirred and reacted for 12 hours, 200mL of water is added for dilution, filtering is carried out, a filter cake is washed by water and ethanol, and then the filter cake is separated and purified by a silica gel column to obtain a compound HK684, namely a yellow solid, wherein the yield is 60-70%.
Experimental data:
CJHK684-1(X＝O)：
MS(MALDI-TOF):m/z 689.2357[M+H]+；1HNMR(δ、CDCl3)：9.06～9.04(1H,m)；8.53～8.46(3H,m)；8.27～8.09(9H,m)；7.95～7.87(3H,m)；7.70～7.67(2H,m)；7.49～7.38(6H,m)；7.34～7.26(4H,m)。
CJHK684-2(X＝S)：
MS(MALDI-TOF):m/z 705.2131[M+H]+；1HNMR(δ、CDCl3)：8.97～8.95(1H,m)；8.52～8.45(4H,m)；8.37(1H,s)；8.25～8.07(10H,m)；7.70～7.67(2H,m)；7.49～7.46(2H,m)；7.42～7.36(4H,m)；7.34～7.36(4H,m)。
example 2
Preparation of the compounds CJHK663 to CJHK683 and CJHK685 to CJHK716, with reference to the preparation method of example 1, the various halides were replaced with the sixth step 2- ([1,1' -biphenyl ] -4-yl) -4-chloro-6-phenyl-1, 3, 5-triazine of example 1, and other experimental parameters were routinely adjusted.
Example 3
The preparation method of the compound CJHK644 comprises the following steps:
the first step is as follows: preparation of Compound Int-6
20.0mmol of the intermediate Int-2 prepared in the second step of example 1 was dissolved in 60mL of dry THF, cooled to 0 ℃ in an ice water bath under the protection of nitrogen, 22.0mmol of a 2.5M n-butyllithium n-hexane solution was added dropwise, stirred for reaction for 1 hour, warmed to room temperature and stirred for reaction for 5 hours, then 24.0mmol of a solution of iodine in THF was added dropwise, stirred for reaction for 2 hours, 20mL of a saturated aqueous solution of sodium bisulfite was added dropwise, extracted with ethyl acetate, the organic phase was collected, dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and then separated and purified by a silica gel column to obtain the compound Int-6 as a white solid with a yield of 62%.
The second step is that: preparation of Compound Int-7
10.0mmol of the intermediate Int-6 prepared in the first step is dissolved in 80mL of N, N-dimethylformamide, 12.0mmol of o-chloroaniline, 10.0mmol of copper powder and 25.0mmol of anhydrous potassium carbonate are added under the protection of nitrogen, the temperature is raised to 100 ℃, the mixture is stirred and reacted for 8 hours, the mixture is cooled to room temperature and filtered, the filtrate is poured into 200mL of ice water and filtered, a filter cake is washed by water and ethanol, and a solid is separated and purified by a silica gel column to obtain a compound Int-7 which is yellow solid with the yield of 84%.
The third step: preparation of Compound Int-8
10.0mmol of the intermediate Int-7 prepared in the second step is dissolved in 80mL of toluene, under the protection of nitrogen, 15.0mmol of anhydrous cesium carbonate, 1.0mmol of cuprous iodide, 1.0mmol of palladium acetate and 2.0mmol of SPhos are added, the temperature is raised to 100 ℃, the mixture is stirred and reacted for 12 hours, the mixture is cooled to room temperature, 100mL of water is added for dilution, ethyl acetate is used for extraction, an organic phase is collected, dried and filtered, filtrate is concentrated under reduced pressure to be dry, and the dry filtrate is separated and purified by a silica gel column to obtain the compound Int-8 which is yellow solid with the yield of 88%.
The fourth step: preparation of Compound CJHK644
10.0mmol of the intermediate Int-8 prepared in the previous step is dissolved in 50mL of dry dimethyl sulfoxide, the temperature is reduced to 5 ℃ by using an ice water bath under the protection of nitrogen, 12.0mmol of 65% sodium hydride is added in batches, the mixture is stirred and reacted for 1 hour, 12.0mmol of 2-chloro-3-phenylquinoxaline is added, the temperature is increased to 60 ℃, the mixture is stirred and reacted for 12 hours, 200mL of water is added for dilution, the filtration is carried out, a filter cake is washed by water and ethanol, and then the mixture is separated and purified by using a silica gel column, so that a compound CJHK644, a yellow solid is obtained, and the yield is 70-80%.
Experimental data:
CJHK644-1(X＝O)：
MS(MALDI-TOF):m/z 586.1937[M+H]+；1HNMR(δ、CDCl3)：8.72(1H,s)；8.52～8.49(1H,m)；8.29～8.23(4H,m)；8.04～7.89(8H,m)；7.81～7.77(3H,m)；7.56～7.46(4H,m)；7.28～7.24(1H,m)；7.16～7.13(1H,m)。
CJHK644-2(X＝S)：
MS(MALDI-TOF):m/z 602.1707[M+H]+；1HNMR(δ、CDCl3)：8.79(1H,s)；8.43～8.40(2H,m)；8.27～8.17(6H,m)；8.06～7.89(5H,m)；7.81～7.79(2H,m)；7.56～7.52(2H,m)；7.44～7.36(3H,m)；7.24～7.20(1H,m)；7.16～7.13(1H,m)。
example 4
The compounds CJHK612 to CJHK643 and CJHK645 to CJHK662 were prepared according to the preparation method of example 3 except that different halides were substituted for the 2-chloro-3-phenylquinoxaline of the fourth step in example 3 and other parameters were adaptively adjusted.
Example 5
The preparation method of the compound CJHK549 comprises the following steps:
the first step is as follows: preparation of Compound Int-9
Under the protection of nitrogen, 15.0mmol of 1-chloro-8-iodo-dibenzo [ b, d ]]Furan or 1-chloro-8-iodo-dibenzo [ b, d ]]Thiophene was dispersed in 60mL of toluene, and 16.0mmol of pinacol o-nitrobenzoate, 30.0mmol of anhydrous sodium carbonate, and 0.15g of Pd (PPh)3)4Adding 30mL of ethanol and 30mL of water into the catalyst, heating, refluxing, stirring and reacting for 8 hours, cooling to room temperature, adding 100mL of water for dilution, extracting with ethyl acetate, collecting an 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 with the yield of 82%.
The second step is that: preparation of Compound Int-10
Under the protection of nitrogen, 10.0mmol of intermediate Int-9 is dissolved in 60mL of N, N-dimethylformamide, 12.0mmol of pinacol diboron, 15.0mmol of anhydrous cesium carbonate, 45.0mg of palladium acetate catalyst and 0.2g of bis (diphenylphosphino) ferrocene are added, the temperature is raised to 90 ℃, the reaction is stirred for 8 hours, the mixture is cooled to the room temperature, 100mL of water is added for dilution, the mixture is extracted by ethyl acetate, an organic phase is collected, dried, filtered, decompressed, concentrated and dried, and separated and purified by a silica gel column to obtain a yellow solid with the yield of 88%.
The third step: preparation of Compound Int-11
Under the protection of nitrogen, 10.0mmol of intermediate Int-10 was dissolved in 60mL of tolueneTo this solution were added 10.0mmol of 1, 8-dibromonaphthalene, 20.0mmol of anhydrous sodium carbonate, and 45.0mg of Pd (PPh)3)4Heating a palladium catalyst, refluxing and stirring for reaction for 10 hours, cooling to room temperature, adding 100mL of water for dilution, extracting with ethyl acetate, collecting an 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 with the yield of 76%.
The fourth step: preparation of Compound Int-12
Under the protection of nitrogen, 10.0mmol of intermediate Int-11 is dissolved in 100mL of chlorobenzene, 30.0mmol of triphenylphosphine is added, the mixture is heated, refluxed and stirred for reaction for 15 hours, cooled to room temperature, decompressed, concentrated and dried, 100mL of dichloromethane is added, the mixture is filtered, and a filter cake is washed by methanol to obtain a yellow solid with the yield of 75-80%.
The fifth step: preparation of Compound Int-13
Dissolving 15.0mmol of intermediate Int-12 in 60mL of dry N, N-dimethylformamide, cooling to 0 ℃ in an ice water bath under the protection of nitrogen, adding 18.0mmol of 65% sodium hydride in batches, stirring for reaction for 1 hour, adding 18.0mmol of N, N-dimethylformamide solution of 5-phenyl-2-bromochlorobenzyl chloride dropwise, heating to room temperature, stirring for reaction for 12 hours, adding 200mL of water for dilution, filtering, washing a filter cake with water and ethanol to obtain a compound Int-13, namely a yellow solid, wherein the yield is 85-90%.
And a sixth step: preparation of Compound Int-14
20.0mmol of intermediate Int-13 is dissolved in 80mL of N, N-dimethylformamide, under the protection of nitrogen, 3.0mmol of palladium acetate, 10.0mmol of benzyltrimethylammonium bromide, 60.0mmol of anhydrous cesium carbonate and 1.0mmol of SPhos ligand are added, the temperature is raised to 90 ℃, the reaction is stirred for 48 hours, the mixture is cooled to room temperature, 200mL of water is added for dilution, the filtration is carried out, a filter cake is washed by water and ethanol, and the solid is separated and purified by a silica gel column, so that the compound Int-14 is obtained and is yellow solid with the yield of 65%.
The seventh step: preparation of compound CJHK549
Dissolving 15.0mmol of intermediate Int-14 in 150mL of chloroform, adding 30.0mmol of potassium permanganate and 1.0g of 18-crown-6, heating, refluxing, stirring and reacting for 48 hours, cooling to room temperature, filtering, washing a filter cake with dichloromethane, collecting a filtrate, separating and purifying a solid by using a silica gel column, and recrystallizing with toluene-THF to obtain a compound CJHK549 as a yellow solid with the yield of 65-70%.
Experimental data:
CJHK549-1(X＝O)：
MS(MALDI-TOF):m/z 560.1667[M+H]+；1HNMR(δ、CDCl3)：8.90～8.88(1H,m)；8.77～8.73(3H,m)；8.38～8.32(4H,m)；8.18～8.10(4H,m)；7.88～7.85(2H,m)；7.65～7.61(1H,m)；7.54～7.49(3H,m)；7.46～7.44(2H,m)；7.39～7.37(1H,m)。
CJHK549-2(X＝S)：
MS(MALDI-TOF):m/z 576.1440[M+H]+；1HNMR(δ、CDCl3)：8.75～8.72(2H,m)；8.68(1H,s)；8.65～8.63(1H,m)；8.45～8.42(1H,m)；8.21～8.12(7H,m)；7.97～7.95(1H,d)；7.92～7.90(1H,d)；7.69～7.65(1H,m)；7.54～7.49(3H,m)；7.47～7.44(2H,m)；7.39～7.37(1H,m)。
example 6
The preparation of CJHK547-548 and CJHK550-557 compounds CJHK549 in example 5 were prepared in accordance with the following method except that 5-phenyl-2-bromochlorobenzyl chloride in the fifth step of example 5 was replaced with different benzyl chloride and other experimental parameters were adaptively adjusted.
Example 7
The preparation method of the compound CJHK579 comprises the following steps:
the first step is as follows: preparation of Compound Int-15
Dissolving 15.0mmol of benzofuran or benzothiophene in 120mL of dry THF, cooling to-78 ℃ with liquid nitrogen under the protection of nitrogen, dropwise adding 18.0mmol of 2.5M n-butyllithium n-hexane solution, stirring for reaction for 1 hour, dropwise adding 12.5mmol of indole-3-formaldehyde solution in THF, heating to room temperature, stirring for reaction for 1 hour, dropwise adding 20mL of saturated ammonium chloride aqueous solution, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying with a silica gel column to obtain the compound Int-15 with the yield of 95%.
The second step is that: preparation of Compound Int-16
Dissolving 15.0mmol of intermediate Int-15 in 80mL of dichloromethane, adding 18.0mmol of triethylsilane under the protection of nitrogen, slowly dropwise adding a solution of 15.0mmol of trifluoroacetic acid in dichloromethane, stirring for reacting for 2 hours, adding 40mL of 10% sodium hydroxide aqueous solution, 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 a compound Int-16 with the yield of 80-90%.
The third step: preparation of Compound Int-17
10.0mmol of intermediate Int-16 was dissolved in 100mL of ethanol and 5.0mmol of intermediate Int-16 was added
And adding 10.0mmol of 8-bromo-1-naphthaldehyde into the mixture, stirring the mixture to react for 12 hours, filtering the mixture, and washing a filter cake by using ethanol to obtain a white solid with the yield of 90-95%.
The fourth step: preparation of Compound Int-18
20.0mmol of intermediate Int-17 was dispersed in 250mL of xylene, warmed to 100 deg.C, and added in portions with 0.20mol of manganese dioxide solids, warmed, refluxed, stirred, reacted for 24 hours, cooled to room temperature, filtered, the filtrate was concentrated to dryness under reduced pressure, and recrystallized with dichloromethane/ethanol to give a yellow solid with a yield of 85%.
The fifth step: preparation of Compound Int-19
Dissolving 10.0mmol of intermediate Int-18 in 50mL of dry N, N-dimethylformamide, cooling to 0 ℃ in an ice water bath under the protection of nitrogen, adding 12.0mmol of 65% sodium hydride in batches, stirring for reaction for 1 hour, adding 12.0mmol of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, stirring for reaction for 12 hours, adding 100mL of water for dilution, filtering, washing a filter cake with water and ethanol to obtain a compound Int-19 as a yellow solid with the yield of 85-90%.
And a sixth step: preparation of compound CJHK579
Dissolving 10.0mmol of intermediate Int-19 in 60mL of xylene, adding 1.0mmol of cuprous iodide and 1.0mmol of palladium acetate under the protection of nitrogen, adding 15.0mmol of anhydrous cesium carbonate and 2.0mmol of SPhos ligand, heating to 110 ℃, stirring for reaction for 12 hours, cooling to room temperature, filtering, washing a filter cake with toluene, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a compound CJHK579, a yellow solid with the yield of 76-85%.
Experimental data:
CJHK579-1(X＝O)：
MS(MALDI-TOF):m/z 613.2042[M+H]+；1HNMR(δ、CDCl3)：8.83～8.81(1H,m)；8.76～8.73(1H,m)；8.60(1H,s)；8.58～8.54(4H,m)；8.41～8.37(5H,m)；8.13～8.03(3H,m)；7.86～7.83(1H,m)；7.52～7.48(1H,m)；7.45～7.40(6H,m)；7.37～7.34(1H,m)。
CJHK579-2(X＝S)：
MS(MALDI-TOF):m/z 629.1818[M+H]+；1HNMR(δ、CDCl3)：8.92～8.89(1H,m)；8.73(1H,s)；8.59～8.54(5H,m)；8.44～8.24(7H,m)；8.16～8.12(2H,m)；7.53～7.49(1H,m)；7.44～7.40(6H,m)；7.36～7.32(1H,m)。
example 8
The compounds CJHK 558-CJHK 578 and CJHK 580-CJHK 611 refer to the preparation of the compound CJHK579 in example 7 except that a different halide is substituted for the 2-chloro-4, 6-diphenyl-1, 3, 5-triazine of the fifth step in example 7 and the other experimental parameters are adaptively adjusted.
Example 9
The preparation method of the compound CJHK497 comprises the following reaction steps:
the first step is as follows: preparation of intermediate Int-20
10.0mmol of the intermediate Int-12 prepared in the fourth step in example 5 was dissolved in 80mL of toluene, 15.0mmol of anhydrous potassium carbonate and 1.0mmol of cuprous iodide were added, 0.1mmol of palladium acetate and 0.2mmol of SPhos ligand were added, the mixture was heated to 100 ℃ and stirred for reaction for 12 hours, cooled to room temperature, filtered, the filter cake was washed with water, and the solid was separated and purified by a silica gel column to obtain an intermediate Int-20 as a yellow solid with a yield of 75-80%.
The second step is that: preparation of compound CJHK497
Under the protection of nitrogen, 10.0mmol of intermediate Int-20 is dissolved in 60mL of toluene, 12.0mmol of 3-bromo-9-phenylcarbazole, 15.0mmol of sodium tert-butoxide and 0.1mmol of Pd2(dba)3 catalyst are added, 0.1mL of 10% tri-tert-butylphosphine toluene solution is added, the temperature is raised to 90 ℃, the mixture is stirred and reacted for 12 hours, the mixture is cooled to room temperature, 20mL of water is added, dichloromethane is used for extraction, an organic phase is collected, the organic phase is dried and filtered, the filtrate is decompressed, concentrated and dried, and is separated and purified by a silica gel column to obtain a product of HK497 which is a light yellow solid with the yield of 75-80%.
CJHK497-1(X＝O)：
MS(MALDI-TOF):m/z 623.2141[M+H]+；1HNMR(δ、CDCl3)：8.63～8.61(1H,m)；8.49～8.47(1H,m)；8.38～8.34(4H,m)；8.06～7.97(5H,m)；7.86～7.82(2H,m)；7.56～7.48(5H,m)；7.37～7.29(5H,m)；7.24～7.19(3H,m)。
CJHK497-2(X＝S)：
MS(MALDI-TOF):m/z 639.1912[M+H]+；1HNMR(δ、CDCl3)：8.55～8.53(2H,m)；8.43～8.42(1H,m)；8.35～8.26(5H,m)；8.17～8.12(4H,m)；8.07(1H,s)；7.54～7.47(5H,m)；7.38～7.28(5H,m)；7.23～7.18(3H,m)。
Example 10
The preparation of the compounds CJHK 486-CJHK 496 and CJHK 498-CJHK 546 was performed according to the preparation method of CJHK497 in example 9, except that different halides were substituted for 3-bromo-9-phenylcarbazole in the second step in example 9 and other experimental parameters were adaptively adjusted.
Preparation of organic electroluminescent element
Comparative example 1
An organic electroluminescent element was prepared as follows using a compound represented by the following formula a as a green host material, a compound represented by the following formula B as a green dopant material, a compound represented by the following formula C as a hole injection material, a compound represented by the following formula D as a hole transport material, a compound represented by the following formula E as a red host material, a compound represented by the following formula F as a red dopant material, a compound represented by the following formula G as an electron transport dopant material, and LiQ as an electron transport host material.
Will be the chemical formula C
/D
/A+B(5％)
/LiQ+G(50％)
/LiF
Al (2nm) was deposited on ITO glass by an EL deposition machine manufactured by DOV to prepare a green light element, and an organic electroluminescent element as a green light comparative example was prepared.
Will be the chemical formula C
/D
/E+F(5％)
/LiQ+G(50％)
/LiF
Al (2nm) was successively deposited on an ITO glass by an EL deposition apparatus manufactured by DOV to prepare a red light element, and an organic material as a comparative example of red light was preparedAn electroluminescent element.
Test example 1
An organic electroluminescent element was fabricated by the method of comparative example 1, substituting compound a with one of compounds CJHK486 to CJHK 716: ITO/C
/D
/[ inventive Compounds CJHK 486-CJHK 716]+B(5％)
/LiQ+G(50％)
/LiF
/Al(2nm)。
The results of measuring the properties of the obtained element are shown in Table 1, in which the driving voltage (V), the current efficiency (LE), the color Coordinate (CIE), and the full width at half maximum (FWHM) were measured at a current density of 10mA/cm2Conditions were obtained and the voltage, LE, FWHM and LT 90% were normalized to the reference.
Table 1: green light element performance detection result
As can be seen from the above, the green light device produced from the organic material of the present invention has a lower driving voltage, a higher current efficiency, and a good color purity than the device produced in comparative example 1, and the emission luminance of the device was initially 2000cd/cm2Under the initial conditions, the service life of the element using the compound of the invention as a green light host material is greatly improved.
The properties of only a portion of the compounds are listed in table 1, and the properties of other compounds are substantially identical to the structures of the compounds listed in the table, and are not listed due to space limitation.
An organic electroluminescent element was fabricated in the same manner as in comparative example 1, except that the aforementioned compound E was replaced with the compounds CJHK486 to CJHK716 of the present invention: ITO/C
/D
/[ inventive Compounds CJHK 486-CJHK 716]+F(5％)
/LiQ+G(50％)
/LiF
/Al(2nm)。
The results of measuring the properties of the obtained element are shown in Table 2, in which the driving voltage (V), the current efficiency (LE), the color Coordinate (CIE), and the full width at half maximum (FWHM) were measured at a current density of 10mA/cm2Conditions were obtained and the voltage, LE, FWHM and LT 90% were normalized to the reference.
TABLE 2 Red light element Performance test results
As can be seen from the performance test results of the red light device in Table 2, the device prepared from the organic material of the present invention has significantly lower driving voltage, high current efficiency and good color purity of light emission compared to the red light device prepared in comparative example 1. At an initial luminance of 2000cd/cm2Under the initial conditions, the LT 90% lifetime of the element using the compound of the present invention as a red light host material was significantly improved.
The properties of only a portion of the compounds are listed in table 1, and the properties of other compounds are substantially identical to the structures of the compounds listed in the table, and are not listed due to space limitation.
As shown in fig. 1 and 2, which are a schematic view of a bottom emission example of the organic electroluminescent device of the present invention and a schematic view of a top emission example of the organic electroluminescent device, respectively, the carbazole derivative prepared in the present invention is contained in the light-emitting layer 5.
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 carbazole derivative having a structural formula represented by formula (I):
wherein R is1～R6Identical or different from hydrogen, deuterium, having C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Alkenyl or alkynyl group of (A), an aromatic ring system or a heteroaromatic ring system having 5 to 60 carbon atoms, R1～R6Each group may be substituted by one or more groups R, and wherein two or more adjacent substituent groups may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;
x is selected from O or S;
w is the same or different at each occurrence and is selected from CR or N, and any two adjacent groups W represent a group of formula (1) or (2):
wherein G is C (R)2NR, oxygen or sulfur; z is the same or different at each occurrence, Z is CR or N, and ^ represents an adjacent group W;
r is the same or different at each occurrence and is selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, a nitro group, and N (Ar)1)2、N(R7)2、C(＝O)Ar1、C(＝O)R7、P(＝O)(Ar1)2Having a structure of C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Alkenyl or alkynyl groups of (A), an aromatic or heteroaromatic ring system having 5 to 80, preferably 5 to 60, carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, each of the R groups being optionally substituted by one or more radicals R7Substituted, or combinations of these systems, wherein one or more non-adjacent-CH2The radicals may be substituted by R7C＝CR7、C≡C、Si(R7)2、Ge(R7)2、Sn(R7)2、C＝O、C＝S、C＝Se、C＝NR7、P(＝O)(R7)、SO、SO2、NR7O, S or CONR7And in which one or more hydrogen atoms are replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, where two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R7Substitution;
R7identical or different at each occurrence and selected from the group consisting of hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar)1)2、N(R8)2、C(＝O)Ar1、C(＝O)R8、P(＝O)(Ar1)2Having a structure of C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40One of alkenyl or alkynyl, aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, R7Each radical in (a) may be substituted by one or more radicals R8Substituted, or combinations of these systems, wherein one or more non-adjacent-CH2The radicals may be substituted by R8C＝CR8、C≡C、Si(R8)2、Ge(R8)2、Sn(R8)2、C＝O、C＝S、C＝Se、C＝NR8、P(＝O)(R8)、SO、SO2、NR8O, S or CONR8And wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, wherein two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R8Substitution;
Ar1identical or different at each occurrence and selected from aromatic or heteroaromatic ring systems having from 5 to 30 carbon atoms which may be substituted by one or more nonaromatic radicals R8Substitution; two groups Ar here bonded to the same nitrogen or phosphorus atom3Can also be selected from N (R) through a single bond8)、C(R8)2Oxygen or sulfur bridging groups;
R8selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, having C1～C20An aliphatic hydrocarbon group, an aromatic or heteroaromatic ring system having 5 to 30 carbon atoms, R8Wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R8Esters which can form a single or multiple ring with one anotherAn aromatic, aromatic or heteroaromatic ring system.
2. The carbazole derivative according to claim 1, wherein R is1～R6The same or different, selected from hydrogen, deuterium, an aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, R1～R6Each group may be substituted by one or more groups R, and wherein two or more adjacent substituent groups may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;
x is selected from O or S;
w is the same or different at each occurrence and is selected from CR or N, and any two adjacent groups W represent a group of formula (1) or (2):
x is selected from O or S;
w is the same or different at each occurrence and is selected from CR or N, and any two adjacent groups W represent a group of formula (1) or (2):
wherein G is C (R)2NR, oxygen or sulfur; z is the same or different at each occurrence, Z is CR or N, and ^ represents an adjacent group W;
r is the same or different at each occurrence and is selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, a nitro group, and N (Ar)1)2、N(R7)2、C(＝O)Ar1、C(＝O)R7、P(＝O)(Ar1)2Having a structure of C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Alkenyl or alkynyl groups of (A), one of an aromatic or heteroaromatic ring system having 5 to 80, preferably 5 to 60, carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, R in the radicalEach radical may be substituted by one or more radicals R7Substituted, or combinations of these systems, wherein one or more non-adjacent-CH2The radicals may be substituted by R7C＝CR7、C≡C、Si(R7)2、Ge(R7)2、Sn(R7)2、C＝O、C＝S、C＝Se、C＝NR7、P(＝O)(R7)、SO、SO2、NR7O, S or CONR7And in which one or more hydrogen atoms are replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, where two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R7Substitution;
R7identical or different at each occurrence and selected from the group consisting of hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar)1)2、N(R8)2、C(＝O)Ar1、C(＝O)R8、P(＝O)(Ar1)2Having a structure of C1～C40Straight chain alkyl of (2) having C1～C40Linear heteroalkyl group of (A) having C3～C40A branched or cyclic alkyl group having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40One of alkenyl or alkynyl, aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, R7Each radical in (a) may be substituted by one or more radicals R8Substituted, or combinations of these systems, wherein one or more non-adjacent-CH2The radicals may be substituted by R8C＝CR8、C≡C、Si(R8)2、Ge(R8)2、Sn(R8)2、C＝O、C＝S、C＝Se、C＝NR8、P(＝O)(R8)、SO、SO2、NR8O, S or CONR8And wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, wherein two or more adjacent substituents R may optionally be joined or fusedCombined to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R8Substitution;
Ar1identical or different at each occurrence and selected from aromatic or heteroaromatic ring systems having from 5 to 30 carbon atoms which may be substituted by one or more nonaromatic radicals R8Substitution; two groups Ar here bonded to the same nitrogen or phosphorus atom3Can also be selected from N (R) through a single bond8)、C(R8)2Oxygen or sulfur bridging groups;
R8selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, having C1～C20An aliphatic hydrocarbon group, an aromatic or heteroaromatic ring system having 5 to 30 carbon atoms, R8Wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R8They can form mono-or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.
3. The carbazole derivative according to claim 1 or 2, wherein the carbazole derivative has a specific structure selected from CJHK486 to CJHK 716:
wherein, X is selected from O or S independently.
4. Use of the carbazole derivative as claimed in any one of claims 1 to 3 in a material for organic elements.
5. The use according to claim 4, wherein the material for organic devices is a material for organic electroluminescent devices, a material for organic field effect transistors, or a material for organic thin film solar cells.
6. The use according to claim 5, wherein the material for an organic electroluminescent element is a material for a light-emitting layer.
7. The use according to claim 5, wherein the material for the organic electroluminescent element is an electron transport layer material, a hole transport layer material or an encapsulation layer material.
8. An organic electroluminescent element comprising a first electrode, a second electrode and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer comprises the carbazole derivative according to any one of claims 1 to 3.
9. A display device comprising the organic electroluminescent element according to claim 8.
10. A lighting device comprising the organic electroluminescent element according to claim 8.
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| WO2022088910A1 (en) * | 2020-11-02 | 2022-05-05 | 北京八亿时空液晶科技股份有限公司 | Carbazole derivative and application thereof |
| WO2023181952A1 (en) * | 2022-03-22 | 2023-09-28 | 住友化学株式会社 | Compound, polymer compound, composition, and light emitting device |
| WO2024012469A1 (en) * | 2022-07-14 | 2024-01-18 | 上海八亿时空先进材料有限公司 | Carbazole derivative and use thereof in organic light-emitting element |
| WO2024012512A1 (en) * | 2022-07-14 | 2024-01-18 | 上海八亿时空先进材料有限公司 | Carbazole derivative and organic light-emitting element having same |
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