WO2022242521A1 - 一种稠合氮杂环化合物及其应用以及包含该化合物的有机电致发光器件 - Google Patents

一种稠合氮杂环化合物及其应用以及包含该化合物的有机电致发光器件 Download PDF

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WO2022242521A1
WO2022242521A1 PCT/CN2022/092188 CN2022092188W WO2022242521A1 WO 2022242521 A1 WO2022242521 A1 WO 2022242521A1 CN 2022092188 W CN2022092188 W CN 2022092188W WO 2022242521 A1 WO2022242521 A1 WO 2022242521A1
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朱运会
王彦杰
张其胜
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Zhejiang Hongwu Technology Co Ltd
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the invention relates to the technical field of organic electroluminescence, in particular to a novel organic compound and its application, and an organic electroluminescent device containing the compound.
  • OLED Organic Light Emitting Devices
  • OLED Organic Light Emitting Devices
  • OLED Organic Light Emitting Devices
  • the holes generated by the anode and the electrons generated by the cathode will move, inject into the hole transport layer and the electron transport layer respectively, and migrate to the light-emitting layer.
  • a Energy excitons which excite light-emitting molecules and eventually produce visible light.
  • OLED has the characteristics of self-illumination, wide viewing angle, wide color gamut, short response time, high luminous efficiency, low operating voltage, low cost, and simple production process. It can be made into large-size and/or flexible ultra-thin panels, which is a development
  • the new display technology with high speed and high process integration has been widely used in display products such as TVs, smart phones, tablet computers, vehicle displays, lighting, etc., and will be further applied in creative display products such as large-size displays and flexible screens .
  • Organic optoelectronic materials applied to OLED devices can be divided into light-emitting layer materials and auxiliary functional layer materials in terms of use.
  • the light-emitting material layer materials include guest materials (also called light-emitting materials, doping materials) and host materials (also called According to different luminescent mechanisms, luminescent materials are divided into fluorescent materials, phosphorescent materials and thermally activated delayed fluorescent materials, and auxiliary functional layer materials are divided into electron injection materials and electron transport materials according to the different properties of electron or hole transport speeds. , Hole blocking materials, electron blocking materials, hole transport materials, hole injection materials.
  • the most studied and most important is the improvement of the performance of the light-emitting devices of the three primary colors of red, green, and blue.
  • the light-emitting dopant used in the light-emitting layer has a decisive impact on the color, efficiency, stability and other properties of the electroluminescent device.
  • light-emitting dopant materials with high efficiency and narrow emission are still in short supply.
  • the current blue light-emitting doped materials have problems such as low efficiency, short lifespan and insufficient color purity, such as patent (CN200310124405.8, application date December 24, 2003) and literature (ACS Appl.Mater.Interfaces 2018, 10,30022-30028) in the pyrene compound, the pyrene molecule has a planar rigid ⁇ -conjugated structure, which is easy to achieve high luminous efficiency, and is a blue light-emitting dopant structure with excellent performance.
  • its molecular structure is prone to intermolecular aggregation, resulting in reduced efficiency and lifetime; on the other hand, its emission spectrum presents a strong shoulder emission, resulting in a wide half-width of the spectrum and low color purity.
  • the present invention provides a novel fused nitrogen heterocyclic organic compound, which is composed of formula (1) and formula (2):
  • Z 1 to Z 14 are independently represented as CR 1 to CR 14 or N; in formula (2), when the L bond is connected to Z 1 to Z 14 , then Z 1 to Z 14 are represented as C ;
  • the substituent group represented by formula (2) when the substituent group represented by formula (2) is substituted by formula (1), it is only substituted at Z 1 , Z 2 , Z 5 , Z 6 , Z 8 , Z 9 , Z 12 or Z 13 ;
  • L is independently selected from single bonds, substituted or unsubstituted linear or branched alkylene groups with 1 to 20 carbon atoms, substituted or unsubstituted ring-forming carbon atoms with 3 to 20 Cycloalkylene, substituted or unsubstituted arylene with 6 to 30 ring carbon atoms, substituted or unsubstituted heteroarylene with 2 to 30 ring carbon atoms, substituted or unsubstituted Subfused aryl rings with 10 to 50 ring carbon atoms, substituted or unsubstituted subfused heterocyclic rings with 6 to 50 ring atoms;
  • L is independently selected from the substituted or unsubstituted following groups, but not limited to the following groups:
  • R 1 to R 14 substituent groups are independently selected from hydrogen atom, deuterium atom, halogen atom, cyano group, nitro group, substituted silicon group, substituted or unsubstituted carbon atoms with 1 to 50 Alkyl, substituted or unsubstituted alkenyl with 1 to 20 carbons, substituted or unsubstituted alkynyl with 1 to 20 carbons, substituted or unsubstituted alkoxy with 1 to 50 carbons, substituted or unsubstituted Substituted fluoroalkyl with 1 to 20 carbons, substituted or unsubstituted fluoroalkoxy with 1 to 20 carbons, substituted or unsubstituted cycloalkyl with 3 to 50 ring carbon atoms, substituted or An unsubstituted aryl group with 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group with 5 to 50 ring atoms;
  • the substituent groups R 15 to R 16 are independently selected from substituted or unsubstituted alkyl groups with 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 50 ring carbon atoms , a substituted or unsubstituted aryl group with 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group with 5 to 50 ring atoms;
  • the substituent groups R 1 to R 16 can bond with each other to form a substituted or unsubstituted saturated or unsaturated ring, and can also form a substituted or unsubstituted saturated or unsaturated ring with an adjacent aromatic ring or heteroaryl ring. the fused ring;
  • R 1 to R 16 substituent groups are independently selected from any one or more of the following groups:
  • substituted in “substituted or unsubstituted” in the above compounds means that the substituents are independently selected from deuterium atoms, tritium atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, monovalent alkyl groups with 1 to 10 carbon atoms Or a cycloalkyl group, a monovalent monocyclic aryl group or a fused ring aryl group with 6 to 30 carbon atoms, a monovalent heterocyclic group or a condensed ring heteroaryl group with a carbon number of 2 to 50;
  • the "substituted" group in “substituted or unsubstituted” is independently any one or more selected from the following groups:
  • formula (1) and formula (2) protected by the present invention can preferably select the following specific structural compounds Compound 1 ⁇ Chem 216, and these compounds are only representative:
  • the second object of the present invention is to provide an organic electroluminescent device.
  • the organic electroluminescent device comprises an anode, a cathode and at least one layer of organic thin film between the anode and the cathode, and the organic thin film contains one or more organic electroluminescence compounds composed of formula (1) and formula (2).
  • Luminescent compound Luminescent compound.
  • the organic layer includes a light-emitting layer and a functional layer, and the compound formed by the combination of formula (1) and formula (2) can be used alone or in combination as a hole injection layer, a hole transport layer or a light-emitting material.
  • the third object of the present invention is to provide an organic electroluminescent device.
  • an organic electroluminescent device with high color purity and low driving voltage, high efficiency and long life is obtained by optimizing the structure of the device.
  • the fused nitrogen heterocyclic compound protected by the present invention is a kind of amino-substituted bis-indolophenazine compound.
  • This kind of material has a planar conjugated rigid structure, can inhibit the twisting of the structural unit in the excited state, and has a narrow emission spectrum, and has high luminous efficiency; the combination of the arylamine unit of formula (2) and the structure of formula (1) can adjust the energy level and band gap of the molecule to obtain fluorescence of a suitable wavelength, and at the same time, the steric hindrance of the arylamine unit, It is beneficial to inhibit the aggregation between material molecules and significantly improve the device performance.
  • Fig. 1 is a schematic diagram of the structure of an organic electroluminescent device applied by the compound of the present invention, wherein, the meanings of each layer structure of the device are as follows:
  • Transparent substrate layer 2. ITO anode layer, 3. Hole injection layer, 4. Hole transport layer A, 5. Hole transport layer B (or electron blocking layer), 6. Light emitting layer, 7. Electron transport Layer B (or hole blocking layer), 8, electron transport layer A, 9, electron injection layer, 10, cathode reflective electrode layer.
  • Figure 2 is the fluorescence spectrum of Comparative Compound-1 in toluene solution at room temperature [25°C, 300K].
  • Figure 3 is the fluorescence spectrum of Comparative Compound-2 in toluene solution at room temperature [25°C, 300K].
  • Figure 4 shows the fluorescence spectrum of CH66 in toluene solution at room temperature [25°C, 300K].
  • the reaction was stopped, cooled to room temperature, extracted three times with ethyl acetate/water, dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated on a silica gel column to obtain 5.48 g of the target product with a yield of 89%.
  • the organic electroluminescence device described in the solution of the present invention comprises an anode layer, a cathode layer and at least one organic layer between the anode and the cathode.
  • the organic layer is a film layer formed by laminating multiple layers of organic compounds.
  • the organic layer may also contain inorganic compounds.
  • At least one of the organic layers of the organic electroluminescent device described in the solution of the present invention is a light-emitting layer.
  • the organic layer may also include other functional layers, for example, there may be one or more hole injection layers, hole transport layers, or electron blocking layers between the anode layer and the light-emitting layer, and between the two light-emitting layers It is also feasible to have an exciton blocking layer or an intermediate layer with similar functions, and one or more hole blocking layers, electron transport layers, or electron injection layers exist between the light emitting layer and the cathode layer. It should be noted that these functional layers do not necessarily exist.
  • the organic electroluminescent device of the present invention can be a fluorescent or phosphorescent device, or a fluorescent and phosphorescent hybrid device; it can be a single light-emitting device, or a series device with a plurality of light-emitting units; in addition, it can be It is a single-color light-emitting device, or a mixed-color device, or a white light-emitting device.
  • the light emitting layer may contain multiple guest materials and multiple host materials.
  • the guest material may be a fluorescent material, a phosphorescent material and/or a thermally activated delayed fluorescent material.
  • the host material refers to the host material that occupies most of the components in the light-emitting layer.
  • the host material that is doped and combined with fluorescent materials is called “fluorescent host”, and the host material that is doped and combined with phosphorescent materials is called “phosphorescent host”. ". It should be noted that the selection of the host material does not depend on its molecular structure, but on the basis of the host material as the guest material.
  • the compounds of the invention according to the above embodiments can be used in different organic layers. Preference is given to organic electroluminescent devices in which the compounds according to the invention are used as hole-injection material, hole-transport material or emitting material of the emitting layer.
  • the use of the compounds according to the invention according to the above embodiments is likewise suitable for use in organic electronic devices.
  • the compounds according to the invention are used as light-emitting materials for the light-emitting layer in organic electroluminescent devices.
  • Device Examples 1-8 Manufacture of an organic electroluminescent device used as a blue light-emitting material for the light-emitting layer
  • ITO indium tin oxide
  • anode an indium tin oxide transparent electrode
  • UV ultraviolet-ozone cleaning
  • the film thickness of ITO was 130 nm.
  • HIL hole injection layer
  • a hole transport layer A (HTL) was vapor-deposited on the hole injection layer to have a film thickness of 60 nm.
  • an electron blocking layer (EBL) was vapor-deposited on the hole transport layer A to have a film thickness of 5 nm.
  • a light-emitting layer (EML) was co-deposited on the electron blocking layer with a film thickness of 20 nm.
  • the light-emitting layer (EML) adopts multi-source co-evaporation to evaporate the light-emitting material BD and the host material BH of the light-emitting layer, wherein the doping concentration of the light-emitting material is 2% by weight.
  • HBL hole blocking layer
  • ETL electron transport material
  • Liq 8-hydroxyquinolate lithium
  • Example 1 The structure of the organic electroluminescent device in Example 1 is shown in Figure 1, and Figure 1 also shows the stacking sequence and function of each functional layer.
  • the molecular structures of the materials used in OLEDs are shown in Table 1.
  • the device structure of the device embodiment 1 is specifically: ITO (130)/HATCN (15)/HTL (60)/EBL (5)/BH:2 (20, weight 2%)/HBL (5)/ETL: Liq(30, 50% by weight)/Liq(1)/Al(100), it should be noted that the numbers in parentheses represent the film thickness (unit: nm).
  • Device Example 2-Device Example 8 The difference between Device Example 2-Device Example 8 and Device Example 1 is that the Compound 2 of the present invention used in the light-emitting layer is replaced by other compounds of the present invention, see Table 2 for details.
  • Comparative Examples 1-2 differ in that the luminescent material in the organic electroluminescent device is changed to Comparative Compound-1-Comparative Compound-2, and the device performance test data obtained are shown in Table 2.
  • the OLEDs were characterized by standard methods. For this purpose, the electroluminescence spectrum, current efficiency (measured in cd/A), power efficiency (measured in lm/W) and external quantum efficiency (EQE, measured in %) were determined as a function of luminous density from the Calculation of current/voltage/luminous density characteristic lines (IUL characteristic lines) of primary emission characteristics. Determine the required voltage V10 at a current density of 10 mA/ cm2 .
  • EQE represents the external quantum efficiency at a current density of 10mA/ cm2
  • T95 represents the working time of the device when the brightness of the device is reduced to 95% at a current density of 10mA/ cm2
  • CIE coordinates are the device at 10mA/ cm2 CIE1931 chromaticity coordinates (x, y) calculated from electroluminescence spectrum at current density.
  • the EQE efficiency and T95 of the device of Compound 1 are 6.8% and 82h, respectively, which is mainly due to the reduction in efficiency and aging of the device due to the aggregation of luminescent molecules (ACS Appl.Mater.Interfaces 2018,10,30022 -30028).
  • the EQE efficiency and T95 lifetime of the device are lower, only 3.6% and 46h, respectively.
  • the performance of its electroluminescent device is significantly improved, especially the efficiency and lifespan.
  • the EQE efficiency of the device embodiment 2 made by applying CH39 can reach 8.9%.
  • the T95 life of the device embodiment 4 made by applying the chemical 94 can reach 129 hours, which is 57% higher than that of the device embodiment 1 and 180% higher than that of the device embodiment 2.
  • Comparative compound 1, comparative compound 2 and CH66 were measured using a spectrofluorophotometer manufactured by Hitachi High-Tech Co., Ltd., a fluorescence spectrometry device, and the test samples were dissolved in a solvent (toluene) (1*10 -5 [mol/L of the concentration] ]), at room temperature (300 [K]), add 360nm excitation light to the sample added in the quartz colorimetric cell, test the fluorescence spectrum, you can get its luminescence peak and half-peak width, as shown in Table 3. Then, the luminescence quantum efficiency (PLQY) of the sample was measured using an absolute PL quantum yield measuring device manufactured by Hamamatsu Photonics.
  • PLQY luminescence quantum efficiency
  • the fluorescence spectrum of the toluene solution of comparative compound-1 is as shown in Figure 2, and its fluorescence peak is 463nm, and luminous efficiency (PLQY) can reach 87%; There are many long-wavelength components, which leads to the color coordinate CIEy of its electroluminescent device as high as 0.15, and the color purity of blue light is not high.
  • the fluorescence spectrum of the toluene solution of comparative compound-2 is shown in Figure 3, and the half-peak width of the fluorescence spectrum is 37nm, which is still relatively broad. However, its fluorescence peak is 428nm, so that the color coordinate CIEy of its electroluminescent device can be as low as 0.04, and the color purity of blue light is high. However, its luminous efficiency (PLQY) is only 56%, resulting in significantly low efficiency and lifetime of the electroluminescent device.
  • the fluorescence spectrum of the toluene solution of 66 of the present invention is shown in Figure 4, the fluorescence peak of its fluorescence spectrum is 457nm, half-maximum width is 21nm, very narrow blue light emission. Therefore, the color coordinate CIEy of its electroluminescent device is as low as 0.07, and the color purity of blue light is high. At the same time, its luminous efficiency (PLQY) is as high as 91%, so that the efficiency and service life of its electroluminescent device are obviously improved.
  • the compound 66 of the present invention has a PLQY and emission wavelength similar to that of the comparative compound 1 of the prior art, but its half-peak width is significantly reduced. At the same time, compared with comparative compound 2, after the molecules of the present invention are connected with aniline units, in addition to the red shift of the luminescence wavelength, the half-peak width is significantly reduced and the luminous efficiency is significantly improved.

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Abstract

本发明公开了一种稠合氮杂环化合物及其应用以及包含该化合物的有机电致发光器件，所述稠合氮杂环化合物具有式(1)和式(2)组合结构，其中Z 1～Z 14各自独立地表示为CR 1～CR 14或者N；环A～环D上Z 1～Z 14各自独立地表示为N时，环A～环D上N的数量之和≤4；且单独的环A～环D上N的数量≤1；式(2)所代表的取代基团在式(1)取代时，只在Z 1、Z 2、Z 5、Z 6、Z 8、Z 9、Z 12或者Z 13位置进行取代。本发明提供的化合物可作为有机电致发光器件的发光材料使用，此类材料具有高发光效率、窄发射光谱的特点，提高了器件的发光色纯度、发光效率和寿命。

Description

一种稠合氮杂环化合物及其应用以及包含该化合物的有机电致发光器件 技术领域
本发明涉及有机电致发光技术领域，特别涉及一种新型有机化合物及其应用，以及包含该化合物的有机电致发光器件。
背景技术
有机电致发光器件(OLED：Organic Light Emitting Devices)，是一种类似三明治结构的电流驱动式薄膜器件，在阳极和阴极之间夹杂单层或者多层有机功能材料层。OLED在电场的作用下，阳极产生的空穴和阴极产生的电子就会发生移动，分别向空穴传输层和电子传输层注入，迁移到发光层，当二者在发光层相遇复合时，产生能量激子，从而激发发光分子最终产生可见光。OLED具有自发光、视角广、色域广、响应时间短、发光效率高、工作电压低、成本低廉、生产工艺简单等特点，可以制作成大尺寸和/或柔性超薄面板，是一种发展迅速、工艺集成度较高的新型显示技术，目前已经广泛应用于电视、智能手机、平板电脑、车载显示、照明等显示产品中，还将进一步应用在大尺寸显示、柔性屏等创意显示产品中。
应用于OLED器件的有机光电材料在用途上可以分为发光层材料和辅助功能层材料，其中，发光材层材料中包括客体材料(又称为发光材料、掺杂材料)和主体材料(又称为基质材料)，发光材料根据不同的发光机理，分成荧光材料、磷光材料和热活化延迟荧光材料，辅助功能层材料按照电子或者空穴传输速度不同的性质，又分成电子注入材料、电子传输材料、空穴阻挡材料、电子阻挡材料、空穴传输材料、空穴注入材料。
在各种颜色的有机电致发光元件中，研究最多、最重要的就是红色、绿色、蓝色三原色的发光器件的性能的提升。发光层里使用的发光掺杂剂对其电致发光器件的颜色、效率、稳定性等性能具有决定性的影响。然而，目前具有高效率、窄发射的发光掺杂剂材料依然非常紧缺。目前的蓝色发光掺杂材料存在着效率偏低、寿命短及色纯度不够等问题，如专利(CN200310124405.8，申请日2003年12月24日)和文献(ACS Appl.Mater.Interfaces 2018,10,30022-30028)中的芘化合物，芘分子具有平面刚性的π共轭结构，容易实现高的发光效率，是性能优异的蓝色发光掺杂剂结构。然而，其分子结构一方面容易发生分子间聚集作用，导致效率和寿命降低；另一方面，其发射光谱呈现出很强的肩峰发射，导致光谱的半峰宽较宽，色纯度不高。
因此，本领域亟需开发一类OLED功能材料，具有高发光效率和窄发射光谱，此类材料 在有机电致发光器件中应用时，具有低驱动电压、高效率、长寿命、高色纯度等优点。
发明内容
为解决上述技术问题，本发明提供了一种新型稠合氮杂环有机化合物，化合物由式(1)和式(2)结构组合构成：
Figure PCTCN2022092188-appb-000001
其中，
式(1)中，Z 1～Z 14各自独立地表示为CR 1～CR 14或者N；式(2)中的L键连至Z 1～Z 14时，则Z 1～Z 14表示为C；
环A～环D上Z 1～Z 14各自独立地表示为N时，环A～环D上N的数量之和≤4；且单独的环A～环D上N的数量≤1；
优选地，式(1)的结构如下表示：
Figure PCTCN2022092188-appb-000002
Figure PCTCN2022092188-appb-000003
式(2)所代表的取代基团在式(1)取代时的数量≤4；且单独的环A～环D上式(2)的取代数量≤1；
优选地，式(2)所代表的取代基团在式(1)取代时，只在Z 1、Z 2、Z 5、Z 6、Z 8、Z 9、Z 12或者Z 13位置进行取代；
式(2)中，L独立地选自单键，取代或未取代的碳原子数为1～20的直链或者支链亚烷基、取代或未取代的成环碳原子数为3～20的亚环烷基、取代或未取代的成环碳原子数为6～30的亚芳基、取代或未取代的成环碳原子数为2～30的亚杂芳基、取代或未取代的成环碳原子数10～50的亚稠合芳基环、取代或未取代的成环原子数6～50的亚稠合杂环；
优选地，L独立地选自取代或未取代的下述基团，但不限于以下基团：
亚苯基、亚萘基、亚芴基、亚茚基、亚吲哚基、亚苯并呋喃基、亚苯并噻吩基；
式(1)中，R 1～R 14取代基团独立地选自氢原子、氘原子、卤素原子、氰基、硝基、取代的硅基、取代或未取代的碳原子数1～50的烷基、取代或未取代的碳数1～20的烯基、取代或未取代的碳数1～20的炔基、取代或未取代的碳原子数1～50的烷氧基、取代或未取代的碳数1～20的氟代烷基、取代或未取代的碳数1～20的氟代烷氧基、取代或未取代的成环碳原子数3～50的环烷基、取代或未取代的成环碳原子数6～50的芳基、或者取代或未取代的成环原 子数5～50的1价杂环基；
式(2)中，R 15～R 16取代基团独立地选自取代或未取代的碳原子数1～50的烷基、取代或未取代的成环碳原子数3～50的环烷基、取代或未取代的成环碳原子数6～50的芳基、或者取代或未取代的成环原子数5～50的1价杂环基；
R 1～R 16取代基团之间彼此可以键合形成取代或未取代的饱和的或者未饱和的环，也可与相邻芳环或杂芳环形成取代或未取代的饱和的或者未饱和的稠合环；
优选地，R 1～R 16取代基团分别独立地选自以下基团中的任意一种或几种：
取代或未取代的甲基、取代或未取代的乙基、取代或未取代的正丙基、取代或未取代的异丙基、取代或未取代的正丁基、取代或未取代的异丁基、取代或未取代的仲丁基、取代或未取代的叔丁基、取代或未取代的2-甲基丁基、取代或未取代的正戊基、取代或未取代的仲戊基、取代或未取代的三氟甲基、取代或未取代的五氟乙基、取代或未取代的2,2,2-三氟乙基、取代或未取代的乙烯基、取代或未取代的丙烯基、取代或未取代的正丁烯基、取代或未取代的异丁烯基、取代或未取代的正戊烯基、取代或未取代的异戊烯基、取代或未取代的新戊烯基、取代或未取代的乙炔基、取代或未取代的丙炔基、取代或未取代的正丁炔基、取代或未取代的异丁炔基、取代或未取代的正戊炔基、取代或未取代的异戊炔基、取代或未取代的新戊炔基、取代或未取代的环丙基、取代或未取代的环丁基、取代或未取代的环戊基、取代或未取代的环己基、取代或未取代的金刚烷基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的联苯基、取代或未取代的萘基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的茚基、取代或未取代的芴基、取代或未取代的螺二芴基、取代或未取代的茚并芴基、取代或未取代的荧蒽基、取代或未取代的芘基、取代或未取代的苝基、取代或未取代的
Figure PCTCN2022092188-appb-000004
基、取代或未取代的并四苯基、取代或未取代的苯并噻咯基、取代或未取代的苯并噻吩基、取代或未取代的苯并呋喃基、取代或未取代的二苯并噻咯基、取代或未取代的二苯并噻吩基、取代或未取代的二苯并呋喃基、取代或未取代的二苯并硒吩基、取代或未取代的咔唑基、取代或未取代的吲哚并[3,2,1-jk]咔唑基；
上述化合物中“取代或未取代”中的“取代”是指取代基独立地选自氘原子、氚原子、卤素原子、氰基、硝基、羟基、碳原子数1～10的1价烷基或者环烷基、碳原子数6～30的1价单环芳基或者稠环芳基、碳原子数2～50的1价杂环基或者稠环杂芳基；
优选地，“取代或未取代”中的“取代”基团独立地为选自以下基团中的任意一种或几种：
氘原子、氚原子、卤素原子、氰基、硝基、羟基、甲基、甲氧基、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、环己基、金刚烷基、2-乙基己基、三氟甲基、五氟乙基、2,2,2-三氟乙基、苯基、氘代苯基、氟代苯基、甲基苯基、正丙基苯基、 叔丁基苯基、三甲基苯基、三苯基苯基、四苯基苯基、氰基苯基、吡啶基、萘基、蒽基、联苯基、二联苯基、三联苯基、芴基、螺二芴基、呋喃基、苯并呋喃基、二苯并呋喃基、氮杂二苯并呋喃基、噻吩基、苯并噻吩基、二苯并噻吩基、氮杂二苯并噻吩基、咔唑基、苯基咔唑基、氮杂咔唑基；
进一步地，本发明所保护的式(1)和式(2)可以优选出以下具体结构化合物化1～化216，这些化合物仅为代表性的：
Figure PCTCN2022092188-appb-000005
Figure PCTCN2022092188-appb-000006
Figure PCTCN2022092188-appb-000007
Figure PCTCN2022092188-appb-000008
Figure PCTCN2022092188-appb-000009
Figure PCTCN2022092188-appb-000010
Figure PCTCN2022092188-appb-000011
Figure PCTCN2022092188-appb-000012
Figure PCTCN2022092188-appb-000013
Figure PCTCN2022092188-appb-000014
Figure PCTCN2022092188-appb-000015
本发明的目的之二，是提供一种有机电致发光器件。有机电致发光器件包括阳极、阴极以及位于所述阳极和阴极之间的至少一层的有机薄膜，有机薄膜中含有式(1)和式(2)组合构成的一种或者多种有机电致发光化合物。所述有机层包括发光层和功能层，式(1)和式(2)组合构成的化合物可以作为空穴注入层、空穴传输层或者发光材料单独或者共同使用。
本发明的目的之三，是提供一种有机电致发光器件。式(1)和式(2)组合构成的化合物在器件中应用时，通过对器件结构的优化，获得一种低驱动电压、高效率、长寿命的具有高色纯度有机电致发光器件。
本发明的有益效果：
本发明所保护的稠合氮杂环化合物是一类胺基取代的双吲哚并吩嗪化合物，此类材料具有平面共轭的刚性结构，能够抑制结构单元在激发态的扭转，具有窄发射光谱，且具有高发光效率；将式(2)的芳胺单元与式(1)结构相结合能够调节分子的能级及带隙得到合适波长的荧光，同时芳胺单元的空间位阻作用，有利于抑制材料分子之间的聚集作用，显著提高器件性能。
附图说明
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本发明化合物应用的有机电致发光器件结构示意图，其中，器件各层结构代表含义如下：
1、透明基板层，2、ITO阳极层，3、空穴注入层，4、空穴传输层A，5、空穴传输层B(或者电子阻挡层)，6、发光层，7、电子传输层B(或者空穴阻挡层)，8、电子传输层A，9、电子注入层，10、阴极反射电极层。
图2为比较化合物-1在甲苯溶液、室温时[25℃，300K]的荧光光谱。
图3为比较化合物-2在甲苯溶液、室温时[25℃，300K]的荧光光谱。
图4为化66在甲苯溶液、室温时[25℃，300K]的荧光光谱。
具体实施方式
下面将以多个合成实施例为例来进一步说明本发明的原理和特征，所举的实施例只用于解释本发明，但并非用于限定本发明的范围。
以下所列举的式(1)的具体化合物的合成方法，除非另有说明，都在保护性气体气氛下在无水溶剂中进行。
Figure PCTCN2022092188-appb-000016
中间体1的合成
称量5.0g(20mmol)的2-碘硝基苯、4.83g(21mmol)的5-溴-2-甲氧基苯基硼酸、0.66g(0.6mmol)的四三苯基膦钯、5.52g(40mmol)的碳酸钾于烧瓶中，加入40ml甲苯、10ml乙醇和15ml水，氮气鼓泡除氧10分钟。加热至90℃，回流搅拌12h。停止反应，冷至室温，乙酸乙酯/水萃取三次，无水硫酸钠干燥，旋蒸浓缩，硅胶柱分离得到目标产物5.48g，收率89％，质谱测得m/z＝308.2。
中间体2的合成
称量5.48g(17.8mmol)的中间体1和10.27g(39.2mmol)的三苯基膦加入烧瓶中，再加入20ml二氯苯。抽换气，氮气保护，180℃加热回流反应14h。停止反应，减压蒸馏除去二氯苯。硅胶柱分离，得到目标产物4.18g，产率85％，质谱测得分子量m/z＝276.2。
中间体3的合成
称量2.76g(10.0mmol)的中间体2、0.11g(0.5mmol)的醋酸钯、0.23g(0.5mmol)的2-二环己基磷-2',6'-二异丙氧基-1,1'-联苯和1.92g(20mmol)的叔丁醇钠于烧瓶中，再加入30ml甲苯。抽换气，氮气保护，120℃回流反应48h。停止反应，冷至室温，二氯甲烷/水萃取，旋蒸除去甲苯。用乙酸乙酯多次重结晶，过滤得到目标产物0.51g，产率26％，质谱测得分子量m/z＝390.5。
中间体4的合成
称量0.78g(2.0mmol)的中间体3溶于40ml无水二氯甲烷中，氮气保护。温度降至-60℃，滴加三溴化硼0.77ml(8.0mmol)，自然回至室温反应过夜。将反应液缓慢倒入冰水中，加入碳酸氢钠中和。旋蒸除去二氯甲烷，过滤得到粗产物，乙醇洗三次。烘干得到目标产物0.54g，产率75％，质谱测得分子量m/z＝362.2。
中间体5的合成
称量0.72g(2.0mmol)的中间体4溶于40ml无水二氯甲烷中，加入0.8g(8.0mmol)的三乙胺和1.13g(4mmol)三氟甲磺酸酐。氮气保护下，室温搅拌过夜。将反应液倒入水中，碳酸钠中和，二氯甲烷萃取。旋蒸，乙酸乙酯重结晶。过滤得到目标产物1.01g，产率81％，质谱测得分子量m/z＝626.1。
合成实施例1：化2的合成
Figure PCTCN2022092188-appb-000017
称量0.63g(1.0mmol)的中间体5、0.51g(3.0mmol)的二苯胺、0.046g(0.05mmol)的三(二亚苄基丙酮)二钯、0.046g(0.20mmol)的三叔丁基四氟硼酸盐和0.29g(3.0mmol)的叔丁醇钠加入10ml的甲苯中。抽换气，氮气保护，120℃回流反应过夜。冷至室温，二氯甲烷/水萃取，无水硫酸钠干燥，旋蒸浓缩。硅胶柱分离得到目标产物化2 0.52g,产率79％， 质谱测得分子量m/z＝664.3。
合成实施例2：化39的合成
Figure PCTCN2022092188-appb-000018
将化2合成中的二苯胺替代为N-(4-叔丁基苯基)-二苯并呋喃-4-胺，相同的反应条件可以得到目标产物化39，产率72％，质谱测得分子量m/z＝956.5。
Figure PCTCN2022092188-appb-000019
中间体6的合成
称量11.4g(50mmol)的2-溴-4-叔丁基苯胺溶于50ml醋酸中，加入5ml浓盐酸，室温搅拌10分钟。降到0℃，缓慢加入亚硝酸钠3.8g(55mmol),低温搅拌0.5h。然后将溶于浓盐酸的22.5g(100mmol)SnCl 2.2H 2O滴加入反应体系中。滴加完毕后，缓慢回到室温搅拌2h。停止反应，过滤，水洗，烘干得到粗产物11.3g，直接下一步反应。
中间体7的合成
称量11.3g(40.5mmol)的中间体6、4.76g(48.6mmol)环己酮和13.78g(80mmol)的对甲苯磺酸溶于80ml乙醇中，80℃回流反应6h。停止反应，冷至室温，旋蒸除去乙醇。乙酸乙酯溶解，碳酸钠溶液中和，乙酸乙酯萃取。无水硫酸钠干燥，旋蒸浓缩。硅胶柱分离得到目标产物10.2g，产率82％，质谱测得分子量m/z＝305.1。
中间体8的合成
称量9.18g(30mmol)的中间体7和1.53g(9mmol)二水合氯化铜溶于40ml的DMSO中。氮气保护，120℃反应12h。冷至室温，加入100ml乙酸乙酯，水洗4次，无水硫酸钠干燥，旋蒸除去溶剂。硅胶柱分离得到目标产物7.7g，产率85％，质谱测得分子量m/z＝301.1。
中间体9的合成
称量3.0g(10mmol)的中间体8、0.38g(2mmol)CuI、0.12g(2mmol)铜粉和4.17g(30mmol)碳酸钾于烧瓶中，加入30ml的二氯苯。抽换气，氮气保护，180℃回流反应48h。停止反应，减压蒸馏除去二氯苯。二氯甲烷溶解，水洗三次，无水硫酸钠干燥，旋蒸干燥。硅胶柱分离得到目标产物0.98g,产率45％，质谱测得分子量m/z＝442.3。
中间体10的合成
称量0.88g(2.0mmol)的中间体9溶于60ml氯仿中，避光室温搅拌。分批次加入0.71g(4.0mmol)的NBS，室温反应过夜。停止反应，反应液倒入碳酸氢钠水溶液中，水洗三次。无水硫酸钠干燥，旋蒸浓缩，氯仿/乙醇重结晶三次，得到目标产物0.46g，产率38％，质谱测得分子量m/z＝598.1。
合成实施例3：化66的合成
Figure PCTCN2022092188-appb-000020
称量0.60g(1.0mmol)的中间体10、0.63g(3.0mmol)的N-(4-异丙基苯基)苯胺、0.046g(0.05mmol)的三(二亚苄基丙酮)二钯、0.046g(0.20mmol)的三叔丁基四氟硼酸盐和0.29g(3.0mmol)的叔丁醇钠加入10ml的甲苯中。抽换气，氮气保护，120℃回流反应过夜。冷至室温，二氯甲烷/水萃取，无水硫酸钠干燥，旋蒸浓缩。硅胶柱分离得到目标产物化66 0.62g,产率72％，质谱测得分子量m/z＝860.5。
中间体11的合成
Figure PCTCN2022092188-appb-000021
称量6.75g(50mmol)的4-异丙基苯胺、14.2g(50mmol)的1-溴-4-苯基萘、0.09g(0.1mmol)的三(二亚苄基丙酮)二钯、0.09g(0.4mmol)的三叔丁基四氟硼酸盐和6.72g(70mmol)的叔丁醇钠加入80ml的甲苯中。抽换气，氮气保护，80℃反应4h。冷至室温，二氯甲烷/ 水萃取，无水硫酸钠干燥，旋蒸浓缩。硅胶柱分离得到目标产物13.7g,产率81％，质谱测得分子量m/z＝337.2。
合成实施例4：化94的合成
Figure PCTCN2022092188-appb-000022
将化66合成中的N-(4-异丙基苯基)苯胺替代为中间体11，相同的反应条件可以得到目标产物化94，产率65％，质谱测得分子量m/z＝1112.7。
Figure PCTCN2022092188-appb-000023
中间体12的合成
称量4.46g(20mmol)2-溴苯肼盐酸盐、4.2g(24mmol)4-苯基环己酮溶于40ml乙醇中，加入4.2g(24mmol)4-甲苯磺酸，80℃回流反应6h。停止反应，冷至室温，旋蒸除去乙醇，乙酸乙酯/水萃取三次，无水硫酸钠干燥，旋干溶剂，硅胶柱分离得到目标产物4.43g，产率68％，质谱测得分子量m/z＝325.1。
中间体13的合成
称量4.9g(15mmol)的中间体12溶于30ml的甲苯中，加入13.6g(60mmol)的DDQ，加热到120℃，回流搅拌反应12h。冷至室温，加入碳酸钠水溶液，乙酸乙酯萃取，收集有机相，无水硫酸钠干燥，旋干溶剂，硅胶柱分离得到目标产物3.38g，产率70％，质谱测得分子量m/z＝321.1。
中间体14的合成
称量3.2g(10mmol)的中间体13、0.38g(2mmol)CuI、0.12g(2mmol)铜粉和4.17g(30mmol)碳酸钾于烧瓶中，加入30ml的二氯苯。抽换气，氮气保护，180℃回流反应48h。停止反应，减压蒸馏除去二氯苯。二氯甲烷溶解，水洗三次，无水硫酸钠干燥，旋蒸干燥。硅胶柱分离得到目标产物0.77g,产率32％，质谱测得分子量m/z＝482.2。
中间体15的合成
称量0.96g(2.0mmol)的中间体14溶于100ml THF中，避光室温搅拌。分批次加入0.71g(4.0mmol)的NBS，室温反应过夜。停止反应，反应液倒入碳酸氢钠水溶液中，水洗三次。无水硫酸钠干燥，旋蒸浓缩，氯仿/乙醇重结晶三次，得到目标产物0.60g，产率47％，质谱测得分子量m/z＝638.1。
合成实施例5：化34的合成
称量0.64g(1.0mmol)的中间体15、0.76g(3.0mmol)的N-(4-叔丁基苯基)-2,4-二甲基苯胺、0.046g(0.05mmol)的三(二亚苄基丙酮)二钯、0.046g(0.20mmol)的三叔丁基四氟硼酸盐和0.29g(3.0mmol)的叔丁醇钠加入10ml的甲苯中。抽换气，氮气保护，120℃回流反应过夜。冷至室温，二氯甲烷/水萃取，无水硫酸钠干燥，旋蒸浓缩。硅胶柱分离得到目标产物化34 0.67g,产率68％，质谱测得分子量m/z＝984.5。
Figure PCTCN2022092188-appb-000024
中间体21的合成
称量7.47g(30mmol)的2-碘硝基苯、5.7g(33mmol)2-硼酸-4-氟-1-氯苯、0.1g(1.0mmol)四三苯基膦钯、8.3g(60mmol)碳酸钾溶于甲苯/乙醇/水(60/20/20ml)中，氮气鼓泡10分钟。加热至90℃回流反应12h。冷至室温，乙酸乙酯萃取，收集有机相，无水硫酸钠干燥，旋蒸干燥。硅胶柱分离得到目标产物5.85g，产率78％，质谱测得分子量m/z＝250.7。
中间体22的合成
称量5.0g(20mmol)中间体21、7.96g(20mmol)的1-溴-3,6-二苯基咔唑、(40mmol)13.0g碳酸铯溶于50ml DMAc中，抽换气，氮气保护，160℃反应24h。冷至室温，倒入水中，二氯甲烷萃取，旋干溶剂。硅胶柱分离得到目标产物7.16g，产率57％，质谱测得分子量m/z＝628.1。
中间体23的合成
称量6.3g(10mmol)的中间体22、7.9g(30mmol)的三苯基膦溶于30ml二氯苯中，氮气保护，180℃回流反应24h。冷至室温，减压蒸馏除去二氯苯。乙酸乙酯和水萃取三次，收集有机相，旋干溶剂。硅胶柱分离得到目标产物4.11g，产率69％，质谱测得分子量m/z＝596.1。
中间体24的合成
称量6.0g(10mmol)的中间体23、0.38g(2mmol)的碘化亚铜、4.9g(15mmol)碳酸铯溶于30ml二氯苯中，氮气保护，180℃回流反应24h。冷至室温，减压蒸馏除去二氯苯。乙酸乙酯和水萃取三次，收集有机相，旋干溶剂。硅胶柱分离得到目标产物2.17g，产率42％，质谱测得分子量m/z＝516.2。
合成实施例6：化147的合成
称量0.52g(1.0mmol)的中间体20、0.76g(3.0mmol)的N-苯基-3(9,9-二甲基-9H-芴)胺、0.046g(0.05mmol)的三(二亚苄基丙酮)二钯、0.046g(0.20mmol)的三叔丁基四氟硼酸盐和0.29g(3.0mmol)的叔丁醇钠加入10ml的甲苯中。抽换气，氮气保护，120℃回流反应过夜。冷至室温，二氯甲烷/水萃取，无水硫酸钠干燥，旋蒸浓缩。硅胶柱分离得到目标产物化147 0.57g,产率75％，质谱测得分子量m/z＝765.3。
Figure PCTCN2022092188-appb-000025
中间体25的合成
称量5.61g(20mmol)的2,4-二溴-3-硝基吡啶、3.28g(21mmol)4-氯苯硼酸、0.1g(1.0 mmol)四三苯基膦钯、5.5g(40mmol)碳酸钾溶于甲苯/乙醇/水(50/20/20ml)中，氮气鼓泡10分钟。加热至90℃回流反应12h。冷至室温，乙酸乙酯萃取，收集有机相，无水硫酸钠干燥，旋蒸干燥。硅胶柱分离得到目标产物4.49g，产率72％，质谱测得分子量m/z＝311.9。
中间体26的合成
称量3.12g(10mmol)的中间体25、7.9g(30mmol)的三苯基膦溶于30ml二氯苯中，氮气保护，180℃回流反应24h。冷至室温，减压蒸馏除去二氯苯。乙酸乙酯和水萃取三次，收集有机相，旋干溶剂。硅胶柱分离得到目标产物1.71g，产率61％，质谱测得分子量m/z＝279.9。
中间体27的合成
称量2.8g(10mmol)的中间体23、0.38g(2mmol)的碘化亚铜、4.14g(30mmol)碳酸钾溶于30ml二氯苯中，氮气保护，180℃回流反应48h。冷至室温，减压蒸馏除去二氯苯。乙酸乙酯和水萃取三次，收集有机相，旋干溶剂。硅胶柱分离得到目标产物1.14g，产率57％，质谱测得分子量m/z＝400.0。
合成实施例7：化170的合成
称量0.40g(1.0mmol)的中间体27、0.76g(3.0mmol)的N-(4-叔丁基苯基)-4-二苯并呋喃胺、0.046g(0.05mmol)的三(二亚苄基丙酮)二钯、0.046g(0.20mmol)的三叔丁基四氟硼酸盐和0.29g(3.0mmol)的叔丁醇钠加入15ml的甲苯中。抽换气，氮气保护，120℃回流反应过夜。冷至室温，二氯甲烷/水萃取，无水硫酸钠干燥，旋蒸浓缩。硅胶柱分离得到目标产物化170 0.60g,产率63％，质谱测得分子量m/z＝958.4。
合成实施例8：化180的合成
Figure PCTCN2022092188-appb-000026
与中间体10的合成步骤相同，将初始原料2-溴-4-叔丁基苯胺替换成2-溴-4,5-二甲基苯胺，可以得到中间体20，质谱测得分子量m/z＝542.1。
称量0.54g(1.0mmol)的中间体20、0.77g(3.0mmol)的N-(4-二苯并呋喃)-苯胺、0.046g(0.05mmol)的三(二亚苄基丙酮)二钯、0.046g(0.20mmol)的三叔丁基四氟硼酸盐和0.29g(3.0mmol)的叔丁醇钠加入10ml的甲苯中。抽换气，氮气保护，120℃回流反应过夜。冷至室温，二氯甲烷/水萃取，无水硫酸钠干燥，旋蒸浓缩。硅胶柱分离得到目标产物化180,约0.55g,产率61％，质谱测得分子量m/z＝900.4。
以下根据本发明的优选方案对涉及到的有机电致发光器件的膜层功能进行说明。
本发明方案所述的有机电致发光器件包含阳极层、阴极层以及阳极和阴极之间的至少一层的有机层。或者，有机层由多层有机化合物层叠构成的膜层。有机层还可以含有无机化合物。
本发明方案所述的有机电致发光器件的有机层中至少一层是发光层。有机层除了发光层，也可以包含其它功能层，例如在阳极层与发光层之间可以存在一层或者多层空穴注入层、空穴传输层、或者电子阻挡层，在两层发光层之间存在激子阻挡层或者具有类似功能的中间层也是可行的，在发光层和阴极层之间存在一层或者多层空穴阻挡层、电子传输层、或者电子注入层。应予说明，这些功能层不是必然存在的。
本发明所述的有机电致发光器件可以是荧光或者磷光器件，也可以是荧光和磷光混合器件；可以是具有单一发光的器件，也可以是具有多个发光单元的串联型器件；此外，可以是单色发光器件，也可以是混合色器件，也可以是白色发光器件。
发光层可以包含多个客体材料和多个主体材料。客体材料可以是荧光材料、磷光材料和/或者热活化延迟荧光材料。主体材料是指在发光层中占有绝大多数组成成分的基质材料，与荧光材料掺杂组合的主体材料称之为“荧光主体”，与磷光材料掺杂组合的主体材料称之为“磷光主体”。应予说明，主体材料的选择并不取决于其分子结构，而是根据作为客体材料的基质材料进行区分。
根据上述实施方案的本发明化合物可以用于不同的有机层中。优选如下有机电致发光器件，本发明化合物作为空穴注入材料、空穴传输材料或者发光层的发光材料应用。上述实施方案的本发明化合物的用途同样适用于有机电子器件。
在本发明的优选实施方案中，有机电致发光器件中本发明化合物作为发光层发光材料使用。
本领域普通技术人员通常已知这些方法，并且能够在不付出创造性劳动的情况下，将这些方法应用于包含本发明化合物的有机电致发光器件。
以下通过器件实施例1～8和器件比较例1～2详细说明本发明化合物在有机电致发光器件中的应用效果，用以验证本发明化合物的在本领域的技术进展和有益效果。实施例和比较例只是进一步详细地阐述本发明，但本发明所述不受技术条件限制。
器件实施例1～8：用作发光层蓝色发光材料的有机电致发光器件的制造
将25mm×75mm×1.1mm厚的带氧化铟锡(ITO)透明电极(阳极)的玻璃基板在异丙醇中进行超声波清洗5分钟后，进行紫外光(UV)-臭氧清洗30分钟。ITO的膜厚为130nm。将清洗后的上述玻璃基板安装于真空蒸镀装置的基板架，抽真空至1×10 -5～1×10 -6Pa，在ITO透明导电层上蒸镀空穴注入层(HIL)HATCN，膜厚15nm。在该空穴注入层之上蒸镀空穴传输层A(HTL)，膜厚60nm。然后，在该空穴传输层A之上蒸镀电子阻挡层(EBL)，膜厚5nm。然后，在该电子阻挡层之上共蒸镀发光层(EML)，膜厚20nm。发光层(EML)采用多源共蒸镀的方式蒸镀发光层的发光材料BD和主体材料BH，其中发光材料的掺杂浓度为2重量％。为保证发光材料的掺杂浓度准确性，需要等待发光材料和主体材料的蒸镀速率稳定后，再打开遮挡隔板，进行多源共蒸镀。然后在该发光层之上蒸镀空穴阻挡层(HBL)，膜厚5nm。然后在该空穴阻挡层之上蒸镀电子传输材料(ETL)和8-羟基喹啉锂(Liq)，膜厚30nm，掺杂比例1:1。然后，在该ETL之上蒸镀电子注入性电极(EIL)Liq，膜厚1nm。然后，在该EIL之上蒸镀金属阴极铝(Al)，膜厚100nm。实施例1的有机电致发光器件结构如图1所示，图1还显示了各功能层的叠加顺序及作用。所述用于OLED的材料分子结构示于表1。
表1用于OLED的材料
Figure PCTCN2022092188-appb-000027
Figure PCTCN2022092188-appb-000028
器件实施例1的器件结构具体的是：ITO(130)/HATCN(15)/HTL(60)/EBL(5)/BH:化2(20,重量2％)/HBL(5)/ETL:Liq(30，重量50％)/Liq(1)/Al(100)，需要说明的是，括弧内的数字表示膜厚(单位：nm)。
器件实施例2～器件实施例8与器件实施例1的区别仅在于将发光层中所用的本发明化合物化2替换为本发明的其它化合物，具体详见表2。
比较例1～2与器件实施例1相比，不同之处在于有机电致发光器件中的发光材料变更为比较化合物-1～比较化合物-2，所得器件性能测试数据如表2所示。
通过标准方法表征所述OLED。为了这个目的，确定电致发光光谱、电流效率(以cd/A度量)、功率效率(以lm/W度量)和外量子效率(EQE，以％度量)，其作为发光密度的函数从呈现朗伯发射特征的电流/电压/发光密度特征线(IUL特征线)计算。在10mA/cm 2的电流密度下确定所需的电压V10。最后，EQE表示在10mA/cm 2的电流密度下的外量子效率，T95表示器件在10mA/cm 2的电流密度下器件亮度减弱到95％的工作时间，CIE坐标是器件在10mA/cm 2的电流密度下电致发光光谱计算的CIE1931色度坐标(x、y)。
表2
Figure PCTCN2022092188-appb-000029
由表2可知，比较化合物1的器件EQE效率和T95分别为6.8％和82h，这主要是由于发光分子间的聚集作用导致器件的效率降低和老化(ACS Appl.Mater.Interfaces 2018,10,30022-30028)。对于比较化合物2的器件，其器件的EQE效率和T95寿命较低，分别只有3.6％和46h。使用本发明的分子作为发光层的掺杂剂后，其电致发光器件的性能得到明显提升，特别是效率和寿命，如应用化39制作的器件实施例2，其EQE效率可达8.9％，相比器件实施例1提升了30.8％，比器件实施例2提升了147％。而应用化94制作的器件实施例4，其T95寿命可达129h，相比器件实施例1提升了57％，比器件实施例2提升了180％。
物性数据
使用荧光谱测定装置日立高新技术公司制的分光荧光光度计对比较化合物1、比较化合物2和化66进行测定，将测试样品溶于溶剂(甲苯)(浓度的1*10 -5[mol/L])，在室温(300[K])下对加入石英比色池中的样照射360nm激发光，测试荧光光谱，可以得到其发光峰值和半峰宽，如表3所示。然后使用滨松光子学公司制的绝对PL量子产率测定装置测定样品的发光量子效率(PLQY)。
表3
样品 发光波长(nm) 半峰宽(nm) PLQY(％)
比较化合物1 463 41 87
比较化合物2 428 37 56
化66 457 21 91
比较化合物-1的甲苯溶液的荧光光谱如图2所示，其荧光峰值为463nm，发光效率(PLQY)可达87％；但是其荧光光谱的半峰宽可达41nm，因此其荧光中具有较多的长波长成分，这导致其电致发光器件的色坐标CIEy高达0.15，蓝光色纯度不高。
比较化合物-2的甲苯溶液的荧光光谱如图3所示，其荧光光谱的半峰宽为37nm，依然较宽。但是其荧光峰值为428nm，使得其电致发光器件的色坐标CIEy可以低至0.04，蓝光色纯度高。但是其发光效率(PLQY)只有56％，导致其电致发光器件的效率和寿命明显偏低。
本发明的化66的甲苯溶液的荧光光谱如图4所示，其荧光光谱的荧光峰值为457nm，半峰宽为21nm，非常窄的蓝光发射。因此其电致发光器件的色坐标CIEy低至0.07，蓝光色纯度高。同时其发光效率(PLQY)高达91％，使得其电致发光器件的效率和寿命明显提高。可以看到本发明的化66具有比现有技术比较化合物1相近的PLQY和发光波长，但是其半峰宽显著降低。同时相比于比较化合物2，本发明的分子连接了苯胺单元以后，除了发光波长红移，更显著的是半峰宽显著降低、发光效率显著提高。

Claims (10)

  1. 一种稠合氮杂环化合物，其特征在于，所述化合物由式(1)和式(2)结构组合构成：
    Figure PCTCN2022092188-appb-100001
    其中，
    式(1)中，Z 1～Z 14各自独立地表示为CR 1～CR 14或者N；式(2)中的L键连至Z 1～Z 14时，则Z 1～Z 14表示为C；
    环A～环D上Z 1～Z 14各自独立地表示为N时，环A～环D上N的数量之和≤4；且单独的环A～环D上N的数量≤1；
    式(2)所代表的取代基团在式(1)取代时的数量≤4；且单独的环A～环D上式(2)的取代数量≤1；
    L独立地选自单键、取代或未取代的碳原子数为1～20的直链或者支链亚烷基、取代或未取代的成环碳原子数为3～20的亚环烷基、取代或未取代的成环碳原子数为6～30的亚芳基、取代或未取代的成环碳原子数为2～30的亚杂芳基、取代或未取代的成环碳原子数10～50的亚稠合芳基环、取代或未取代的成环原子数6～50的亚稠合杂环；
    R 1～R 14取代基团独立地选自氢原子、氘原子、卤素原子、氰基、硝基、取代的硅基、取代或未取代的碳原子数1～50的烷基、取代或未取代的碳数1～20的烯基、取代或未取代的碳数1～20的炔基、取代或未取代的碳原子数1～50的烷氧基、取代或未取代的碳数1～20的氟代烷基、取代或未取代的碳数1～20的氟代烷氧基、取代或未取代的成环碳原子数3～50的环烷基、取代或未取代的成环碳原子数6～50的芳基、或者取代或未取代的成环原子数5～50的1价杂环基；
    R 15～R 16取代基团独立地选自取代或未取代的碳原子数1～50的烷基、取代或未取代的成环碳原子数3～50的环烷基、取代或未取代的成环碳原子数6～50的芳基、或者取代或未取代的成环原子数5～50的1价杂环基；
    R 1～R 16取代基团之间彼此可以键合形成取代或未取代的饱和的或者未饱和的环，也可与相邻芳环或杂芳环形成取代或未取代的饱和的或者未饱和的稠合环。
  2. 根据权利要求1所述的稠合氮杂环化合物，其特征在于，式(1)的优选结构如下表示：
    Figure PCTCN2022092188-appb-100002
    其中，R 1～R 14的定义如权利要求1中对式(1)的定义。
  3. 根据权利要求1所述的稠合氮杂环化合物，其特征在于，式(2)所代表的取代基团在式(1)取代时，只在Z 1、Z 2、Z 5、Z 6、Z 8、Z 9、Z 12或者Z 13位置进行取代。
  4. 根据权利要求1所述的稠合氮杂环化合物，其特征在于，所述式(2)中的L独立地选自单键，或者以下取代或未取代的基团中的任意一种或几种：亚苯基、亚萘基、亚芴基、亚茚基、亚吲哚基、亚苯并呋喃基、亚苯并噻吩基。
  5. 根据权利要求1所述的稠合氮杂环化合物，其特征在于，所述R 1～R 16取代基团分别独立地选自以下基团中的任意一种或几种：
    取代或未取代的甲基、取代或未取代的乙基、取代或未取代的正丙基、取代或未取代的异丙基、取代或未取代的正丁基、取代或未取代的异丁基、取代或未取代的仲丁基、取代或未取代的叔丁基、取代或未取代的2-甲基丁基、取代或未取代的正戊基、取代或未取代的仲戊基、取代或未取代的三氟甲基、取代或未取代的五氟乙基、取代或未取代的2,2,2-三氟乙基、取代或未取代的乙烯基、取代或未取代的丙烯基、取代或未取代的正丁烯基、取代或未取代的异丁烯基、取代或未取代的正戊烯基、取代或未取代的异戊烯基、取代或未取代的新戊烯基、取代或未取代的乙炔基、取代或未取代的丙炔基、取代或未取代的正丁炔基、取代或未取代的异丁炔基、取代或未取代的正戊炔基、取代或未取代的异戊炔基、取代或未取代的新戊炔基、取代或未取代的环丙基、取代或未取代的环丁基、取代或未取代的环戊基、取代或未取代的环己基、取代或未取代的金刚烷基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的联苯基、取代或未取代的萘基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的茚基、取代或未取代的芴基、取代或未取代的螺二芴基、取代或未取代的茚并芴基、取代或未取代的荧蒽基、取代或未取代的芘基、取代或未取代的苝基、取代或未取代的
    Figure PCTCN2022092188-appb-100003
    基、取代或未取代的并四苯基、取代或未取代的苯并噻咯基、取代或未取代的苯并噻吩基、取代或未取代的苯并呋喃基、取代或未取代的二苯并噻咯基、取代或未取代的二苯并噻吩基、取代或未取代的二苯并呋喃基、取代或未取代的二苯并硒吩基、取代或未取代的咔唑基、取代或未取代的吲哚并[3,2,1-jk]咔唑基；
    此外，R 1～R 14取代基团还可以选自以下基团中的任意一种或几种：氢原子、氘原子、氯原子、溴原子、碘原子、氰基、硝基、取代的硅基。
  6. 根据权利要求1所述的稠合氮杂环化合物，其特征在于，所述化合物中“取代或未取代”中的“取代”是指取代基独立地选自氘原子、氚原子、卤素原子、氰基、硝基、羟基、碳原子数1～10的1价烷基或者环烷基、碳原子数6～30的1价单环芳基或者稠环芳基、碳原子数2～50的1价杂环基或者稠环杂芳基。
  7. 根据权利要求1所述的稠合氮杂环化合物，其特征在于，所述稠合氮杂环化合物选自如下结构：
    Figure PCTCN2022092188-appb-100004
    Figure PCTCN2022092188-appb-100005
    Figure PCTCN2022092188-appb-100006
    Figure PCTCN2022092188-appb-100007
    Figure PCTCN2022092188-appb-100008
    Figure PCTCN2022092188-appb-100009
    Figure PCTCN2022092188-appb-100010
    Figure PCTCN2022092188-appb-100011
    Figure PCTCN2022092188-appb-100012
    Figure PCTCN2022092188-appb-100013
    Figure PCTCN2022092188-appb-100014
  8. 一种有机电致发光器件，其特征在于，所述有机电致发光器件包括阳极、阴极以及位于所述阳极和阴极之间的至少一层的有机薄膜，所述有机薄膜中含有权利要求1～7中任一项所述的化合物。
  9. 根据权利要求8所述的有机电致发光器件，其特征在于，所述有机薄膜包括空穴注入层、空穴传输层、电子阻挡层、发光层、激子阻挡层、空穴阻挡层、电子传输层、电子注入层中任意一种或者至少两种组合，且所述空穴注入层、空穴传输层、发光层中至少一层含有权利要求1～8中任一项所述的化合物。
  10. 根据权利要求8或9所述的有机电致发光器件，其特征在于，所述化合物在有机电致发光器件中选择作为空穴注入材料、空穴传输材料或者发光层的荧光材料应用。
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