WO2023160187A1 - Carbazole derivative and use thereof - Google Patents

Carbazole derivative and use thereof Download PDF

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WO2023160187A1
WO2023160187A1 PCT/CN2022/140647 CN2022140647W WO2023160187A1 WO 2023160187 A1 WO2023160187 A1 WO 2023160187A1 CN 2022140647 W CN2022140647 W CN 2022140647W WO 2023160187 A1 WO2023160187 A1 WO 2023160187A1
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substituted
unsubstituted
carbazole derivative
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曹建华
姜卫东
唐怡杰
邸庆童
郭文龙
边坤
刘赛赛
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上海八亿时空先进材料有限公司
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Definitions

  • the invention relates to the technical field of organic electroluminescent materials, in particular to a carbazole derivative and its application.
  • Organic electroluminescence is mainly divided into fluorescence and phosphorescence, but according to the spin quantum statistical theory, the probability of singlet excitons and triplet excitons is 1:3, which is the theoretical limit of fluorescence from radiative transitions of singlet excitons The theoretical limit of fluorescence for triplet exciton radiative transitions is 25% and 75%. How to utilize the energy of 75% triplet excitons has become a top priority.
  • Forrest et al. discovered that the phenomenon of phosphorescence electroluminescence broke through the limit of 25% efficiency of the quantum efficiency of organic electroluminescent materials, which aroused people's widespread attention on metal complex phosphorescent materials. Since then, a lot of research has been done on phosphorescent materials.
  • the present invention provides a carbazole derivative and its application.
  • the carbazole derivative can be used as a raw material for an organic electroluminescence element material, which can provide reduced starting voltage and high luminous efficiency.
  • the present invention provides a kind of carbazole derivative, its structure is as shown in formula (I):
  • W 1 , W 2 , W 3 , and W 4 each independently represent CR 9 , the adjacent two groups W 1 and W 2 , W 3 and W 4 represent groups of the following formula (II), and W At least one of 1 and W 2 or W 3 and W 4 is a group of formula (II);
  • Z represents CR 0 or N identically or differently at each occurrence, and " ⁇ " indicates adjacent groups W 1 and W 2 or W 3 and W 4 in formula (I);
  • X stands for CR 10 or N
  • R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same or different, each independently selected from the group consisting of: hydrogen , deuterium, straight-chain alkyl with C 1 to C 40 , straight-chain heteroalkyl with C 1 to C 40 , branched or cyclic alkyl with C 3 to C 40 , C 3 to C 40 branched or cyclic heteroalkyl, alkenyl or alkynyl with C 2 to C 40 , aryl with 5 to 60 carbon atoms, heteroaryl with 5 to 60 carbon atoms, R 0 to Two or more adjacent substituent groups in R can optionally be joined or fused to form a monocyclic or polycyclic aliphatic, aromatic or aromatic ring system, heteroaromatic or heteroaromatic ring Tie;
  • Ar 1 is selected from the group consisting of aryl having 5-60 carbon atoms or heteroaryl having 5-60 carbon atoms.
  • An aryl or aromatic group in the sense of the present invention contains 5 to 60 carbon atoms
  • a heteroaryl group in the sense of the present invention contains 2 to 60 carbon atoms and at least one heteroatom, with the proviso that carbon atoms and heteroatoms The sum of is at least 5; said heteroatoms are preferably selected from N, O or S.
  • Aryl or heteroaryl here encompasses monocyclic groups and polycyclic ring systems.
  • a polycyclic ring may have two carbons common to two adjacent rings or two or more rings known as "fused", where at least one of the rings is aromatic, e.g. the other rings may be rings Alkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl.
  • aryl or heteroaryl groups may also be linked by non-aromatic units such as C, N, O or S atoms, for example, as in systems where two or more aryl groups are linked by, for example, short alkyl groups , such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, dibenzofuran or dibenzothiophene, etc.
  • short alkyl groups such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, dibenzofuran or dibenzothiophene, etc.
  • the alkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms.
  • a monovalent functional group obtained by removing one hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms.
  • Heteroalkyl means that the hydrogen atom or -CH2- on the alkyl group is replaced by at least one heteroatom selected from halogen, nitrile, N, O, S or silicon.
  • the alkenyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon double bonds and having 2 to 40 carbon atoms.
  • a monovalent functional group obtained by removing one hydrogen atom from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon double bonds and having 2 to 40 carbon atoms.
  • the alkynyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon triple bonds and having carbon atoms ranging from 2 to 40.
  • a monovalent functional group obtained by removing one hydrogen atom from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon triple bonds and having carbon atoms ranging from 2 to 40.
  • cycloalkyl and cycloalkenyl refer to monovalent functional groups obtained by removing one hydrogen atom from monocyclic or polycyclic non-aromatic hydrocarbons with 3 to 40 carbon atoms.
  • the heterocycloalkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having 3 to 40 atomic nuclei.
  • one or more carbons, preferably 1 to 3 carbons in the ring are substituted with heteroatoms such as N, O or S.
  • heteroatoms such as N, O or S.
  • the aryloxy or heteroaryloxy group used in the present invention refers to a monovalent functional group represented by RO-, where R is an aryl group with 6 to 60 carbon atoms or a heteroaryl group with 5 to 60 carbon atoms.
  • R is an aryl group with 6 to 60 carbon atoms or a heteroaryl group with 5 to 60 carbon atoms.
  • aryloxy or heteroaryloxy there are phenoxy, naphthyloxy, biphenoxy, 2-pyridyloxy, 3-pyridyloxy, 4-pyridyloxy and the like.
  • Group ring systems in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenyl, terphenyl, tripolyphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis Or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, tripolyindene, isotripolyindene,
  • a combination thereof or “group” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can conceive from the applicable list.
  • alkyl and deuterium can be combined to form partially or fully deuterated alkyl
  • halogen and alkyl can be combined to form haloalkyl substituents, such as trifluoromethyl, etc.
  • halogen, alkyl and aryl can be combined to form Haloaralkyl.
  • the carbazole derivative is selected from one or more of formula (I)-1 to formula (I)-8:
  • R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different, each independently selected from the group consisting of the following groups : hydrogen, deuterium, an aryl group with 5 to 60 carbon atoms, a heteroaryl group with 5 to 60 carbon atoms, two or more adjacent substituent groups in R 0 to R 10 can be optionally are joined or fused to form monocyclic or polycyclic aliphatic, aromatic or aromatic ring systems, heteroaromatic or heteroaromatic ring systems;
  • Ar 1 is selected from the group consisting of aryl having 5-60 carbon atoms or heteroaryl having 5-60 carbon atoms.
  • the Ar 1 is represented as a -(L) n Ar 2 group, wherein L is selected from the group consisting of a single bond, a C 6 -C 60 arylene group, and a C 5 -C 60 heteroarylene group Group; n is 0, 1 or 2; Ar 2 is selected from the group consisting of the following groups shown in II-1 to II-17:
  • Z 1 and Z 2 are each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid group or sulfonate thereof , phosphate group or its phosphate salt, C 1 ⁇ C 60 alkyl group, C 2 ⁇ C 60 alkenyl group, C 2 ⁇ C 60 alkynyl group, C 1 ⁇ C 60 alkoxy group, C 3 ⁇ C 60 cycloalkane group, C 3 ⁇ C 60 cycloalkene group, substituted or unsubstituted C 6 ⁇ C 60 aryl group, substituted or unsubstituted C 6 ⁇ C 60 aryloxy group, substituted or unsubstituted C 6 ⁇ C 60 arylsulfide group , or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aromatic groups
  • T 1 means O, S, CR'R" or NAr';
  • R' and R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
  • Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused-ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
  • R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from hydrogen or deuterium.
  • the carbazole derivative is selected from one or more of the following structures shown in CJHM515 to CJHM877:
  • *—T 2 —* is selected from *—O—*, *—S—* or one of the following structures:
  • the present invention also provides the application of the above-mentioned carbazole derivatives in organic electroluminescent elements.
  • the carbazole derivative is used as a light-emitting layer material, a hole transport layer material, a hole blocking layer material or an encapsulation layer material in an organic electroluminescent element.
  • the present invention also provides an organic electroluminescent element, comprising: a first electrode, a second electrode, and at least one organic layer between the first electrode and the second electrode, at least one of the organic layers
  • the layer comprises the carbazole derivatives described above.
  • the organic electroluminescent element comprises a cathode, an anode and at least one light-emitting layer. Besides these layers it may also contain further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, excitation layers, sub-blocking layer, electron blocking layer and/or charge generating layer. Interlayers having, for example, an exciton-blocking function can likewise be introduced between two emitting layers. It should be noted, however, that not every one of these layers is required to be present.
  • the organic electroluminescent device described herein may comprise one light-emitting layer, or it may comprise a plurality of light-emitting layers.
  • various light-emitting compounds capable of emitting light are used in the light-emitting layer.
  • Particular preference is given to systems with three emitting layers, the three layers being able to exhibit blue, green and red emission. If more than one emitting layer is present, according to the invention at least one of these layers comprises a carbazole derivative according to the invention.
  • organic electroluminescent components in which one or more layers are applied by means of a sublimation method by vapor deposition in a vacuum sublimation apparatus at an initial pressure below 10 ⁇ 5 Pa, preferably below 10 ⁇ 6 Pa. Apply the material.
  • the initial pressure may also be even lower, for example below 10 ⁇ 7 Pa.
  • a particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is thus structured.
  • organic electroluminescent elements which, from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithography, photoinduced thermography, thermal transfer, spray Ink printing or nozzle printing to produce one or more layers.
  • Soluble compounds are obtained, for example, by appropriately substituting the compound represented by formula (I).
  • These methods are also particularly suitable for oligomers, dendrimers and polymers.
  • hybrid methods in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
  • the organic layer further includes one or more selected from electron injection layer, electron transport layer, hole blocking layer, electron blocking layer, hole transport layer, hole injection layer, light emitting layer, and photorefractive layer.
  • the organic electroluminescent element of the present invention can be either a top-emitting light element or a bottom-emitting light element.
  • the structure and preparation method of the organic electroluminescent element of the present invention are not limited.
  • the organic electroluminescent element prepared by using the compound of the invention can reduce the starting voltage and improve the luminous efficiency and brightness.
  • the present invention also provides a display device comprising the organic electroluminescent element described above.
  • the present invention also provides an illuminating device, comprising the above-mentioned organic electroluminescence element.
  • the material for an organic electroluminescent device of the present invention contains the carbazole derivative of the present invention.
  • the material for an organic electroluminescent element may be constituted by using the compound of the present invention alone, or may contain other compounds together.
  • the carbazole derivative of the present invention contained in the material for an organic electroluminescence device of the present invention can be used as a host material.
  • the material for an organic electroluminescent element of the present invention may contain other compounds as dopant materials.
  • the material for organic electroluminescent elements of the present invention can also be used as a material for hole transport layer, enhancement layer, light emitting layer, electron transport layer, charge generation layer, electron blocking layer, encapsulation layer or photorefractive layer.
  • the carbazole derivatives of the present invention have a novel structure of naphthocarbazole or naphtholine indole, have bipolarity for transporting electrons and holes, and are suitable for use as materials for organic electroluminescent elements;
  • the material for the organic electroluminescent element of the carbazole derivative has the characteristics of low starting voltage, high luminous efficiency and brightness.
  • the carbazole derivatives of the present invention have good thermal stability and film-forming performance, and can be used in materials for organic electroluminescent elements, organic electroluminescent elements, display devices, and lighting devices to prolong the service life, thereby enabling Reduce power consumption and manufacturing costs.
  • FIG. 1 is a schematic diagram of an organic light-emitting device 100 of the present invention
  • 101 is a substrate
  • 102 is an anode
  • 103 is a hole injection layer
  • 104 is a hole transport layer
  • 105 is an electron blocking layer
  • 106 is a light-emitting layer
  • 107 is a hole blocking layer
  • 108 is an electron transport layer
  • 110 is a cathode
  • 111 is a capping layer (CPL).
  • CPL capping layer
  • FIG. 2 is a schematic diagram of an inverted organic light-emitting device 200 of the present invention.
  • 201 is a substrate
  • 202 is a cathode
  • 203 is a light emitting layer
  • 204 is a hole transport layer
  • 205 is an anode.
  • Luminance and chromaticity coordinates tested using spectral scanner PhotoResearch PR-715;
  • Life test use LTS-1004AC life test device.
  • the preparation method of intermediate A1 comprises the steps:
  • the first step preparation of compound Int-1
  • the preparation method of intermediate A2 comprises the steps:
  • the mixture of the following compounds A1 and A2 is used as the green light host material, wherein the mass ratio of A1 and A2 is 11:9, the following compound B is used as the green light doping material, and the compound C is used as the hole injection material, and the compound D is used as a hole transport material, compound E is used as a red light material, compound F is used as a red light dopant material, compound G is used as an electron transport dopant material, and LiQ is used as an electron transport host material.
  • the EL vapor deposition machine manufactured by DOV company is used to vapor-deposit on the ITO glass to make a green light element in turn, and a green organic electroluminescence element is obtained.
  • the EL vapor deposition machine manufactured by DOV company is used to vapor-deposit it on the ITO glass to make a red light element, and to obtain a red light organic electroluminescence element.
  • the component structure is: any one or more of
  • the performance testing results of the obtained green organic electroluminescent element are listed in Table 4, wherein the driving voltage (V), current efficiency (LE), and half-maximum width (FWHM) are under the condition that the current density of the element is 10mA/cm obtained, and the voltage, LE, FWHM and LT90% were compared with the reference element and the data were normalized.
  • V driving voltage
  • LE current efficiency
  • FWHM half-maximum width
  • the carbazole derivative of the present invention has the advantages of low driving voltage and high current efficiency, and when the initial current density of the element is 50mA/cm 2 , The LT90% lifetime of components is even increased several times.
  • Table 4 only lists the properties of some compounds in CJHM515 ⁇ CJHM877, and the properties of other compounds are basically consistent with the structures of the compounds listed in the table. Due to limited space, they are not listed one by one.
  • Red light elements were prepared according to the method of Comparative Example 1, wherein the compound E in Comparative Example 1 was replaced by any one or more of the compounds CJHM517 to CJHM847 of the present invention to prepare organic electroluminescent elements,
  • Component structure any one or more of
  • the performance testing results of the obtained element are listed in Table 5, wherein the driving voltage (V), current efficiency (LE), and half-maximum width (FWHM) are obtained under the condition that the current density of the element is 10mA/cm 2 , and the voltage, LE, FWHM, and LT90% were normalized compared to the reference components.
  • Table 5 only lists the properties of some compounds in CJHM517 ⁇ CJHM847, and the properties of other compounds are basically consistent with the structures of the compounds listed in the table. Due to limited space, they are not listed one by one.

Abstract

A derivative of a naphthyl carbazole or naphthyl carboline structure, the use thereof respectively as a luminescent material layer, a hole transport layer, a hole barrier layer or an encapsulation layer material in an organic electroluminescent element, and the use thereof in a display device and a lighting device. The organic electroluminescent element containing the derivative has the characteristics of a low starting voltage, high luminous efficiency, high brightness, and a prolonged service life.

Description

一种咔唑衍生物及其应用A kind of carbazole derivative and its application
交叉引用cross reference
本申请要求2022年2月28日提交的专利名称为“一种咔唑衍生物及其应用”的第202210186320.5号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。This application claims the priority of Chinese Patent Application No. 202210186320.5 filed on February 28, 2022, with the patent title "A Carbazole Derivative and Its Application", the entire disclosure content of which is incorporated herein by reference in its entirety.
技术领域technical field
本发明涉及有机电致发光材料技术领域，尤其涉及一种咔唑衍生物及其应用。The invention relates to the technical field of organic electroluminescent materials, in particular to a carbazole derivative and its application.
背景技术Background technique
最近几年有机电致发光显示技术已趋于成熟，一些产品已进入市场，但在产业化过程中，仍有许多问题亟待解决，特别是用于制作元件的各种有机材料，其载流子注入、传输性能，材料电发光性能、使用寿命、色纯度、各种材料之间及与各电极之间的匹配等，尚有许多问题还未解决。尤其是发光元件在发光效率和使用寿命方面还达不到实用化要求，这大大限制了OLED技术的发展。In recent years, organic electroluminescent display technology has become mature, and some products have entered the market, but in the process of industrialization, there are still many problems to be solved, especially the various organic materials used to make components, the carrier Injection, transmission performance, material electroluminescence performance, service life, color purity, matching between various materials and electrodes, etc., there are still many problems that have not been resolved. In particular, the luminous efficiency and service life of light-emitting elements have not yet met the practical requirements, which greatly limits the development of OLED technology.
有机电致发光主要分为荧光和磷光，但根据自旋量子统计理论，单重态激子和三重态激子的概率为1:3，即来自单重态激子辐射跃迁的荧光的理论极限为25％，三重态激子辐射跃迁的荧光的理论极限为75％。如何利用75％的三线态激子的能量成为当务之急。1997年Forrest等发现磷光电致发光现象突破了有机电致发光材料量子效率25％效率的限制，引起人们对金属配合物磷光材料的广泛关注。从此，人们对磷光材料进行大量的研究。Organic electroluminescence is mainly divided into fluorescence and phosphorescence, but according to the spin quantum statistical theory, the probability of singlet excitons and triplet excitons is 1:3, which is the theoretical limit of fluorescence from radiative transitions of singlet excitons The theoretical limit of fluorescence for triplet exciton radiative transitions is 25% and 75%. How to utilize the energy of 75% triplet excitons has become a top priority. In 1997, Forrest et al. discovered that the phenomenon of phosphorescence electroluminescence broke through the limit of 25% efficiency of the quantum efficiency of organic electroluminescent materials, which aroused people's widespread attention on metal complex phosphorescent materials. Since then, a lot of research has been done on phosphorescent materials.
鉴于以上原因，特提出本发明。In view of the above reasons, the present invention is proposed.
发明内容Contents of the invention
为了解决现有技术存在的以上问题，本发明提供了一种咔唑衍生物及其应用，将该咔唑衍生物作为有机电致发光元件用材料的原料，能够提供启动电压降低、发光效率高、亮度提高的有机电致发光元件用材料以及有机电致发光元件。In order to solve the above problems in the prior art, the present invention provides a carbazole derivative and its application. The carbazole derivative can be used as a raw material for an organic electroluminescence element material, which can provide reduced starting voltage and high luminous efficiency. , A material for an organic electroluminescent element with improved brightness, and an organic electroluminescent element.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
本发明提供一种咔唑衍生物，其结构如式(I)所示：The present invention provides a kind of carbazole derivative, its structure is as shown in formula (I):
Figure PCTCN2022140647-appb-000001
Figure PCTCN2022140647-appb-000001
其中，W 1、W 2、W 3、W 4各自独立地表示CR 9，相邻的两个基团W 1和W 2、W 3和W 4代表下式(II)的基团，并且W 1和W 2或W 3和W 4至少有一者为式(II)基团； Wherein, W 1 , W 2 , W 3 , and W 4 each independently represent CR 9 , the adjacent two groups W 1 and W 2 , W 3 and W 4 represent groups of the following formula (II), and W At least one of 1 and W 2 or W 3 and W 4 is a group of formula (II);
Figure PCTCN2022140647-appb-000002
Figure PCTCN2022140647-appb-000002
Z在每次出现时相同或不同地代表CR 0或N，并且“^”指示式(I)中相邻的基团W 1和W 2或W 3和W 4； Z represents CR 0 or N identically or differently at each occurrence, and "^" indicates adjacent groups W 1 and W 2 or W 3 and W 4 in formula (I);
X代表CR 10或N； X stands for CR 10 or N;
R 0、R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10相同或者不同，各自独立地选自由以下基团组成的群组：氢、氘、具有C 1～C 40的直链烷基、具有C 1～C 40的直链杂烷基、具有C 3～C 40的支链或环状的烷基、具有C 3～C 40的支链或环状的杂烷基、具有C 2～C 40的烯基或炔基、具有5～60个碳原子的芳基、具有5～60个碳原子的杂芳基，R 0～R 10中的两个或更多个相邻的取代基团可以任选地接合或稠合形成单环或多环的脂族、芳族或芳族环系、杂芳族或杂芳族环系； R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same or different, each independently selected from the group consisting of: hydrogen , deuterium, straight-chain alkyl with C 1 to C 40 , straight-chain heteroalkyl with C 1 to C 40 , branched or cyclic alkyl with C 3 to C 40 , C 3 to C 40 branched or cyclic heteroalkyl, alkenyl or alkynyl with C 2 to C 40 , aryl with 5 to 60 carbon atoms, heteroaryl with 5 to 60 carbon atoms, R 0 to Two or more adjacent substituent groups in R can optionally be joined or fused to form a monocyclic or polycyclic aliphatic, aromatic or aromatic ring system, heteroaromatic or heteroaromatic ring Tie;
Ar 1选自由以下基团组成的群组：具有5～60个碳原子的芳基或具有5～60个碳原子的杂芳基。 Ar 1 is selected from the group consisting of aryl having 5-60 carbon atoms or heteroaryl having 5-60 carbon atoms.
本发明意义上的芳基或芳香族基团含有5～60个碳原子，在本发明意义上的杂芳基含有2～60个碳原子和至少一个杂原子，其条件是碳原子和杂原子的总和至少是5；所述杂原子优选选自N、O或S。此处的芳基或杂芳基涵盖单环基团和多环系统。多环可以具有两个碳为两个邻接环或称为“稠合的”共用的两个或更多个环，其中所述环中的至少一者是芳香族的，例如其它环可以是环烷基、环烯基、芳基、杂环和/或杂芳基。另外，多个芳基或杂芳基还可以由非芳族单元例如C、N、O或S原子连接，例如，和其中两个或更多个芳基被例如短的烷基连接的体系一样，诸如芴、9,9’-螺二芴、9,9-二芳基芴，三芳基胺、二芳基醚、二苯并呋喃或二苯并噻吩等。An aryl or aromatic group in the sense of the present invention contains 5 to 60 carbon atoms, a heteroaryl group in the sense of the present invention contains 2 to 60 carbon atoms and at least one heteroatom, with the proviso that carbon atoms and heteroatoms The sum of is at least 5; said heteroatoms are preferably selected from N, O or S. Aryl or heteroaryl here encompasses monocyclic groups and polycyclic ring systems. A polycyclic ring may have two carbons common to two adjacent rings or two or more rings known as "fused", where at least one of the rings is aromatic, e.g. the other rings may be rings Alkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl. In addition, multiple aryl or heteroaryl groups may also be linked by non-aromatic units such as C, N, O or S atoms, for example, as in systems where two or more aryl groups are linked by, for example, short alkyl groups , such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, dibenzofuran or dibenzothiophene, etc.
本发明中使用的烷基是指碳原子数从1至40的直链或支链的饱和烃去除一个氢原子而得到的一价官能团。作为其非限制性例子，有甲基、乙基、丙基、异丁基、仲丁基、戊基、异戊基、己基等。杂烷基是指烷基上的氢原子或-CH 2-被至少一个杂原子取代，所述杂原子选自卤素、腈基、N、O、S或硅，作为非限制性的例子，有二氟甲基、三氟甲基、三氟乙基、五氟乙基、腈基、乙腈基、甲氧基甲基、甲氧基乙基、三甲基硅基、三异丙基硅基等。 The alkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. As non-limiting examples thereof, there are methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, and the like. Heteroalkyl means that the hydrogen atom or -CH2- on the alkyl group is replaced by at least one heteroatom selected from halogen, nitrile, N, O, S or silicon. As non-limiting examples, there are Difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, nitrile, acetonitrile, methoxymethyl, methoxyethyl, trimethylsilyl, triisopropylsilyl wait.
本发明中使用的烯基是指从具有一个以上碳碳双键的碳原子数从2至40的直链或支链的不饱和烃去除一个氢原子而得到的一价官能团。作为其非限制性例子，有乙烯基、烯丙基、异丙烯基、2-丁烯基等。The alkenyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon double bonds and having 2 to 40 carbon atoms. As non-limiting examples thereof, there are vinyl, allyl, isopropenyl, 2-butenyl and the like.
本发明中使用的炔基是指具有一个以上碳碳三键的碳原子数从2至40的直链或支链的不饱和烃去除一个氢原子而得到的一价官能团。作为其非限制性例子，有乙炔基、2-丙炔基等。The alkynyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon triple bonds and having carbon atoms ranging from 2 to 40. As non-limiting examples thereof, there are ethynyl, 2-propynyl and the like.
一般来说，根据本发明的环烷基、环烯基是指碳原子数从3至40的单环或多环非芳族烃去除一个氢原子而得到的一价官能团。作为其非限制性例子，有环丙基、环丁基、环戊基、环己基、降冰片基、金刚烷基、环丁烯基、环戊烯基、环己烯基、环庚基、环庚烯基，其中一个或多个-CH 2-基团可被上述基团代替；此外，一个或多个氢原子还可被氘原子、卤素原子或腈基代替。 In general, cycloalkyl and cycloalkenyl according to the present invention refer to monovalent functional groups obtained by removing one hydrogen atom from monocyclic or polycyclic non-aromatic hydrocarbons with 3 to 40 carbon atoms. As non-limiting examples thereof, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, Cycloheptenyl, wherein one or more -CH 2 - groups can be replaced by the above-mentioned groups; in addition, one or more hydrogen atoms can also be replaced by deuterium atoms, halogen atoms or nitrile groups.
本发明中使用的杂环烷基是指原子核数从3至40的非芳香族烃去除一个氢原子而得到的一价官能团。此时，环中一个以上的碳、优选为1至3个碳被诸如N、O或S之类的杂原子取代。作为其非限制性例子，有四氢呋喃、四氢噻吩、吗啉、哌嗪等。The heterocycloalkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having 3 to 40 atomic nuclei. In this case, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with heteroatoms such as N, O or S. As non-limiting examples thereof, there are tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine, and the like.
本发明中使用的芳氧基或杂芳氧基是指RO-所表示的一价官能团，上述R是碳原子数从6至60的芳基或碳原数从5至60的杂芳基。作为这样的芳氧基或杂芳氧基的非限制性例子，有苯氧基、萘氧基、联苯氧基、2-吡啶氧基、3-吡啶氧基、4-吡啶氧基等。The aryloxy or heteroaryloxy group used in the present invention refers to a monovalent functional group represented by RO-, where R is an aryl group with 6 to 60 carbon atoms or a heteroaryl group with 5 to 60 carbon atoms. As non-limiting examples of such aryloxy or heteroaryloxy, there are phenoxy, naphthyloxy, biphenoxy, 2-pyridyloxy, 3-pyridyloxy, 4-pyridyloxy and the like.
根据本发明的芳族、杂芳族或芳族环系、杂芳族环系，在每种情况下，芳族或杂芳族环上的原子还可被取代的芳族环系或杂芳族环系，特别是指衍生自如下物质的基团：苯、萘、蒽、苯并蒽、菲、芘、
Figure PCTCN2022140647-appb-000003
苝、荧蒽、并四苯、并五苯、苯并芘、联苯、偶苯、三联苯、三聚苯、芴、螺二芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、顺式或反式茚并咔唑、顺式或反式吲哚并咔唑、三聚茚、异三聚茚、螺三聚茚、螺异三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并[5,6]喹啉、苯并[6,7]喹啉、苯并[7,8]喹啉、吩噻嗪、吩噁嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、噁唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、异噁唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、六氮杂苯并菲、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1,5-二氮杂蒽、2,7-二氮杂芘、2,3-二氮杂芘、1,6-二氮杂芘、1,8-二氮杂芘、4,5-二氮杂芘，4,5,9,10-四氮杂苝、吡嗪、吩嗪、吩噁嗪、吩噻嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-噁二唑、1,2,4-噁二唑、1,2,5-噁二唑、1,3,4-噁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑、1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、吲嗪和苯并噻 二唑或者衍生自这些体系的组合的基团。 Aromatic, heteroaromatic or aromatic ring systems, heteroaromatic ring systems, aromatic ring systems or heteroaromatic ring systems in each case in which atoms on the aromatic or heteroaromatic ring may also be substituted according to the invention Group ring systems, in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,
Figure PCTCN2022140647-appb-000003
Perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenyl, terphenyl, tripolyphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis Or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, tripolyindene, isotripolyindene, spirothree polyindene, spiroisotripolyindene, furan, Benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline , acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyrazole, indazole , imidazole, benzimidazole, naphthimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthoxazole, anthraxazole, phenanthrene Oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diazapyrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene Pyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorochrome, naphthyridine, azacarbazole, benzocarboline, carboline, phenanthrene oxadiazole, 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 groups derived from combinations of these systems.
如本文所使用，“其组合”或“群组”表示适用清单的一或多个成员被组合以形成本领域普通技术人员能够从适用清单中设想的已知或化学稳定的布置。举例来说，烷基和氘可以组合形成部分或完全氘化的烷基；卤素和烷基可以组合形成卤代烷基取代基，例如三氟甲基等；并且卤素、烷基和芳基可以组合形成卤代芳烷基。As used herein, "a combination thereof" or "group" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can conceive from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl; halogen and alkyl can be combined to form haloalkyl substituents, such as trifluoromethyl, etc.; and halogen, alkyl and aryl can be combined to form Haloaralkyl.
作为优选，所述咔唑衍生物选自式(I)-1～式(I)-8中的一种或多种：Preferably, the carbazole derivative is selected from one or more of formula (I)-1 to formula (I)-8:
Figure PCTCN2022140647-appb-000004
Figure PCTCN2022140647-appb-000004
其中，R 0、R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10相同或者不同，各自独立地选自由以下基团组成的群组：氢、氘、具有5～60个碳原子的芳基、具有5～60个碳原子的杂芳基，R 0～R 10中的两个或更多个相邻的取代基团可以任选地接合或稠合形成单环或多环的脂族、芳族或芳族环系、杂芳族或杂芳族环系； Wherein, R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different, each independently selected from the group consisting of the following groups : hydrogen, deuterium, an aryl group with 5 to 60 carbon atoms, a heteroaryl group with 5 to 60 carbon atoms, two or more adjacent substituent groups in R 0 to R 10 can be optionally are joined or fused to form monocyclic or polycyclic aliphatic, aromatic or aromatic ring systems, heteroaromatic or heteroaromatic ring systems;
Ar 1选自由以下基团组成的群组：具有5～60个碳原子的芳基或具有5～60个碳原子的杂芳基。 Ar 1 is selected from the group consisting of aryl having 5-60 carbon atoms or heteroaryl having 5-60 carbon atoms.
作为优选，所述Ar 1表示为-(L) nAr 2基团，其中，L选自由单键、C 6-C 60的亚芳基、C 5-C 60的杂亚芳基组成的群组；n为0、1或2；Ar 2选自由以下II-1～II-17所示基团组成的群组： Preferably, the Ar 1 is represented as a -(L) n Ar 2 group, wherein L is selected from the group consisting of a single bond, a C 6 -C 60 arylene group, and a C 5 -C 60 heteroarylene group Group; n is 0, 1 or 2; Ar 2 is selected from the group consisting of the following groups shown in II-1 to II-17:
Figure PCTCN2022140647-appb-000005
Figure PCTCN2022140647-appb-000005
其中，in,
Z 1、Z 2各自独立地选自由氢、氘、卤素、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧 酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C 1～C 60烷基、C 2～C 60烯基、C 2～C 60炔基、C 1～C 60烷氧基、C 3～C 60环烷烃基、C 3～C 60环烯烃基、取代或未取代的C 6～C 60芳基、取代或未取代的C 6～C 60芳氧基、取代或未取代的C 6～C 60芳硫醚基、或者取代或未取代的C 2～C 60杂环芳基组成的群组； Z 1 and Z 2 are each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid group or sulfonate thereof , phosphate group or its phosphate salt, C 1 ~C 60 alkyl group, C 2 ~C 60 alkenyl group, C 2 ~C 60 alkynyl group, C 1 ~C 60 alkoxy group, C 3 ~C 60 cycloalkane group, C 3 ~C 60 cycloalkene group, substituted or unsubstituted C 6 ~C 60 aryl group, substituted or unsubstituted C 6 ~C 60 aryloxy group, substituted or unsubstituted C 6 ~C 60 arylsulfide group , or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aromatic groups;
x1表示1-4的整数；x2表示1-3的整数；x3表示1或2；x4表示1-6的整数；x5表示1-5的整数；x1 represents an integer of 1-4; x2 represents an integer of 1-3; x3 represents an integer of 1 or 2; x4 represents an integer of 1-6; x5 represents an integer of 1-5;
T 1表示O、S、CR’R”或NAr’； T 1 means O, S, CR'R" or NAr';
R’、R”各自独立地选自由氢、氘、C 1～C 60的烷基、C 1～C 60的杂烷基、取代或未取代的C 6～C 60芳基、取代或未取代的C 6～C 60芳胺基、或者取代或未取代的C 2～C 60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基； R' and R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
Ar’选自由C 1～C 60的烷基、C 1～C 60的杂烷基、C 3～C 60的环烷基、取代或未取代的C 6～C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6～C 60芳胺基、或者取代或未取代的C 2～C 60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基、联苯基或萘基； Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused-ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
Figure PCTCN2022140647-appb-000006
表示取代基与L的连接键。
Figure PCTCN2022140647-appb-000006
Indicates the link between the substituent and L.
作为优选，R 0、R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10各自独立地选自氢或氘。 Preferably, R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from hydrogen or deuterium.
作为优选，所述咔唑衍生物选自以下CJHM515～CJHM877所示的结构中的一种或多种：Preferably, the carbazole derivative is selected from one or more of the following structures shown in CJHM515 to CJHM877:
Figure PCTCN2022140647-appb-000007
Figure PCTCN2022140647-appb-000007
Figure PCTCN2022140647-appb-000008
Figure PCTCN2022140647-appb-000008
Figure PCTCN2022140647-appb-000009
Figure PCTCN2022140647-appb-000009
Figure PCTCN2022140647-appb-000010
Figure PCTCN2022140647-appb-000010
Figure PCTCN2022140647-appb-000011
Figure PCTCN2022140647-appb-000011
Figure PCTCN2022140647-appb-000012
Figure PCTCN2022140647-appb-000012
Figure PCTCN2022140647-appb-000013
Figure PCTCN2022140647-appb-000013
Figure PCTCN2022140647-appb-000014
Figure PCTCN2022140647-appb-000014
Figure PCTCN2022140647-appb-000015
Figure PCTCN2022140647-appb-000015
Figure PCTCN2022140647-appb-000016
Figure PCTCN2022140647-appb-000016
Figure PCTCN2022140647-appb-000017
Figure PCTCN2022140647-appb-000017
Figure PCTCN2022140647-appb-000018
Figure PCTCN2022140647-appb-000018
Figure PCTCN2022140647-appb-000019
Figure PCTCN2022140647-appb-000019
Figure PCTCN2022140647-appb-000020
Figure PCTCN2022140647-appb-000020
其中，*—T 2—*选自*—O—*、*—S—*或下述结构中的一种： Wherein, *—T 2 —* is selected from *—O—*, *—S—* or one of the following structures:
Figure PCTCN2022140647-appb-000021
Figure PCTCN2022140647-appb-000021
Figure PCTCN2022140647-appb-000022
Figure PCTCN2022140647-appb-000022
*—和—*表示连接键。*— and —* indicate connecting keys.
本发明还提供以上所述的咔唑衍生物在有机电致发光元件中的应用。The present invention also provides the application of the above-mentioned carbazole derivatives in organic electroluminescent elements.
作为优选，所述咔唑衍生物在有机电致发光元件中用作发光层材料、空穴输送层材料、空穴阻挡层材料或封装层材料。Preferably, the carbazole derivative is used as a light-emitting layer material, a hole transport layer material, a hole blocking layer material or an encapsulation layer material in an organic electroluminescent element.
本发明还提供一种有机电致发光元件，包括：第一电极、第二电极和位于所述第一电极和所述第二电极之间的至少一层有机层，所述有机层中至少一层包括以上所述的咔唑衍生物。The present invention also provides an organic electroluminescent element, comprising: a first electrode, a second electrode, and at least one organic layer between the first electrode and the second electrode, at least one of the organic layers The layer comprises the carbazole derivatives described above.
所述有机电致发光元件包含阴极、阳极和至少一个发光层。除了这些层之外，它还可以包含其它的层，例如在每种情况下，包含一个或多个空穴注入层、空穴传输层、空穴阻挡层、电子传输层、电子注入层、激子阻挡层、电子阻挡层和/或电荷产生层。具有例如激子阻挡功能的中间层同样可引入两个发光层之间。然而，应当指出，这些层中的每个并非必须都存在。此处所述有机电致发光装置可包含一个发光层，或者它可包含多个发光层。即，将能够发光的多种发光化合物用于所述发光层中。特别优选具有三个发光层的体系，其中所述三个层可显示蓝色、绿色和红色发光。如果存在多于一个的发光层，则根据本发明，这些层中的至少一个层包含本发明的咔唑衍生物。The organic electroluminescent element comprises a cathode, an anode and at least one light-emitting layer. Besides these layers it may also contain further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, excitation layers, sub-blocking layer, electron blocking layer and/or charge generating layer. Interlayers having, for example, an exciton-blocking function can likewise be introduced between two emitting layers. It should be noted, however, that not every one of these layers is required to be present. The organic electroluminescent device described herein may comprise one light-emitting layer, or it may comprise a plurality of light-emitting layers. That is, various light-emitting compounds capable of emitting light are used in the light-emitting layer. Particular preference is given to systems with three emitting layers, the three layers being able to exhibit blue, green and red emission. If more than one emitting layer is present, according to the invention at least one of these layers comprises a carbazole derivative according to the invention.
在根据本发明的有机电致发光元件的其它层中，特别是在空穴传输层中以及在空穴阻挡层和薄膜封装层中，所有材料可以按照根据现有技术通常所使用的方式来使用。本领域普通技术人员因此将能够在不付出创造性劳动的情况下与根据本发明的发光层组合使用关于有机电致发光元件所知的所有材料。In the other layers of the organic electroluminescent component according to the invention, in particular in the hole-transport layer as well as in the hole-blocking layer and the thin-film encapsulation layer, all materials can be used in the manner usually used according to the prior art . A person skilled in the art will therefore be able to use, without inventive step, all materials known for organic electroluminescent elements in combination with the emitting layer according to the invention.
此外优选如下的有机电致发光元件，借助于升华方法施加一个或多个层，其中在真空升华装置中在低于10 -5Pa、优选低于10 -6Pa的初压下通过气相沉积来施加所述材料。然而，所述初压还可能甚至更低，例如低于10 -7Pa。 Furthermore, preference is given to organic electroluminescent components in which one or more layers are applied by means of a sublimation method by vapor deposition in a vacuum sublimation apparatus at an initial pressure below 10 −5 Pa, preferably below 10 −6 Pa. Apply the material. However, the initial pressure may also be even lower, for example below 10 −7 Pa.
同样优选如下的有机电致发光元件，借助于有机气相沉积方法或借助于载气升华来施加一个或多个层，其中，在10 -5Pa至1Pa之间的压力下施加所述材料。该方法的特别的例子是有机蒸汽喷印方法，其中所述材料通过喷嘴直接施加，并且因此是结构化的。 Preference is likewise given to organic electroluminescent components in which one or more layers are applied by means of organic vapor deposition methods or by means of carrier gas sublimation, the materials being applied at a pressure of between 10 −5 Pa and 1 Pa. A particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is thus structured.
此外优选如下的有机电致发光元件，从溶液中，例如通过旋涂，或借助于任何所希望的印刷方法例如丝网印刷、柔性版印刷、平版印刷、光引发热成像、热转印、喷墨印刷或喷嘴印刷，来产生一个或多个层。可溶性化合物，例如通过适当的取代式(I)所示的化合物获得可溶性化合物。这些方法也特别适于低聚物、树枝状大分子和聚合物。此外可行的是混合方法，其中例如从溶液中施加一个或多个层并且通过气相沉积施加一个或多个另外的层。Furthermore, preference is given to organic electroluminescent elements which, from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithography, photoinduced thermography, thermal transfer, spray Ink printing or nozzle printing to produce one or more layers. Soluble compounds are obtained, for example, by appropriately substituting the compound represented by formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers. Also possible are hybrid methods in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
进一步地，所述有机层还包括选自电子注入层、电子输送层、空穴阻挡层、电子阻挡层、空穴输送层、空穴注入层、发光层、光折射层的一种以上。Further, the organic layer further includes one or more selected from electron injection layer, electron transport layer, hole blocking layer, electron blocking layer, hole transport layer, hole injection layer, light emitting layer, and photorefractive layer.
本发明的有机电致发光元件既可以是顶发射光元件，又可以是底发射光元件。本发明的有机电致发光元件的结构和制备方法没有限定。采用本发明的化合物制得的有机电致发光元件可降低启动电压、提高发光效率和亮度。The organic electroluminescent element of the present invention can be either a top-emitting light element or a bottom-emitting light element. The structure and preparation method of the organic electroluminescent element of the present invention are not limited. The organic electroluminescent element prepared by using the compound of the invention can reduce the starting voltage and improve the luminous efficiency and brightness.
本发明同时提供一种显示装置，包括以上所述的有机电致发光元件。The present invention also provides a display device comprising the organic electroluminescent element described above.
本发明同时提供一种照明装置，包括以上所述的有机电致发光元件。The present invention also provides an illuminating device, comprising the above-mentioned organic electroluminescence element.
本发明的有机电致发光元件用材料含有本发明的咔唑衍生物。有机电致发光元件用材料可以单独使用本发明的化合物构成，也可以同时含有其他化合物。The material for an organic electroluminescent device of the present invention contains the carbazole derivative of the present invention. The material for an organic electroluminescent element may be constituted by using the compound of the present invention alone, or may contain other compounds together.
本发明的有机电致发光元件用材料中所含有的本发明的咔唑衍生物可以用作主体材料。此时，本发明的有机电致发光元件用材料中可以含有作为掺杂材料的其他化合物。The carbazole derivative of the present invention contained in the material for an organic electroluminescence device 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 other compounds as dopant materials.
本发明的有机电致发光元件用材料还可以作为空穴传输层、增强层、发光层、电子传输层、电荷产生层、电子阻挡层、封装层或光折射层用材料。The material for organic electroluminescent elements of the present invention can also be used as a material for hole transport layer, enhancement layer, light emitting layer, electron transport layer, charge generation layer, electron blocking layer, encapsulation layer or photorefractive layer.
与现有技术相比，本发明的有益效果为：Compared with prior art, the beneficial effect of the present invention is:
本发明所述的咔唑衍生物具有萘联咔唑或萘联咔啉并吲哚的新颖结构，具有输送电子和空穴的双极性，适宜作为有机电致发光元件用材料使用；含有所述咔唑衍生物的有机电致发光元件用材料，具有启动 电压低，发光效率和亮度高的特点。另外，本发明的咔唑衍生物具有良好的热稳定性和成膜性能，应用在有机电致发光元件用材料、有机电致发光元件、显示装置、照明装置中，能够延长使用寿命，从而能够降低功耗和制造成本。The carbazole derivatives of the present invention have a novel structure of naphthocarbazole or naphtholine indole, have bipolarity for transporting electrons and holes, and are suitable for use as materials for organic electroluminescent elements; The material for the organic electroluminescent element of the carbazole derivative has the characteristics of low starting voltage, high luminous efficiency and brightness. In addition, the carbazole derivatives of the present invention have good thermal stability and film-forming performance, and can be used in materials for organic electroluminescent elements, organic electroluminescent elements, display devices, and lighting devices to prolong the service life, thereby enabling Reduce power consumption and manufacturing costs.
附图说明Description of drawings
图1为本发明的有机发光装置100示意图；FIG. 1 is a schematic diagram of an organic light-emitting device 100 of the present invention;
图1中，101是衬底、102是阳极、103是空穴注入层、104是空穴传输层、105是电子阻挡层、106是发光层、107是空穴阻挡层、108是电子传输层、109是电子注入层、110是阴极、111是封盖层(CPL)。In Fig. 1, 101 is a substrate, 102 is an anode, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light-emitting layer, 107 is a hole blocking layer, and 108 is an electron transport layer , 109 is an electron injection layer, 110 is a cathode, and 111 is a capping layer (CPL).
图2为本发明倒转的有机发光装置200示意图；FIG. 2 is a schematic diagram of an inverted organic light-emitting device 200 of the present invention;
图2中，201是衬底、202是阴极、203是发光层、204是空穴传输层、205是阳极。In FIG. 2 , 201 is a substrate, 202 is a cathode, 203 is a light emitting layer, 204 is a hole transport layer, and 205 is an anode.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明的技术方案进行详细的描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施方式，都属于本发明所保护的范围。In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other implementations obtained by persons of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.
以下实施例中OLED材料及元件进行性能测试的测试仪器及方法如下：The testing instrument and method that OLED material and element carry out performance test in following embodiment are as follows:
OLED元件性能检测条件：OLED component performance testing conditions:
亮度和色度坐标：使用光谱扫描仪PhotoResearch PR-715测试；Luminance and chromaticity coordinates: tested using spectral scanner PhotoResearch PR-715;
电流密度和起亮电压：使用数字源表Keithley 2420测试；Current density and lighting voltage: Tested with Keithley 2420 digital source meter;
功率效率：使用NEWPORT 1931-C测试；Power efficiency: tested with NEWPORT 1931-C;
寿命测试：使用LTS-1004AC寿命测试装置。Life test: use LTS-1004AC life test device.
实施例1Example 1
中间体A1的制备方法，包括如下步骤：The preparation method of intermediate A1, comprises the steps:
第一步：化合物Int-1的制备The first step: preparation of compound Int-1
Figure PCTCN2022140647-appb-000023
Figure PCTCN2022140647-appb-000023
12.0mmol的苯并[kl]吲哚[3,2,1-de]吖啶-7-基硼酸、10.0mmol的邻溴硝基苯、40.0mmol的无水碳酸钾和0.01mmol的Pd132溶解于40mL的甲苯、20mL的乙醇和20mL的水中，在氮气保护下，升温回流搅拌反应12小时，降到室温，加入50mL水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-1，黄色固体，收率：85％。12.0 mmol of benzo[kl]indol[3,2,1-de]acridin-7-ylboronic acid, 10.0 mmol of o-bromonitrobenzene, 40.0 mmol of anhydrous potassium carbonate and 0.01 mmol of Pd132 were dissolved in 40mL of toluene, 20mL of ethanol and 20mL of water, under the protection of nitrogen, raise the temperature and reflux to stir for 12 hours, lower to room temperature, add 50mL of water to dilute, extract with ethyl acetate, collect the organic phase, dry, filter, and depressurize the filtrate Concentrate to dryness, separate and purify with silica gel column to obtain compound Int-1, yellow solid, yield: 85%.
第二步：化合物A1的制备The second step: the preparation of compound A1
Figure PCTCN2022140647-appb-000024
Figure PCTCN2022140647-appb-000024
在氮气保护下，20.0mmol的中间体Int-1溶于60mL的邻二氯苯中，加入0.1mol的三苯基磷，升温至回流搅拌反应8小时，降到室温，加入100mL的甲苯稀释，加入0.1mol的氯化锌搅拌反应2小时，过滤，滤液减压浓缩干燥，用硅胶柱分离纯化，得到中间体A1，收率：82％，HRMS：m/z 381.1401[M+H] +。 Under the protection of nitrogen, 20.0 mmol of intermediate Int-1 was dissolved in 60 mL of o-dichlorobenzene, 0.1 mol of triphenylphosphine was added, the temperature was raised to reflux and stirred for 8 hours, then cooled to room temperature, and 100 mL of toluene was added to dilute. Add 0.1 mol of zinc chloride and stir for 2 hours, filter, concentrate and dry the filtrate under reduced pressure, separate and purify with silica gel column to obtain intermediate A1, yield: 82%, HRMS: m/z 381.1401[M+H] + .
实施例2Example 2
中间体A2的制备方法，包括如下步骤：The preparation method of intermediate A2, comprises the steps:
第一步：化合物Int-2的制备The first step: preparation of compound Int-2
Figure PCTCN2022140647-appb-000025
Figure PCTCN2022140647-appb-000025
20.0mmol的8-氯苯并[kl]吲哚[3,2,1-de]吖啶(参考专利CN112707904A中实施例1的合成方法制备)、24.0mmol的联硼酸频哪醇酯、30.0mmol的无水醋酸钾和0.2mmol的PdCl 2(dppf)溶解于50mL的DMF中，在氮气保护下，升温至100℃搅拌反应12小时，降到室温，加入200mL水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-2，白色固体，收率：86％。 20.0mmol of 8-chlorobenzo[kl]indole[3,2,1-de]acridine (prepared by the synthetic method of Example 1 in the reference patent CN112707904A), 24.0mmol of biboronic acid pinacol ester, 30.0mmol Anhydrous potassium acetate and 0.2mmol of PdCl 2 (dppf) were dissolved in 50mL of DMF, under the protection of nitrogen, the temperature was raised to 100°C and stirred for 12 hours, cooled to room temperature, diluted with 200mL of water, extracted with ethyl acetate, The organic phase was collected, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure, separated and purified by silica gel column to obtain compound Int-2 as a white solid, yield: 86%.
第二步：化合物Int-3的制备The second step: the preparation of compound Int-3
Figure PCTCN2022140647-appb-000026
Figure PCTCN2022140647-appb-000026
参照实施例1第一步的合成方法，仅将实施例1第一步的苯并[kl]吲哚[3,2,1-de]吖啶-7-基硼酸替换为Int-2，制备化合物Int-3，黄色固体，收率87％。With reference to the synthetic method of the first step of Example 1, only the benzo[kl]indole[3,2,1-de]acridin-7-ylboronic acid in the first step of Example 1 was replaced by Int-2 to prepare Compound Int-3, yellow solid, yield 87%.
第三步：化合物A2的制备The third step: the preparation of compound A2
Figure PCTCN2022140647-appb-000027
Figure PCTCN2022140647-appb-000027
在氮气保护下，20.0mmol的中间体Int-3和0.1mol的三苯基磷混合均匀，升温至180℃搅拌反应5小时，降温到120℃，滴加入100mL的甲苯稀释，加入0.1mol的氯化锌，升温回流搅拌反应2小时，降到室温，过滤，滤液减压浓缩干燥，用硅胶柱分离纯化，得到中间体A2，收率：76％，HRMS：m/z381.1405[M+H] +。 Under the protection of nitrogen, mix 20.0mmol of intermediate Int-3 and 0.1mol of triphenylphosphine evenly, raise the temperature to 180°C and stir for 5 hours, cool down to 120°C, add 100mL of toluene dropwise for dilution, and add 0.1mol of chlorine Feed zinc, raise the temperature and reflux and stir for 2 hours, cool down to room temperature, filter, concentrate and dry the filtrate under reduced pressure, separate and purify with silica gel column to obtain intermediate A2, yield: 76%, HRMS: m/z381.1405 [M+H ] + .
参照上述实施例1和实施例2类似的合成方法，制备以下表1所示的化合物；With reference to the above-mentioned synthesis method similar to Example 1 and Example 2, the compounds shown in the following Table 1 were prepared;
表1Table 1
Figure PCTCN2022140647-appb-000028
Figure PCTCN2022140647-appb-000028
Figure PCTCN2022140647-appb-000029
Figure PCTCN2022140647-appb-000029
实施例3Example 3
化合物CJHM520的制备：Preparation of compound CJHM520:
Figure PCTCN2022140647-appb-000030
Figure PCTCN2022140647-appb-000030
10.0mmol中间体A2溶解于80mL干燥的THF中，在氮气保护下，用冰水浴降温至0℃，加入12.0mmol的65％氢化钠固体，搅拌反应1小时，加入11.0mmol的2-([1,1'-联苯]-2-基)-4-氯-6-苯基-1,3,5-三嗪，搅拌反应24小时，加入50mL水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物CJHM520，黄色固体，收率75％，MS(MALDI-TOF)：m/z 688.2515[M+H] +； 1HNMR(δ、CDCl 3)：9.11(1H,s)；8.83(1H,s)；8.74～8.71(1H,m)；8.63～8.56(3H,m)；8.46～8.35(4H,m)；8.17～8.13(2H,m)；8.06～8.04(1H,m)；7.89～7.85(1H,m)；7.61～7.55(3H,m)；7.46～7.27(10H,m)；7.22～7.18(2H,m)。 10.0mmol of intermediate A2 was dissolved in 80mL of dry THF, and under the protection of nitrogen, the temperature was cooled to 0°C with an ice-water bath, 12.0mmol of 65% sodium hydride solid was added, the reaction was stirred for 1 hour, and 11.0mmol of 2-([1 ,1'-biphenyl]-2-yl)-4-chloro-6-phenyl-1,3,5-triazine, stirred for 24 hours, diluted with 50 mL of water, extracted with ethyl acetate, collected the organic phase , dried, filtered, the filtrate was concentrated to dryness under reduced pressure, separated and purified with a silica gel column to obtain compound CJHM520, yellow solid, yield 75%, MS (MALDI-TOF): m/z 688.2515[M+H] + ; 1 HNMR ( δ, CDCl 3 ): 9.11(1H,s); 8.83(1H,s); 8.74～8.71(1H,m); 8.63～8.56(3H,m); 8.46～8.35(4H,m); 8.17～8.13 (2H,m); 8.06～8.04(1H,m); 7.89～7.85(1H,m); 7.61～7.55(3H,m); 7.46～7.27(10H,m); 7.22～7.18(2H,m) .
参照上述实施例3类似的合成方法，制备以下表2所示的化合物；Referring to the similar synthesis method of the above-mentioned Example 3, the compounds shown in the following Table 2 were prepared;
表2Table 2
Figure PCTCN2022140647-appb-000031
Figure PCTCN2022140647-appb-000031
Figure PCTCN2022140647-appb-000032
Figure PCTCN2022140647-appb-000032
Figure PCTCN2022140647-appb-000033
Figure PCTCN2022140647-appb-000033
Figure PCTCN2022140647-appb-000034
Figure PCTCN2022140647-appb-000034
Figure PCTCN2022140647-appb-000035
Figure PCTCN2022140647-appb-000035
Figure PCTCN2022140647-appb-000036
Figure PCTCN2022140647-appb-000036
Figure PCTCN2022140647-appb-000037
Figure PCTCN2022140647-appb-000037
Figure PCTCN2022140647-appb-000038
Figure PCTCN2022140647-appb-000038
Figure PCTCN2022140647-appb-000039
Figure PCTCN2022140647-appb-000039
Figure PCTCN2022140647-appb-000040
Figure PCTCN2022140647-appb-000040
Figure PCTCN2022140647-appb-000041
Figure PCTCN2022140647-appb-000041
Figure PCTCN2022140647-appb-000042
Figure PCTCN2022140647-appb-000042
Figure PCTCN2022140647-appb-000043
Figure PCTCN2022140647-appb-000043
实施例4Example 4
化合物CJHM599的制备：Preparation of compound CJHM599:
Figure PCTCN2022140647-appb-000044
Figure PCTCN2022140647-appb-000044
15.0mmol化合物A1溶解于80mL干燥的甲苯中，在氮气保护下，加入16.5mmol的2-(3-溴苯基)-4,6-二苯基-1,3,5-三嗪和22.5mmol的叔丁醇钠，再加入0.1mmol的Pd 2(dba) 3CHCl 3和0.02mL的10％三叔丁磷甲苯溶液，升温至100℃，搅拌反应15小时，冷却到室温，加入50mL水稀释，用二氯甲烷萃取，收集有机相，干燥，过滤，滤液减压浓缩干燥，用硅胶柱分离纯化，得到化合物CJHM599，黄色固体，收率86％，MS(MALDI-TOF)：m/z 662.2441[M+H] +； 1HNMR(δ、CDCl 3)：8.81～8.78(4H,m)；8.65(1H,s)；8.47～8.33(5H,m)；8.21～8.15(2H,m)；7.93～7.85(3H,m)；7.65～7.62(1H,m)；7.55～7.50(5H,m)；7.48～7.41(4H,m)；7.37～7.29(4H,m)。 15.0mmol of compound A1 was dissolved in 80mL of dry toluene, under nitrogen protection, 16.5mmol of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine and 22.5mmol of Sodium tert-butoxide, then add 0.1mmol of Pd 2 (dba) 3 CHCl 3 and 0.02mL of 10% tri-tert-butylphosphonium toluene solution, heat up to 100°C, stir for 15 hours, cool to room temperature, add 50mL of water to dilute , extracted with dichloromethane, collected the organic phase, dried, filtered, the filtrate was concentrated and dried under reduced pressure, separated and purified by silica gel column to obtain compound CJHM599, yellow solid, yield 86%, MS (MALDI-TOF): m/z 662.2441 [M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.81～8.78(4H,m); 8.65(1H,s); 8.47～8.33(5H,m); 8.21～8.15(2H,m); 7.93～7.85(3H,m); 7.65～7.62(1H,m); 7.55～7.50(5H,m); 7.48～7.41(4H,m); 7.37～7.29(4H,m).
参照上述实施例4类似的合成方法，制备以下表3所示的化合物：With reference to the similar synthetic method of the above-mentioned Example 4, the compounds shown in the following table 3 were prepared:
表3table 3
Figure PCTCN2022140647-appb-000045
Figure PCTCN2022140647-appb-000045
Figure PCTCN2022140647-appb-000046
Figure PCTCN2022140647-appb-000046
Figure PCTCN2022140647-appb-000047
Figure PCTCN2022140647-appb-000047
Figure PCTCN2022140647-appb-000048
Figure PCTCN2022140647-appb-000048
Figure PCTCN2022140647-appb-000049
Figure PCTCN2022140647-appb-000049
Figure PCTCN2022140647-appb-000050
Figure PCTCN2022140647-appb-000050
Figure PCTCN2022140647-appb-000051
Figure PCTCN2022140647-appb-000051
Figure PCTCN2022140647-appb-000052
Figure PCTCN2022140647-appb-000052
Figure PCTCN2022140647-appb-000053
Figure PCTCN2022140647-appb-000053
Figure PCTCN2022140647-appb-000054
Figure PCTCN2022140647-appb-000054
Figure PCTCN2022140647-appb-000055
Figure PCTCN2022140647-appb-000055
有机电致发光元件(如图1和图2所示)的制备Preparation of organic electroluminescent elements (as shown in Figure 1 and Figure 2)
对比例1Comparative example 1
将下述的化合物A1和A2的混合物作为绿光主体材料，其中A1和A2的质量比为11:9，使用下述的化合物B作为绿光掺杂材料，化合物C作为空穴注入材料，化合物D作为空穴传输材料、化合物E作为红光材料，化合物F作为红光掺杂材料，化合物G作为电子传输掺杂材料，LiQ作为电子传输主体材料。The mixture of the following compounds A1 and A2 is used as the green light host material, wherein the mass ratio of A1 and A2 is 11:9, the following compound B is used as the green light doping material, and the compound C is used as the hole injection material, and the compound D is used as a hole transport material, compound E is used as a red light material, compound F is used as a red light dopant material, compound G is used as an electron transport dopant material, and LiQ is used as an electron transport host material.
Figure PCTCN2022140647-appb-000056
Figure PCTCN2022140647-appb-000056
将化合物
Figure PCTCN2022140647-appb-000057
依次采用DOV公司制造的EL蒸镀机蒸镀到ITO玻璃上制作绿光元件，制得作为绿光的有机电致发光元件。 compound
Figure PCTCN2022140647-appb-000057
The EL vapor deposition machine manufactured by DOV company is used to vapor-deposit on the ITO glass to make a green light element in turn, and a green organic electroluminescence element is obtained.
将化合物
Figure PCTCN2022140647-appb-000058
依次采用DOV公司制造的EL蒸镀机蒸镀到ITO玻璃上制作红光元件，制得作为红光的有机电致发光元件。 compound
Figure PCTCN2022140647-appb-000058
The EL vapor deposition machine manufactured by DOV company is used to vapor-deposit it on the ITO glass to make a red light element, and to obtain a red light organic electroluminescence element.
试验例1Test example 1
将对比例1中化合物A1和A2替换为本发明的化合物CJHM515～CJHM877中的任一种或多种，按照对比例1的方法制备绿光有机电致发光元件，Replace the compounds A1 and A2 in Comparative Example 1 with any one or more of the compounds CJHM515-CJHM877 of the present invention, and prepare a green organic electroluminescent element according to the method of Comparative Example 1,
元件结构为：
Figure PCTCN2022140647-appb-000059
中的任一种或多种
Figure PCTCN2022140647-appb-000060
The component structure is:
Figure PCTCN2022140647-appb-000059
any one or more of
Figure PCTCN2022140647-appb-000060
所得绿光有机电致发光元件的性能检测结果列于表4中，其中驱动电压(V)、电流效率(LE)、半峰宽(FWHM)是在元件的电流密度为10mA/cm 2条件下得出，且电压、LE、FWHM和LT90％相较对比元件进行了数据归一化处理。 The performance testing results of the obtained green organic electroluminescent element are listed in Table 4, wherein the driving voltage (V), current efficiency (LE), and half-maximum width (FWHM) are under the condition that the current density of the element is 10mA/cm obtained, and the voltage, LE, FWHM and LT90% were compared with the reference element and the data were normalized.
表4绿光元件数据Table 4 Green light component data
Figure PCTCN2022140647-appb-000061
Figure PCTCN2022140647-appb-000061
Figure PCTCN2022140647-appb-000062
Figure PCTCN2022140647-appb-000062
Figure PCTCN2022140647-appb-000063
Figure PCTCN2022140647-appb-000063
Figure PCTCN2022140647-appb-000064
Figure PCTCN2022140647-appb-000064
Figure PCTCN2022140647-appb-000065
Figure PCTCN2022140647-appb-000065
由表4可知，本发明的咔唑衍生物相较于对比例1使用的混合物主体材料，具有驱动电压低，电流效率较高等优势，而且在元件初始电流密度为50mA/cm 2的情况下，元件的LT90％寿命甚至提高数倍。 It can be seen from Table 4 that, compared with the mixture host material used in Comparative Example 1, the carbazole derivative of the present invention has the advantages of low driving voltage and high current efficiency, and when the initial current density of the element is 50mA/cm 2 , The LT90% lifetime of components is even increased several times.
表4中仅列举了CJHM515～CJHM877中部分化合物的性能，其他化合物性能与表中列举的化合物的结构基本一致，由于篇幅有限，不再一一列举。Table 4 only lists the properties of some compounds in CJHM515~CJHM877, and the properties of other compounds are basically consistent with the structures of the compounds listed in the table. Due to limited space, they are not listed one by one.
试验例2Test example 2
按照对比例1的方法制备红光元件，其中，将对比例1中化合物E替换为本发明的化合物CJHM517～CJHM847中的任一种或多种，制备有机电致发光元件，Red light elements were prepared according to the method of Comparative Example 1, wherein the compound E in Comparative Example 1 was replaced by any one or more of the compounds CJHM517 to CJHM847 of the present invention to prepare organic electroluminescent elements,
元件结构：
Figure PCTCN2022140647-appb-000066
中的任一种或多种
Figure PCTCN2022140647-appb-000067
Figure PCTCN2022140647-appb-000068
Component structure:
Figure PCTCN2022140647-appb-000066
any one or more of
Figure PCTCN2022140647-appb-000067
Figure PCTCN2022140647-appb-000068
所得元件的性能检测结果列于表5中，其中驱动电压(V)、电流效率(LE)、半峰宽(FWHM)是在元件的电流密度为10mA/cm 2条件下得出，且电压、LE、FWHM和LT90％相较对比元件进行了数据归一化处理。 The performance testing results of the obtained element are listed in Table 5, wherein the driving voltage (V), current efficiency (LE), and half-maximum width (FWHM) are obtained under the condition that the current density of the element is 10mA/cm 2 , and the voltage, LE, FWHM, and LT90% were normalized compared to the reference components.
表5红光元件数据Table 5 Red light component data
Figure PCTCN2022140647-appb-000069
Figure PCTCN2022140647-appb-000069
Figure PCTCN2022140647-appb-000070
Figure PCTCN2022140647-appb-000070
Figure PCTCN2022140647-appb-000071
Figure PCTCN2022140647-appb-000071
Figure PCTCN2022140647-appb-000072
Figure PCTCN2022140647-appb-000072
Figure PCTCN2022140647-appb-000073
Figure PCTCN2022140647-appb-000073
Figure PCTCN2022140647-appb-000074
Figure PCTCN2022140647-appb-000074
由表5的元件数据可以看出，本发明的咔唑衍生物相较于对比例1驱动电压明显降低，发光效率提高。在元件初始电流密度为50mA/cm 2的条件下，元件LT90％寿命具有明显的优势。 It can be seen from the device data in Table 5 that the driving voltage of the carbazole derivative of the present invention is significantly lower than that of Comparative Example 1, and the luminous efficiency is improved. Under the condition that the initial current density of the element is 50mA/cm 2 , the LT90% lifetime of the element has obvious advantages.
表5中仅列举了CJHM517～CJHM847中部分化合物的性能，其他化合物性能与表中列举的化合物的结构基本一致，由于篇幅有限，不再一一列举。Table 5 only lists the properties of some compounds in CJHM517~CJHM847, and the properties of other compounds are basically consistent with the structures of the compounds listed in the table. Due to limited space, they are not listed one by one.
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (10)

  1. 一种咔唑衍生物，其特征在于，其结构如式(I)所示：A kind of carbazole derivative, is characterized in that, its structure is as shown in formula (I):
    Figure PCTCN2022140647-appb-100001
    Figure PCTCN2022140647-appb-100001
    其中，W 1、W 2、W 3、W 4各自独立地表示CR 9，相邻的两个基团W 1和W 2、W 3和W 4代表下式(II)的基团，并且W 1和W 2或W 3和W 4至少有一者为式(II)基团； Wherein, W 1 , W 2 , W 3 , and W 4 each independently represent CR 9 , the adjacent two groups W 1 and W 2 , W 3 and W 4 represent groups of the following formula (II), and W At least one of 1 and W 2 or W 3 and W 4 is a group of formula (II);
    Figure PCTCN2022140647-appb-100002
    Figure PCTCN2022140647-appb-100002
    Z在每次出现时相同或不同地代表CR 0或N，并且“^”指示式(I)中相邻的基团W 1和W 2或W 3和W 4； Z represents CR 0 or N identically or differently at each occurrence, and "^" indicates adjacent groups W 1 and W 2 or W 3 and W 4 in formula (I);
    X代表CR 10或N； X stands for CR 10 or N;
    R 0、R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10相同或者不同，各自独立地选自由以下基团组成的群组：氢、氘、具有C 1～C 40的直链烷基、具有C 1～C 40的直链杂烷基、具有C 3～C 40的支链或环状的烷基、具有C 3～C 40的支链或环状的杂烷基、具有C 2～C 40的烯基或炔基、具有5～60个碳原子的芳基、具有5～60个碳原子的杂芳基，R 0～R 10中的两个或更多个相邻的取代基团可以任选地接合或稠合形成单环或多环的脂族、芳族或芳族环系、杂芳族或杂芳族环系； R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same or different, each independently selected from the group consisting of: hydrogen , deuterium, straight-chain alkyl with C 1 to C 40 , straight-chain heteroalkyl with C 1 to C 40 , branched or cyclic alkyl with C 3 to C 40 , C 3 to C 40 branched or cyclic heteroalkyl, alkenyl or alkynyl with C 2 to C 40 , aryl with 5 to 60 carbon atoms, heteroaryl with 5 to 60 carbon atoms, R 0 to Two or more adjacent substituent groups in R can optionally be joined or fused to form a monocyclic or polycyclic aliphatic, aromatic or aromatic ring system, heteroaromatic or heteroaromatic ring Tie;
    Ar 1选自由以下基团组成的群组：具有5～60个碳原子的芳基或具有5～60个碳原子的杂芳基。 Ar 1 is selected from the group consisting of aryl having 5-60 carbon atoms or heteroaryl having 5-60 carbon atoms.
  2. 根据权利要求1所述的咔唑衍生物，其特征在于，所述咔唑衍生物选自式(I)-1～式(I)-8中的一种或多种：The carbazole derivative according to claim 1, wherein the carbazole derivative is selected from one or more of formula (I)-1 to formula (I)-8:
    Figure PCTCN2022140647-appb-100003
    Figure PCTCN2022140647-appb-100003
    其中，R 0、R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10相同或者不同，各自独立地选 自由以下基团组成的群组：氢、氘、具有5～60个碳原子的芳基、具有5～60个碳原子的杂芳基，R 0～R 10中的两个或更多个相邻的取代基团可以任选地接合或稠合形成单环或多环的脂族、芳族或芳族环系、杂芳族或杂芳族环系； Wherein, R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different, each independently selected from the group consisting of the following groups : hydrogen, deuterium, an aryl group with 5 to 60 carbon atoms, a heteroaryl group with 5 to 60 carbon atoms, two or more adjacent substituent groups in R 0 to R 10 can be optionally are joined or fused to form monocyclic or polycyclic aliphatic, aromatic or aromatic ring systems, heteroaromatic or heteroaromatic ring systems;
    Ar 1选自由以下基团组成的群组：具有5～60个碳原子的芳基或具有5～60个碳原子的杂芳基。 Ar 1 is selected from the group consisting of aryl having 5-60 carbon atoms or heteroaryl having 5-60 carbon atoms.
  3. 根据权利要求1或2所述的咔唑衍生物，其特征在于，所述Ar 1表示为-(L) nAr 2基团，其中，L选自由单键、C 6-C 60的亚芳基、C 5-C 60的杂亚芳基组成的群组；n为0、1或2；Ar 2选自由以下II-1～II-17所示基团组成的群组： The carbazole derivative according to claim 1 or 2, wherein said Ar 1 is represented as -(L) n Ar 2 group, wherein, L is selected from single bond, C 6 -C 60 arylene A group consisting of C 5 -C 60 heteroarylene groups; n is 0, 1 or 2; Ar 2 is selected from the group consisting of the following groups shown in II-1 to II-17:
    Figure PCTCN2022140647-appb-100004
    Figure PCTCN2022140647-appb-100004
    其中，in,
    Z 1、Z 2各自独立地选自由氢、氘、卤素、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C 1～C 60烷基、C 2～C 60烯基、C 2～C 60炔基、C 1～C 60烷氧基、C 3～C 60环烷烃基、C 3～C 60环烯烃基、取代或未取代的C 6～C 60芳基、取代或未取代的C 6～C 60芳氧基、取代或未取代的C 6～C 60芳硫醚基、或者取代或未取代的C 2～C 60杂环芳基组成的群组； Z 1 and Z 2 are each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid group or sulfonate thereof , phosphate group or its phosphate salt, C 1 ~C 60 alkyl group, C 2 ~C 60 alkenyl group, C 2 ~C 60 alkynyl group, C 1 ~C 60 alkoxy group, C 3 ~C 60 cycloalkane group, C 3 ~C 60 cycloalkene group, substituted or unsubstituted C 6 ~C 60 aryl group, substituted or unsubstituted C 6 ~C 60 aryloxy group, substituted or unsubstituted C 6 ~C 60 arylsulfide group , or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aromatic groups;
    x1表示1-4的整数；x2表示1-3的整数；x3表示1或2；x4表示1-6的整数；x5表示1-5的整数；x1 represents an integer of 1-4; x2 represents an integer of 1-3; x3 represents an integer of 1 or 2; x4 represents an integer of 1-6; x5 represents an integer of 1-5;
    T 1表示O、S、CR’R”或NAr’； T 1 means O, S, CR'R" or NAr';
    R’、R”各自独立地选自由氢、氘、C 1～C 60的烷基、C 1～C 60的杂烷基、取代或未取代的C 6～C 60芳基、取代或未取代的C 6～C 60芳胺基、或者取代或未取代的C 2～C 60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基； R' and R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
    Ar’选自由C 1～C 60的烷基、C 1～C 60的杂烷基、C 3～C 60的环烷基、取代或未取代的C 6～C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6～C 60芳胺基、或者取代或未取代的C 2～C 60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基、联苯基或萘基； Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused-ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
    Figure PCTCN2022140647-appb-100005
    表示取代基与L的连接键。
    Figure PCTCN2022140647-appb-100005
    Indicates the link between the substituent and L.
  4. 根据权利要求1-3任一项所述的咔唑衍生物，其特征在于，R 0、R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10各自独立地选自氢或氘。 The carbazole derivative according to any one of claims 1-3, characterized in that, R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen or deuterium.
  5. 根据权利要求1-4任一项所述的咔唑衍生物，其特征在于，所述咔唑衍生物选自以下CJHM515～CJHM877所示的结构中的一种或多种：The carbazole derivative according to any one of claims 1-4, characterized in that, the carbazole derivative is selected from one or more of the following structures shown in CJHM515 to CJHM877:
    Figure PCTCN2022140647-appb-100006
    Figure PCTCN2022140647-appb-100006
    Figure PCTCN2022140647-appb-100007
    Figure PCTCN2022140647-appb-100007
    Figure PCTCN2022140647-appb-100008
    Figure PCTCN2022140647-appb-100008
    Figure PCTCN2022140647-appb-100009
    Figure PCTCN2022140647-appb-100009
    Figure PCTCN2022140647-appb-100010
    Figure PCTCN2022140647-appb-100010
    Figure PCTCN2022140647-appb-100011
    Figure PCTCN2022140647-appb-100011
    Figure PCTCN2022140647-appb-100012
    Figure PCTCN2022140647-appb-100012
    Figure PCTCN2022140647-appb-100013
    Figure PCTCN2022140647-appb-100013
    Figure PCTCN2022140647-appb-100014
    Figure PCTCN2022140647-appb-100014
    Figure PCTCN2022140647-appb-100015
    Figure PCTCN2022140647-appb-100015
    Figure PCTCN2022140647-appb-100016
    Figure PCTCN2022140647-appb-100016
    Figure PCTCN2022140647-appb-100017
    Figure PCTCN2022140647-appb-100017
    Figure PCTCN2022140647-appb-100018
    Figure PCTCN2022140647-appb-100018
    Figure PCTCN2022140647-appb-100019
    Figure PCTCN2022140647-appb-100019
    Figure PCTCN2022140647-appb-100020
    Figure PCTCN2022140647-appb-100020
    其中，*—T 2—*选自*—O—*、*—S—*或下述结构中的一种： Wherein, *—T 2 —* is selected from *—O—*, *—S—* or one of the following structures:
    Figure PCTCN2022140647-appb-100021
    Figure PCTCN2022140647-appb-100021
    *—和—*表示连接键。*— and —* indicate connecting keys.
  6. 权利要求1-5任一项所述的咔唑衍生物在有机电致发光元件中的应用。The application of the carbazole derivative described in any one of claims 1-5 in organic electroluminescent elements.
  7. 根据权利要求6所述的应用，其特征在于，所述咔唑衍生物在有机电致发光元件中 用作发光层材料、空穴输送层材料、空穴阻挡层材料或封装层材料。The application according to claim 6, characterized in that, the carbazole derivative is used as a light-emitting layer material, a hole transport layer material, a hole blocking layer material or an encapsulation layer material in an organic electroluminescence element.
  8. 一种有机电致发光元件，其特征在于，包括：第一电极、第二电极和位于所述第一电极和所述第二电极之间的至少一层有机层，所述有机层中至少一层包括权利要求1-5任一项所述的咔唑衍生物。An organic electroluminescent element, characterized in that it comprises: a first electrode, a second electrode, and at least one organic layer located between the first electrode and the second electrode, at least one of the organic layers The layer comprises the carbazole derivative according to any one of claims 1-5.
  9. 一种显示装置，其特征在于，包括权利要求8所述的有机电致发光元件。A display device, characterized by comprising the organic electroluminescence element according to claim 8.
  10. 一种照明装置，其特征在于，包括权利要求8所述的有机电致发光元件。A lighting device, characterized by comprising the organic electroluminescent element as claimed in claim 8.
PCT/CN2022/140647 2022-02-28 2022-12-21 Carbazole derivative and use thereof WO2023160187A1 (en)

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