WO2022199464A1 - 咔唑衍生物及其应用，有机电致发光元件、显示装置和照明装置 - Google Patents

咔唑衍生物及其应用，有机电致发光元件、显示装置和照明装置 Download PDF

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WO2022199464A1
WO2022199464A1 PCT/CN2022/081590 CN2022081590W WO2022199464A1 WO 2022199464 A1 WO2022199464 A1 WO 2022199464A1 CN 2022081590 W CN2022081590 W CN 2022081590W WO 2022199464 A1 WO2022199464 A1 WO 2022199464A1
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aromatic
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substituted
heteroaromatic ring
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曹建华
戴雄
唐怡杰
侯斌
王学涛
白爽
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北京八亿时空液晶科技股份有限公司
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention belongs to the technical field of materials for organic electroluminescence elements, and particularly relates to a carbazole derivative and its application, as well as an organic electroluminescence element, a display device and a lighting device containing the carbazole derivative.
  • Organic electroluminescence is mainly divided into fluorescence and phosphorescence, but according to the theory of spin quantum statistics, the probability of singlet excitons and triplet excitons is 1:3, that is, the theory of fluorescence from white singlet exciton radiation transitions The limit is 25%, and the theoretical limit for fluorescence of triplet exciton radiative transitions is 75%. How to utilize the energy of 75% triplet excitons becomes a top priority. In 1997, Forrest et al. found that the phenomenon of phosphorescent electroluminescence broke through the limit of 25% quantum efficiency of organic electroluminescent materials, which aroused extensive attention to metal complex phosphorescent materials. Since then, people have carried out a lot of research on phosphorescent materials.
  • the present invention provides a novel carbazole derivative.
  • the carbazole derivative of the present invention as a raw material for materials for organic electroluminescence elements, can provide reduced startup voltage and high luminous efficiency.
  • a carbazole derivative the structural formula of the carbazole derivative is shown in formula (I):
  • any two adjacent groups W 1 , W 2 , W 3 , W 4 represent groups of the following formula (II),
  • Z represents, identically or differently, CR or N at each occurrence, and ⁇ indicates the corresponding adjacent groups W and W, W and W , or W and W in formula I ;
  • T 1 represents a single bond, O, S, NAr 2 or CR 10 R 11 ;
  • R 1 to R 11 are the same or different, and are selected from hydrogen, deuterium, straight chain alkyl with C 1 to C 40 , straight chain heteroalkyl with C 1 to C 40 , branched chain with C 3 to C 40 or Cyclic alkyl, branched or cyclic heteroalkyl with C3 - C40 , alkenyl or alkynyl with C2 - C40 , aromatic ring system or heteroalkyl with 5-60 carbon atoms
  • An aromatic ring system in which each of R 1 to R 11 may be substituted with one or more groups R, and in which two or more adjacent substituted groups may be optionally joined or fused to form monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring systems;
  • Ar 1 and Ar 2 are the same or different, and are selected from linear alkyl groups with C 1 to C 40 , linear heteroalkyl groups with C 1 to C 40 , branched or cyclic alkanes with C 3 to C 40 group, branched or cyclic heteroalkyl group with C3 - C40 , alkenyl or alkynyl group with C2 - C40 , aromatic ring system or heteroaromatic ring system with 5-60 carbon atoms , the ring system may be substituted by one or more groups R;
  • Ar 3 is the same or different at each occurrence and is selected from aromatic or heteroaromatic ring systems having 5 to 30 carbon atoms, which may be substituted by one or more non-aromatic groups R 13 ; this The two groups Ar 3 bound to the same nitrogen or phosphorus atom can also be bridged to each other by a single bond or a bridging group selected from N(R 13 ), C(R 13 ) 2 , oxygen or sulfur;
  • R 13 is selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, aliphatic hydrocarbon group with C 1 -C 20 , aromatic ring or heteroaromatic ring system with 5-30 carbon atoms, wherein one of R 13 or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms or nitrile groups, wherein two or more adjacent substituents R 13 may form with each other a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring Tie.
  • An aromatic or heteroaromatic ring system in the sense of the present invention is intended to be taken to mean a system which does not necessarily have to contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups can also consist of non-aromatic units For example C, N, O or S atoms are attached.
  • aryl or heteroaryl groups can also consist of non-aromatic units For example C, N, O or S atoms are attached.
  • two or more aryl groups are linked by, for example, short alkyl groups, such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine
  • Systems of diaryl ethers and the like are also taken to mean aromatic ring systems in the sense of the present invention.
  • Aryl in the sense of the present invention contains 5 to 60 carbon atoms
  • heteroaryl in the sense of the present invention contains 5 to 60 carbon atoms and at least one heteroatom, provided 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 here is taken to mean simple aromatic rings, i.e., benzene, naphthalene, etc., or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc., or fused aryl or heteroaryl groups bases, such as anthracene, phenanthrene, quinoline, isoquinoline, etc.
  • Aromatic rings connected to each other by single bonds, such as biphenyls, are on the contrary not referred to as aryl or heteroaryl groups, but as aromatic ring systems.
  • aliphatic hydrocarbon radicals or alkyl radicals or alkenyl radicals or alkynyl radicals which contain from 1 to 40 carbon atoms in the sense of the present invention and in which individual hydrogen atoms or -CH 2 - radicals can also be substituted by the aforementioned radicals are preferably considered to be Refers to the following groups: 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, hep
  • the alkoxy group preferably has 1 to 40 carbon atoms and is considered to be methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy base, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-heptyloxy Octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.
  • Heteroalkyl groups preferably have 1 to 40 carbon atoms, and refer to groups in which individual hydrogen atoms or -CH 2 - groups may be substituted by oxygen, sulfur, halogen atoms, and are considered to refer to alkoxy, Alkylthio, fluoroalkoxy, fluoroalkylthio, especially methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy Oxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio group, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroe
  • cycloalkyl, cycloalkenyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl , cycloheptenyl, wherein one or more -CH 2 - groups may be replaced by the above-mentioned groups; in addition, one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms or nitrile groups.
  • aromatic or heteroaromatic ring atoms according to the invention which in each case may also be substituted by the aforementioned radicals R 13 , are in particular radicals derived from benzene, Naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, benzene, terphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, trimerindene, heterotrimerindene, spirotrimerindene, spiroheterotrimerindene, furan, benzofuran, is
  • R 1 to R 8 are the same or different, and are selected from hydrogen or deuterium, wherein each group may be substituted by one or more groups R;
  • R 9 to R 11 are the same or different, and are selected from hydrogen, deuterium, straight-chain alkyl groups with C 1 to C 40 , aromatic ring systems or heteroaromatic ring systems with 5 to 60 carbon atoms
  • One of, or R 10 and R 11 are optionally joined or fused to form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system;
  • Ar 1 and Ar 2 are selected from an aromatic ring system or a heteroaromatic ring system having 5-60 carbon atoms, and the ring system may be substituted by one or more groups R.
  • carbazole derivatives mainly include the following CJHL017 ⁇ CJHL238:
  • carbazole derivatives are materials for organic electroluminescence elements, materials for organic field effect transistors or materials for organic thin film solar cells.
  • An organic electroluminescence element comprising a first electrode, a second electrode and a multilayer organic layer between the first electrode and the second electrode, at least one of the organic layers comprises 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 contain other 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. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that each of these layers does not have to be present.
  • the organic electroluminescent device described herein may comprise one light-emitting layer, or it may comprise multiple light-emitting layers.
  • various light-emitting compounds capable of emitting light are used in the light-emitting layer.
  • Particular preference is given to systems having three emitting layers, wherein the three layers can exhibit blue, green and red emission. If more than one light-emitting layer is present, according to the present invention, at least one of these layers comprises the carbazole derivative of the present invention.
  • organic electroluminescent elements in which one or more layers are applied by means of a sublimation method, in which the layer or layers are applied by vapor deposition in a vacuum sublimation device at an initial pressure of less than 10 ⁇ 5 Pa, preferably less than 10 ⁇ 6 Pa The material is applied.
  • the initial pressure may also be even lower, eg 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 from solution, for example by spin coating, or by means of any desired printing method such as screen printing, flexographic printing, lithographic printing, photoinduced thermography, thermal transfer printing, spraying Ink printing or nozzle printing to create one or more layers.
  • Soluble compounds for example, can be obtained by appropriately substituting the compounds represented by the formula (I) of the present invention. 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 vapour deposition.
  • the organic layer further includes one or more selected from the group consisting of 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-emitting light-emitting element or a bottom-emitting light-emitting element.
  • the structure and preparation method of the organic electroluminescence element of the present invention are not limited.
  • the organic electroluminescent element prepared by using the compound of the present invention can reduce the start-up voltage and improve the luminous efficiency and brightness.
  • a display device comprising the organic electroluminescence element.
  • a lighting device comprising the organic electroluminescence element.
  • the material for organic elements of the present invention contains the carbazole derivative of the present invention.
  • the material for organic elements may be constituted 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 element of the present invention can be used as a host material.
  • the material for organic electroluminescence elements of the present invention may contain other compounds as dopant materials.
  • the material for an organic electroluminescent element of the present invention can also be used as a material for a hole transport layer, enhancement layer, light emitting layer, electron transport layer, charge generation layer, electron blocking layer, encapsulation layer or photorefractive layer.
  • the beneficial effects of the present invention are as follows: the carbazole derivatives described in the present invention have higher triplet energy level and high glass transition temperature, are suitable for use as materials for organic electroluminescence elements, and contain
  • the carbazole derivative-based material for an organic electroluminescent element has the characteristics of low startup voltage, high luminous efficiency and high brightness.
  • the carbazole derivatives of the present invention have good thermal stability and film-forming properties, are used in materials for organic electroluminescence elements, organic electroluminescence elements, display devices, and lighting devices, and can prolong the service life, thereby enabling Reduce the manufacturing cost of materials for organic electroluminescence elements, organic electroluminescence elements, display devices, and lighting devices.
  • FIG. 1 is a schematic diagram of a bottom emission example of the organic electroluminescence device of the present invention.
  • FIG. 2 is a schematic diagram of a top emission example of the organic electroluminescent device of the present invention.
  • test instruments and methods for performance testing of OLED materials and components in the following examples are as follows:
  • Luminance and chromaticity coordinates tested with a spectral scanner PhotoResearch PR-715;
  • Life Test Use LTS-1004AC Life Test Device.
  • the preparation method of intermediate A comprises the steps:
  • the preparation method of intermediate B comprises the steps:
  • reaction was stirred at room temperature for 30 minutes, 50.0 mmol of intermediate Int-6 was added, the reaction was stirred at room temperature for 1 hour, heated to reflux for 5 hours, cooled to room temperature, concentrated to dryness under reduced pressure, added with 200 mL of toluene and 60.0 mmol of anhydrous magnesium chloride, The mixture was heated and refluxed for 30 minutes, cooled to room temperature, filtered, and the filtrate was concentrated to dryness under reduced pressure, and was separated and purified with a silica gel column to obtain the intermediate Int-7 with a yield of 90-95%.
  • the following compound A is used as a green light host material
  • the following compound B is used as a green light doping material
  • compound C is used as a hole injection material
  • 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 doping material
  • compound G as electron transporting doping material
  • LiQ electron transporting host material
  • the green light element was fabricated by successively using an EL vapor deposition machine manufactured by DOV Corporation to vapor-deposit on ITO glass, and an organic electroluminescent element as a green light was fabricated.
  • the red light element was fabricated by successively using an EL vapor deposition machine manufactured by DOV Company to vapor-deposit on the ITO glass, and an organic electroluminescence element as a red light was fabricated.
  • Compound A was replaced with compounds CJHL017-CJHL238 of the present invention, and green light organic electroluminescence elements were prepared according to the method of Comparative Example 1.
  • the performance test results of the obtained green light organic electroluminescent element are listed in Table 1, where the driving voltage (V), current efficiency (LE), color coordinate (CIE), and half-peak width (FWHM) are measured when the current density of the element is 10 mA/cm 2 and data normalized for voltage, LE, FWHM and LT90% compared to the reference element.
  • the green light element prepared from the organic material of the present invention has lower driving voltage, higher current efficiency, and better color purity than the element prepared in Comparative Example 1, and the luminous brightness of the element is initially 2000cd/cm 2 . Under the initial conditions, the lifetime of the device using the compound of the present invention as the green host material is greatly improved.
  • a red light element was prepared according to the method of Comparative Example 1, wherein the aforementioned compound E was replaced with the compounds CJHL017-CJHL238 of the present invention, except that,
  • the element prepared from the organic material of the present invention has significantly lower driving voltage, higher current efficiency and better luminous color purity than that of the red light element prepared in Comparative Example 1.
  • the LT90% lifetime of the element using the compound of the present invention as the red light host material is 1.1 to 2.7 times that of the comparative element.
  • 1 and 2 are respectively a schematic diagram of a bottom emission example of the organic electroluminescence device of the present invention and a schematic diagram of a top emission example of the organic electroluminescence device, the carbazole derivatives prepared by the present invention are contained in in the light-emitting layer 5.

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Abstract

本发明涉及一系列咔唑衍生物及其应用，以及含有该咔唑衍生物的有机电致发光元件、显示装置和照明装置。所述咔唑衍生物的结构式如式(I)所示，本发明所述的咔唑衍生物具有较高的稳定性和三重态能级，适宜作为有机电致发光元件用材料使用，含有所述的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。

Description

咔唑衍生物及其应用，有机电致发光元件、显示装置和照明装置 技术领域
本发明属于有机电致发光元件用材料技术领域，具体涉及一种咔唑衍生物及其应用，以及含有该咔唑衍生物的有机电致发光元件、显示装置和照明装置。
背景技术
最近几年有机电致发光显示技术己趋于成熟，一些产品已进入市场，但在产业化时程中，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还达不到实用化要求，这大大限制了OLED技术的发展。
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，即来白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。
鉴于以上原因，特提出本发明。
发明内容
为了解决现有技术存在的以上问题，本发明提供了一种新型的咔唑衍生物，本发明的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。
为了实现上述目的，本发明采用如下技术方案：
一种咔唑衍生物，所述咔唑衍生物的结构式如式(I)所示：
Figure PCTCN2022081590-appb-000001
其中，任意两个相邻的基团W 1、W 2、W 3、W 4代表下式(II)的基团，
Figure PCTCN2022081590-appb-000002
其中，Z在每次出现时相同或不同地代表CR 9或N，并且^指示式I中的相应的相邻基团W 1和W 2、W 2和W 3或W 3和W 4；
T 1表示单键、O、S、NAr 2或CR 10R 11；
R 1～R 11相同或者不同，选自氢、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个碳原子的芳香族环系或杂芳族环系中的一种，R 1～R 11中的每个基团可被一个或多个基团R取代，且其中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、芳族或杂芳族环系；
Ar 1、Ar 2相同或者不同，选自具有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个碳原子的芳香族环系或杂芳族环系，所述环系可被一个或多个基团R取代；
所述R每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、硝基、N(Ar 3) 2、N(R 12) 2、C(＝O)Ar 3、C(＝O)R 12、P(＝O)(Ar 3) 2、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5～80个碳原子的芳族环或杂芳族环系、具有5～60个碳原子的芳氧基或杂芳氧基中的一种，R基团中的每个基团可被一个或多个基团R 12取代，或这些体系的组合，其中一个或多个非相邻的-CH 2-基团可被R 12C＝CR 12、C≡C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝NR 12、P(＝O)(R 12)、SO、SO 2、NR 12、O、S或CONR 12代替，并且其中一个或多个氢原子或被氘原子、卤素原子、腈基或硝基代替，其中两个或更多个相邻的取代基R可以任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系，所述环系可被一个或多个基团R 12取代；
R 12每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、硝基、N(Ar 3) 2、N(R 13) 2、C(＝O)Ar 3、C(＝O)R 13、P(＝O)(Ar 3) 2、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个碳原子的芳族环或杂芳族环系、具有5～60个碳原子的芳氧基或杂芳氧基中的一种，R 12中的每个基团可被一个或多个基团R 13取代，或这些体系的组合，其中一个或多个非相邻的-CH 2-基团可被R 13C＝CR 13、C≡C、Si(R 13) 2、Ge(R 13) 2、Sn(R 13) 2、C＝O、C＝S、C＝Se、C＝NR 13、P(＝O)(R 13)、SO、SO 2、NR 13、O、S或CONR 13代替，并且其中一个或多个氢原子可被氘原子、卤素原子、腈基或硝基代替，其中两个或更多个相邻的取代基R 12可以任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系，所述环系可被一个或多个基团R 13取代；
Ar 3在每次出现时相同或不同，选自具有5～30个碳原子的芳族或杂芳族环系，所述环系可被一个或多个非芳族基团R 13取代；此处键合至同一氮原子或磷原子的两个基团Ar 3也可通过单键或选自N(R 13)、C(R 13) 2、氧或硫的桥连基彼此桥连；
R 13选自氢原子、氘原子、氟原子、腈基、具有C 1～C 20的脂族烃基、具有5～30个碳原子的芳族环或杂芳族环系，其中R 13中一个或多个氢原子可被氘原子、卤素原子或腈基代替，其中两个或更多个相邻的取代基R 13可彼此形成单环或多环的脂族、芳族或杂芳族环系。
在本发明意义上的芳族或杂芳族环系旨在被认为是指不必仅含有芳基或杂芳基的体系，而是其中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。因此，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、二芳基醚等的体系也被认为是指在本发明意义上的芳族环系。
本发明意义上的芳基含有5～60个碳原子，在本发明意义上的杂芳基含有5～60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被认为是指简单的芳族环，即苯、萘等，或简单的杂芳族环，如吡啶、嘧啶、噻吩等，或稠合的芳基或杂芳基，如蒽、菲、喹啉、异喹啉等。通过单键彼此连接的芳族环，例如联苯，相反地不被称为芳基或杂芳基，而是称为芳族环系。
对于本发明意义上的含有1～40个碳原子并且其中单独的氢原子或-CH 2-基团还可被上述基团取代的脂族烃基或者烷基或者烯基或炔基优选被认为是指如下基团：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、新戊基、环戊基、正己基、新己基、环己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、环己烯基、庚烯基、环庚烯基、辛烯基、环辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基、庚炔基或辛炔基。烷氧基优选具有1～40个碳原子的烷氧基被认为是指甲氧基、三氟甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、仲戊氧基、2-甲基丁氧基、正己氧基、环己氧基、正庚氧基、环庚氧基、正辛氧基、环辛氧基、2-乙基己氧基、五氟乙氧基和2,2,2-三氟乙氧基。杂烷基优选具有1～40个碳原子的烷基，是指其中单独的氢原子或-CH 2-基 团可被氧、硫、卤素原子取代的基团，被认为是指烷氧基、烷硫基、氟代的烷氧基、氟代的烷硫基，特别是指甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、甲硫基、乙硫基、正丙硫基、异丙硫基、正丁硫基、异丁硫基、仲丁硫基、叔丁硫基、三氟甲硫基、三氟甲氧基、五氟乙氧基、五氟乙硫基、2,2,2-三氟乙氧基、2,2,2-三氟乙硫基、乙烯氧基、乙烯硫基、丙烯氧基、丙烯硫基、丁烯硫基、丁烯氧基、戊烯氧基、戊烯硫基、环戊烯氧基、环戊烯硫基、己烯氧基、己烯硫基、环己烯氧基、环己烯硫基、乙炔氧基、乙炔硫基、丙炔氧基、丙炔硫基、丁炔氧基、丁炔硫基、戊炔氧基、戊炔硫基、己炔氧基、己炔硫基。
一般来说，根据本发明的环烷基、环烯基可为环丙基、环丁基、环戊基、环己基、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。
根据本发明的芳族或杂芳族环原子，在每种情况下还可被上述基团R 13取代的芳族或杂芳族环系，特别是指衍生自如下物质的基团：苯、萘、蒽、苯并蒽、菲、芘、
Figure PCTCN2022081590-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-***、1,2,4- ***、苯并***、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。
进一步的，所述R 1～R 8相同或者不同，选自氢或氘，其中每个基团可被一个或多个基团R取代；
进一步的，所述R 9～R 11相同或者不同，选自氢、氘、具有C 1～C 40的直链烷基、具有5～60个碳原子的芳香族环系或杂芳族环系中的一种，或者R 10和R 11任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系；
进一步的，所述Ar 1、Ar 2选自具有5～60个碳原子的芳香族环系或杂芳族环系，所述环系可被一个或多个基团R取代。
进一步的，所述咔唑衍生物主要包括如下CJHL017～CJHL238所示：
Figure PCTCN2022081590-appb-000004
Figure PCTCN2022081590-appb-000005
Figure PCTCN2022081590-appb-000006
Figure PCTCN2022081590-appb-000007
Figure PCTCN2022081590-appb-000008
Figure PCTCN2022081590-appb-000009
Figure PCTCN2022081590-appb-000010
Figure PCTCN2022081590-appb-000011
Figure PCTCN2022081590-appb-000012
Figure PCTCN2022081590-appb-000013
Figure PCTCN2022081590-appb-000014
Figure PCTCN2022081590-appb-000015
Figure PCTCN2022081590-appb-000016
一种所述的咔唑衍生物在有机元件用材料中的应用。
进一步的，所述咔唑衍生物为有机电致发光元件用材料、有机场效应晶体管用材料或有机薄膜太阳能电池用材料。
进一步的，所述咔唑衍生物在发光层材料、空穴输送/空穴阻挡层材料或封装层材料中的应用。
一种有机电致发光元件，包括第一电极、第二电极和位于第一电极和第二电极之间的多层有机层，所述有机层中的至少一层包含所述的咔唑衍生物。
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。
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。
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。
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气喷印方法，其中所述材料通过喷嘴直接施加，并且因此是结构化的。
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本发明式(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。
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。
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。
一种显示装置，包括所述的有机电致发光元件。
一种照明装置，包括所述的有机电致发光元件。
本发明的有机元件用材料含有本发明的咔唑衍生物。有机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。
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。
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。
与现有技术相比，本发明的有益效果为：本发明所述的咔唑衍生物具有较高的三重态能级、高的玻璃化温度，适宜作为有机电致发光元件用材料使用，含有所述的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、照明装置的制造成本。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明的有机电致发光装置的一个底部发光例子的示意图；
图2是本发明的有机电致发光装置的一个顶部发光例子的示意图。
附图标记
1-基板、2-阳极、3-空穴注入层、4-空穴传输/电子阻挡层、5-发光层、6-空穴阻挡/电子传输层、7-电子注入层、8-阴极。
具体实施方式
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。
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：
OLED元件性能检测条件：
亮度和色度坐标：使用光谱扫描仪PhotoResearch PR-715测试；
电流密度和起亮电压：使用数字源表Keithley 2420测试；
功率效率：使用NEWPORT 1931-C测试；
寿命测试：使用LTS-1004AC寿命测试装置。
实施例1
中间体A的制备方法，包括如下步骤：
第一步：化合物Int-1的制备
Figure PCTCN2022081590-appb-000017
0.10mol的1-甲基咔唑、0.15mol的吡啶和200mL的二氯甲烷，于5℃以下滴加入0.12mol的三氟乙酸酐，搅拌反应2小时，加入100mL的1N稀盐酸水溶液，分出有机相，用水洗，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，收率96％。
第二步：化合物Int-2的制备
Figure PCTCN2022081590-appb-000018
0.10mol第一步制备的中间体Int-1分散在200mL的四氯化碳中，加入0.11mol的NBS和5mg的偶氮二异丁腈，升温回流搅拌反应5小时，冷却到室温，过滤，滤液用饱和的亚硫酸氢钠水溶液洗，有机相干燥，减压浓缩干，再用硅胶柱分离纯化，得到淡黄色中间体Int-2，收率92％。
第三步：化合物Int-3的制备
Figure PCTCN2022081590-appb-000019
56.0mmol第二步制备的中间体Int-2溶解在100mL的亚磷酸三乙酯中，升温回流搅拌反应3小时，冷却到室温，减压浓缩干，用硅胶柱分离纯化，得到中间体Int-3，收率86％。
第四步：化合物Int-4的制备
Figure PCTCN2022081590-appb-000020
50.0mmol中间体Int-3溶解于150mL干燥的THF中，在氮气保护下，降温至-25℃，分批加入55.0mmol的氢化钠，搅拌反应10分钟，再滴加入55.0mmol的酮溶于THF的溶液，升至室温搅拌反应5小时，滴加入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，得到中间体Int-4，收率90～96％。
第五步：中间体Int-5的制备
Figure PCTCN2022081590-appb-000021
20.0mmol第四步制备的中间体Int-4溶解于120mL的1,2-二氯乙烷中，加入4.0mmol的无水三氯化铁，升温至50℃搅拌反应12小时，冷却到室温，加入20mL的1N稀盐酸水溶液，分出有机相，用水洗，有机相干燥，过滤，滤液浓缩干，用硅胶柱分离纯化，得到中间体Int-5，收率90％。
第六步：中间体A的制备
Figure PCTCN2022081590-appb-000022
50.0mmol第五步制备的中间体Int-5溶解于80mL的DMF中，加入20mL的水和4g(0.1mol)的氢氧化钠，升温回流搅拌反应2小时，冷却到室温，加入100mL的2N稀盐酸水溶液，过滤，滤饼用水洗、乙醇洗，再用甲苯-THF重结晶，得到中间体A，收率98％。
以上述类似的合成方法，制备以下化合物：
Figure PCTCN2022081590-appb-000023
Figure PCTCN2022081590-appb-000024
实施例2
中间体B的制备方法，包括如下步骤：
第一步：化合物Int-6的制备
Figure PCTCN2022081590-appb-000025
0.12mol的咔唑-4-硼酸频那醇酯、0.10mol的1-卤代酮溶解于160mL的THF和80mL的水中，在氮气保护下，加入0.40mol的无水碳酸钠和1.2g的Pd(PPh 3) 4催化剂，升温回流搅拌反应15小时，冷却到室温，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-6，收率82～90％。
第二步：化合物Int-7的制备
Figure PCTCN2022081590-appb-000026
55.0mmol的甲氧基甲基三苯基氯化膦溶解于150mL干燥的THF中，在氮气保护下，降温至-25℃，分批加入60.0mmol的叔丁醇钾，搅拌反应10分钟，升至室温搅拌反应30分钟，加入50.0mmol的中间体Int-6，于室温搅拌反应1小时，升温回流反应5小时，冷却到室温，减压浓缩干，加入200mL甲苯和60.0mmol的无水氯化镁，升温回流30分钟，冷却到室温，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到中间体Int-7，收率90～95％。
第三步：化合物B的制备
Figure PCTCN2022081590-appb-000027
40.0mmol的中间体Int-7溶解于150mL的二氯甲烷中，在氮气保护下，冰水浴降温至0℃，加入80.0mmol的三氟甲基磺酸，搅拌反应2小时，加入 150mL的饱和碳酸钠水溶液，升温回流30分钟，冷却到室温，过滤，滤饼用水洗、乙醇洗，用硅胶柱分离纯化，得到中间体B。
以上述类似的合成方法，制备以下化合物：
Figure PCTCN2022081590-appb-000028
Figure PCTCN2022081590-appb-000029
Figure PCTCN2022081590-appb-000030
实施例3
化合物CJHL192的制备：
Figure PCTCN2022081590-appb-000031
10.0mmol中间体B13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11.0mmol的65％氢化钠固体，搅拌反应1小时，加入11.0mmol的2-氯-4,6-二苯基-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CJHL192，白色固体，收率74％。
化合物CJHL192的MS和 1HNMR测试结果如下：
MS(MALDI-TOF)：m/z 589.2046[M+H] +； 1HNMR(δ、CDCl 3)：9.06(s,1H)；8.68～8.66(d,1H)；8.35～8.28(m,5H)；8.08(s,1H)；7.93～7.90(m,2H)；7.73～7.71(d,1H)；7.63～7.57(m,3H)；7.45～7.35(m,9H)；7.18～7.16(m,1H)。
以上述类似的合成方法，制备以下化合物：
Figure PCTCN2022081590-appb-000032
Figure PCTCN2022081590-appb-000033
Figure PCTCN2022081590-appb-000034
实施例4
化合物CJHL103的制备：
Figure PCTCN2022081590-appb-000035
15.0mmol中间体A4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(CAS:864377-31-1)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CJHL103，黄色固体，收率78％。
化合物CJHL103的MS和 1HNMR测试结果如下：
MS(MALDI-TOF)：m/z 740.2830[M+H] +； 1HNMR(δ、CDCl 3)：8.90～8.88(d,1H)；8.81～8.78(m,4H)；8.50～8.48(d,1H)；8.32～8.29(m,1H)；8.21(s,1H)；8.18～8.16(d,1H)；8.03(s,1H)；7.93～7.90(m,3H)；7.55～7.50(m,4H)；7.48～7.40(m,4H)；7.36～7.25(m,5H)；7.22～7.17(m,5H)；7.05～6.99(m,2H)。
以上述类似的合成方法，制备以下化合物：
Figure PCTCN2022081590-appb-000036
Figure PCTCN2022081590-appb-000037
有机电致发光元件的制备
对比例1
将下述的化合物A作为绿光主体材料，使用下述的化合物B作为绿光掺杂材料，化合物C作为孔穴注入材料，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。
Figure PCTCN2022081590-appb-000038
将化合物
Figure PCTCN2022081590-appb-000039
Figure PCTCN2022081590-appb-000040
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。
将化学式
Figure PCTCN2022081590-appb-000041
Figure PCTCN2022081590-appb-000042
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。
试验例1
将化合物A替换为本发明的化合物CJHL017～CJHL238，按照对比例1的方法制备绿光有机电致发光元件。
所得绿光有机电致发光元件的性能检测结果列于表1中，其中驱动电压(V)、电流效率(LE)、色坐标(CIE)、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％相较参比元件进行了数据 归一化处理。
表1绿光元件性能检测结果
Figure PCTCN2022081590-appb-000043
由表1可知，本发明的有机材料制备成的绿光元件相较于对比例1制备的元件，驱动电压低，电流效率较高，色纯度好，而且在元件发光亮度初始为2000cd/cm 2为初始的条件下，使用本发明的化合物作为绿光主体材料的元件寿命有很大提高。
表1中仅列举了部分的CJHL017～CJHL238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。
按照对比例1的方法制备红光元件，其中，将前述的化合物E替换为本发明的化合物CJHL017～CJHL238，除此之外，
Figure PCTCN2022081590-appb-000044
Figure PCTCN2022081590-appb-000045
Figure PCTCN2022081590-appb-000046
所得元件的性能检测结果列于表2中，其中驱动电压(V)、电流效率(LE)、色坐标(CIE)、半峰宽(FWHM)是在元件的电流密度为10mA/cm2条件下得出，且电压、LE、FWHM和LT90％相较参比元件进行了数据归一化处理。
表2红光元件性能检测结果
Figure PCTCN2022081590-appb-000047
Figure PCTCN2022081590-appb-000048
由表2的红光元件性能测试结果可知，本发明的有机材料制备成的元件相较于对比例1制备的红光元件驱动电压明显降低，电流效率高，发光色纯度好。在元件初始亮度为2000cd/cm 2为初始的条件下，使用本发明的化合物作为红光主体材料的元件LT90％寿命是对比元件1.1倍至2.7倍。
表2中仅列举了部分的CJHL017～CJHL238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。
如图1和图2所示，分别为本发明的有机电致发光装置的一个底部发光例子的示意图和有机电致发光装置的一个顶部发光例子的示意图，本发明制备的咔唑衍生物包含在发光层5中。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (10)

  1. 一种咔唑衍生物，其特征在于，所述咔唑衍生物的结构如式(I)所示：
    Figure PCTCN2022081590-appb-100001
    其中，任意两个相邻的基团W 1、W 2、W 3、W 4代表下式(II)的基团，
    Figure PCTCN2022081590-appb-100002
    其中，Z在每次出现时相同或不同地代表CR 9或N，并且^指示式I中的相应的相邻基团W 1和W 2、W 2和W 3或W 3和W 4；
    T 1表示单键、O、S、NAr 2或CR 10R 11；
    R 1～R 11相同或者不同，选自氢、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个碳原子的芳香族环系或杂芳族环系中的一种，R 1～R 11中的每个基团可被一个或多个基团R取代，且其中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、芳族或杂芳族环系；
    Ar 1、Ar 2相同或者不同，选自具有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个碳原子的芳香族环系或杂芳族环系，所述环系可被一个或多个基团R取代；
    所述R每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、硝基、N(Ar 3) 2、N(R 12) 2、C(＝O)Ar 3、C(＝O)R 12、P(＝O)(Ar 3) 2、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5～80个碳原子的芳族环或杂芳族环系、具有5～60个碳原子的芳氧基或杂芳氧基中的一种，R基团中的每个基团可被一个或多个基团R 12取代，或这些体系的组合，其中一个或多个非相邻的-CH 2-基团可被R 12C＝CR 12、C≡C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝NR 12、P(＝O)(R 12)、SO、SO 2、NR 12、O、S或CONR 12代替，并且其中一个或多个氢原子或被氘原子、卤素原子、腈基或硝基代替，其中两个或更多个相邻的取代基R可以任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系，所述环系可被一个或多个基团R 12取代；
    R 12每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、硝基、N(Ar 3) 2、N(R 13) 2、C(＝O)Ar 3、C(＝O)R 13、P(＝O)(Ar 3) 2、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个碳原子的芳族环或杂芳族环系、具有5～60个碳原子的芳氧基或杂芳氧基中的一种，R 12中的每个基团可被一个或多个基团R 13取代，或这些体系的组合，其中一个或多个非相邻的-CH 2-基团可被R 13C＝CR 13、C≡C、Si(R 13) 2、Ge(R 13) 2、Sn(R 13) 2、C＝O、C＝S、C＝Se、C＝NR 13、P(＝O)(R 13)、SO、SO 2、NR 13、O、S或CONR 13代替，并且其中一个或多个氢原子可被氘原子、卤素原子、腈基或硝基代替，其中两个或更多个相邻的取代基R 12可以任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系，所述环系可被一个或多个基团R 13取代；
    Ar 3在每次出现时相同或不同，选自具有5～30个碳原子的芳族或杂芳族环系，所述环系可被一个或多个非芳族基团R 13取代；此处键合至同一氮原子或磷原子的两个基团Ar 3也可通过单键或选自N(R 13)、C(R 13) 2、氧或硫的桥连基彼此桥连；
    R 13选自氢原子、氘原子、氟原子、腈基、具有C 1～C 20的脂族烃基、具有5～30个碳原子的芳族环或杂芳族环系，其中R 13中一个或多个氢原子可被氘原子、卤素原子、或腈基代替，其中两个或更多个相邻的取代基R 13可彼此形成单环或多环的脂族、芳族或杂芳族环系。
  2. 根据权利要求1所述的咔唑衍生物，其特征在于，所述R 1～R 11相同或者不同，选自氢、氘、具有C 1～C 40的直链烷基、具有5～60个碳原子的芳香族环系或杂芳族环系中的一种，所述R 1～R 11中的每个基团可被一个或多个基团R取代，且其中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、芳族或杂芳族环系；
    所述Ar 1、Ar 2选自具有5～60个碳原子的芳香族环系或杂芳族环系，所述环系可被一个或多个基团R取代。
  3. 根据权利要求1或2所述的咔唑衍生物，其特征在于，所述咔唑衍生物包括以下CJHL017～CJHL238所示的结构：
    Figure PCTCN2022081590-appb-100003
    Figure PCTCN2022081590-appb-100004
    Figure PCTCN2022081590-appb-100005
    Figure PCTCN2022081590-appb-100006
    Figure PCTCN2022081590-appb-100007
    Figure PCTCN2022081590-appb-100008
    Figure PCTCN2022081590-appb-100009
    Figure PCTCN2022081590-appb-100010
    Figure PCTCN2022081590-appb-100011
    Figure PCTCN2022081590-appb-100012
    Figure PCTCN2022081590-appb-100013
    Figure PCTCN2022081590-appb-100014
    Figure PCTCN2022081590-appb-100015
  4. 根据权利要求1所述的咔唑衍生物，其特征在于，所述R 1～R 8相同或者不同，选自氢或氘，其中每个基团可被一个或多个基团R取代；
    R 9～R 11相同或者不同，选自氢、氘、具有C 1～C 40的直链烷基、具有5～60个碳原子的芳香族环系或杂芳族环系中的一种，或者R 10和R 11任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系；
    所述Ar 1、Ar 2选自具有5～60个碳原子的芳香族环系或杂芳族环系，所述环系可被一个或多个基团R取代。
  5. 一种权利要求1～4任意一项所述的咔唑衍生物在有机元件用材料中的应用。
  6. 根据权利要求5所述的应用，其特征在于，所述的咔唑衍生物为有机电致发光元件用材料、有机场效应晶体管用材料或有机薄膜太阳能电池用材料。
  7. 根据权利要求6所述的应用，其特征在于，所述的咔唑衍生物在发光层材料、空穴输送/空穴阻挡层材料或封装层材料中的应用。
  8. 一种有机电致发光元件，其特征在于，包括第一电极、第二电极和位于第一电极和第二电极之间的多层有机层，所述有机层中的至少一层包含权利要求1～4任意一项所述的咔唑衍生物。
  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。
  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。
PCT/CN2022/081590 2021-03-23 2022-03-18 咔唑衍生物及其应用，有机电致发光元件、显示装置和照明装置 WO2022199464A1 (zh)

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