WO2023202502A1 - 一种含有唑类的有机化合物及其应用 - Google Patents

一种含有唑类的有机化合物及其应用 Download PDF

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WO2023202502A1
WO2023202502A1 PCT/CN2023/088564 CN2023088564W WO2023202502A1 WO 2023202502 A1 WO2023202502 A1 WO 2023202502A1 CN 2023088564 W CN2023088564 W CN 2023088564W WO 2023202502 A1 WO2023202502 A1 WO 2023202502A1
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organic
azole
layer
substituted
structural formula
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French (fr)
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苏艳
周海涛
罗鑫
王宜凡
吴海发
杨之武
黄珠菊
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上海传勤新材料有限公司
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Definitions

  • the present invention relates to the technical field of organic electroluminescence, and more specifically, to an organic compound containing azoles and its application.
  • OLEDs organic electroluminescent devices
  • OLEDs organic electroluminescent devices
  • LCDs organic electroluminescent devices
  • driving voltage can reduce energy consumption
  • the use of organic materials makes the device It is thinner, lighter and more environmentally friendly
  • the diversified selection of substrates provides the possibility for flexible and transparent displays, which are widely used in mobile phones, flat panel displays, TVs, lighting, vehicle displays and other fields.
  • General organic electroluminescent devices adopt a sandwich structure, that is, the organic layer is sandwiched between the anode and cathode on both sides.
  • the organic layer is divided into a hole transport layer, an electron transport layer, and a light-emitting layer according to the different photoelectric properties of various materials. Hole blocking layer and electron blocking layer, etc.
  • the main luminescence mechanism of the device is: driven by an external voltage, holes and electrons overcome energy barriers and are injected into the hole transport layer and electron transport layer from the anode and cathode respectively, and then recombine and release energy in the luminescent layer, and transfer the energy to organic luminescent substances.
  • the luminescent substance obtains energy and causes it to transition from the ground state to the excited state. When the excited molecules transition to the ground state again, the luminescence phenomenon occurs.
  • Electron transport materials are materials that transport electrons from the cathode to the light-emitting layer. They are an important part of organic electroluminescent devices. They help reduce the injection energy barrier of electrons and avoid Avoid contact between the cathode and the luminescent layer, causing luminescence quenching. Electron transport materials generally require better thermal stability and film-forming properties, higher electron mobility, larger electron affinity and higher excited state energy levels.
  • Tris(8-hydroxyquinoline)aluminum, TBPi, Bphen, including other azoles, phenanthroline and other compounds have been used as electron transport materials in organic electroluminescent devices.
  • Adachi reported that the oxazole compound PBD (2-(4-biphenyl)-5-(4-tert-buylphenyl)-1,3,4-0xadiazole was used as an electron transport material in double-layer OLEDs (Appl. Phys. Lett., 1989, 55, 1489), however, the glass transition temperature of PBD is about 60 degrees, and it will crystallize when the device is working, resulting in shortened device life.
  • Patent US5646948 discloses an imidazole compound 1,3,5-tris( N-phenyl-benzimidizol-2-yl) (TPBI) is used as an electron transport material in organic electroluminescent devices.
  • Patent CN112279844 discloses that a fluorenazole compound is connected to a triazine and used as a green light host material, and is not considered to be disclosed The properties of compounds and triazine connected at other positions as electron transport materials.
  • Patent KR20200100972 discloses that azole derivatives connected to aromatic amines are used as light extraction layer materials, without considering the performance of the disclosed compounds as electron transport materials.
  • Patent WO2010126270 discloses Benzoxazole group connected to triazine It is an electron transport material used in organic electroluminescent devices, but does not show the properties of other group azoles.
  • Patent CN107311955A discloses benzoxazole series compounds at the 4,7-position of indeno, but did not realize the advantages of compounds introducing different groups at the 5,6-position.
  • the present invention studies an azole organic compound and its application as an electron transport material in an organic electroluminescent device.
  • the synthesized device has excellent device performance.
  • the present invention provides an organic compound containing azoles and its application.
  • the present invention adopts the following technical solution: introducing azole derivatives into the compound and connecting the triazine and pyridyl groups through chemical bonds or aromatic groups, which can enhance the stability of the material and improve the electron transmission performance of the compound.
  • the structure is shown in structural formula I,
  • Ar 1 -Ar 3 is one of C 6 -C 30 substituted or unsubstituted aryl groups and C 3 -C 30 substituted or unsubstituted heteroaryl groups;
  • More than one of Z 1 -Z 3 is N, and the rest are CH;
  • L is a single bond, C 6 -C 30 substituted or unsubstituted aryl group, C 3 -C 30 substituted or unsubstituted One of the substituted heteroaryl groups;
  • A is CR 101 R 102 , ethylene, vinylene, phenylene, O, S, SO 2 , Se or NR 103 ;
  • R 101 -R 103 is a substituted or unsubstituted alkyl group of C 1 -C 20 R _ _ _ _ _ 101 and R 102 can be connected through chemical bonds;
  • B is -NR 104 , -O- or -S-;
  • R 104 is C 1 -C 20 substituted or unsubstituted alkyl, C 3 -C 20 substituted or unsubstituted cycloalkyl, C 6 -C 30 substituted or unsubstituted aryl group, one of C 3 -C 30 substituted or unsubstituted heteroaryl group.
  • Ar 1 -Ar 3 are phenyl, tolyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, perylene, fluoranthyl, pyrenyl, phenylnaphthyl, naphthylphenyl, diphenyl phenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirodifluorenyl, benzofuranyl, benzothienyl, dibenzofuranyl, di Benzothienyl, benzophenanthyl, spiro[fluorene-9,9'-xanthene], pyridyl, benzylphenyl, pyridylphenyl, indolyl, carbazole indolyl, fluorene carbazole base, imidazolyl, oxazolyl, thiazolyl,
  • L is preferably a single bond, phenyl, naphthyl, biphenyl, anthracenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirodifluorenyl, benzo Furyl or dibenzothienyl;
  • R 101 to R 104 are methyl, ethyl, isopropyl, propyl, butyl, phenyl, biphenyl, naphthyl or tolyl.
  • the azole-containing compound is a compound of the following structural formula 1-96:
  • the above-mentioned azole-containing compounds can be used to synthesize organic electroluminescent devices.
  • the organic electroluminescent devices include an anode, a cathode and an organic layer; the organic layer includes a light-emitting layer, a hole injection layer, a hole transport layer, and a hole blocking layer. layer, electron injection layer, and electron transport layer.
  • At least one of the organic layers contains an azole-containing compound represented by structural formula I.
  • the light-emitting layer of the organic layer contains an azole-containing compound represented by structural formula I.
  • the organic layer electron transport layer or electron injection layer contains an azole-containing compound represented by structural formula I.
  • the hole blocking layer in the organic layer contains an azole-containing compound represented by structural formula I.
  • the total thickness of the organic layer is 1-1000 nm; further preferably, the total thickness of the organic layer is 50-500 nm.
  • Each layer of the organic layer in the organic electroluminescent device of the present invention can be formed by vacuum evaporation, molecular beam evaporation, solvent-soluble dip coating, spin coating, rod coating or inkjet printing. Synthesis, metal electrodes can be synthesized using evaporation or sputtering.
  • Azole-containing compounds represented by structural formula I can also be used to produce organic solar cells, organic thin film transistors, organic photodetectors, organic field effect transistors, organic integrated circuits and organic photoreceptors.
  • the invention provides an organic compound containing azoles and its application.
  • the introduction of azoles is connected with a triazine group, which is beneficial to improving the thermal stability and electron mobility of the material.
  • Organic electroluminescent devices produced using the organic electroluminescent compound can reduce driving voltage, improve luminous efficiency, have excellent color purity, and extend device life.
  • Figure 1 is a schematic structural diagram of an organic electroluminescent device of the present invention.
  • the specific device structure is as follows: glass/anode (ITO)/hole injection layer (HIL)/hole transport layer (HTL)/electron blocking layer (EBL)/luminescence Layer (EML, host material BH: blue luminescent material BD)/electron transport layer (ETL, electron transport material: lithium 8-hydroxyquinolate)/electron injection layer (EIL)/cathode (Mg:Ag, 10:1) .
  • ITO glass/anode
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EML luminescence Layer
  • EML host material BH: blue luminescent material BD
  • ETL electron transport material: lithium 8-hydroxyquinolate
  • EIL electroluminescent devices
  • Compound 1 prepared in Example 1 was used to prepare OLED.
  • the transparent conductive ITO glass substrate 110 (with the anode 120 on it) (China Southern Glass Group Co., Ltd.) is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, and then washed with ethanol, acetone and deionized water in sequence. Bake in a clean environment until the moisture is completely removed, clean with ultraviolet photosynthetic ozone, and then treat with oxygen plasma for 30 seconds.
  • HIL hole injection layer 130 on the ITO at a evaporation rate of 0.1 nm/s.
  • Compound HT is evaporated on the hole injection layer to form a hole transport layer 140 with a thickness of 80 nm, and the evaporation rate is 0.1 nm/s.
  • EB is evaporated on the empty transport layer to form a 10 nm thick electron blocking layer 150 .
  • the evaporation rate is 0.1nm/s.
  • a 30 nm thick light-emitting layer 160 was evaporated on the hole blocking layer, in which BH was the host light-emitting material, and BD with a weight ratio of 2% was used as the doped guest material.
  • the evaporation rate was 0.1 nm/s.
  • a 30 nm thick mixture of 50% by weight Compound 1 and 50% by weight LiQ was evaporated on the light-emitting layer as the electron transport layer 170 .
  • the evaporation rate is 0.1nm/s
  • LiQ was evaporated to a thickness of 1 nm as the electron injection layer 180 on the electron transport layer.
  • Magnesium silver with a thickness of 100 nm and a doping ratio of 10:1 is evaporated on the electron injection layer to serve as the device cathode 190 .
  • Example 13 The only difference from Example 13 is that compound 1 was replaced with other compounds of the present invention as the electron transport material.
  • Example 13 The only difference from Example 13 is that compound 1 was replaced with compound TPBI as the electron transport material.
  • the above-mentioned organic materials are all existing known materials and are purchased from the market.
  • the operating voltage, efficiency, and emission wavelength of the prepared device were measured at a current density of 10 mA/cm 2 using a Photo Research PR655 spectrometer, and the current was measured at 15 mA/cm 2
  • the time (T95) for the brightness to become 95% of the initial brightness under the density is shown in Table 2.
  • the voltage of the organic electroluminescent device prepared by using the electron transport material of the present invention is reduced by 0.3-0.4V, the current efficiency is improved, and the T95 is increased from 51 hours at a current density of 15mA/cm 2 To 76-119 hours, the lifespan is greatly improved.
  • the compound of the present invention shows good performance. This is because the azole is connected with the triazine, which is beneficial to increasing the stability of the material and improving the conjugation, improving the electron mobility of the material, and enhancing the balance of holes and electrons in the device, which can Effectively transport electrons to the light-emitting layer, thereby improving device performance.

Abstract

涉及一种含有唑类的有机化合物及其应用,其结构如结构式I所示，其中，Ar 1-Ar 3为C 6-C 30取代或者未取代的芳基，C 3-C 30取代或者未取代的杂芳基中的一种；Z 1-Z 3中一个以上为N，其余为CH；L为单键，C 6-C 30取代或者未取代的芳基，C 3-C 30取代或者未取代的杂芳基中的一种。

Description

一种含有唑类的有机化合物及其应用 技术领域：
本发明涉及有机电致发光技术领域，更具体地说，是涉及一种含有唑类的有机化合物及其应用。
背景技术：
有机电致发光器件(OLEDs)作为一种新型的显示技术，每个像素切换自如，且主动发光，使得显示响应时间短，色彩对比度高；驱动电压低可减少能耗；有机材料的使用使得器件更加轻薄，环保；而基板的多元化选择为柔性和透明显示提供可能，广泛应用在手机、平板显示器、电视、照明和车载显示等领域。
一般的有机电致发光器件采用夹层式三明治结构，即有机层夹在两侧阳极和阴极之间，有机层按照各种材料不同的光电特性分为空穴传输层、电子传输层、发光层、空穴阻挡层和电子阻挡层等。器件的发光机理主要为：在外界电压驱动下，空穴和电子克服能垒，分别由阳极和阴极注入到空穴传输层和电子传输层，然后在发光层中复合并释放能量，并把能量传递给有机发光物质。发光物质得到能量，并使其从基态跃迁到激发态，当受激发分子重新跃迁到基态，就产生了发光现象。
电子传输材料就是把阴极上的电子传输到发光层的材料，是有机电致发光器件的重要组成部分，有利于降低电子的注入能垒，还可避 免阴极与发光层接触，导致发光猝灭。电子传输材料一般要求较好的热稳定性和成膜性，较高的电子迁移率、较大的电子亲和能和较高的激发态能级。
由于大多有机电致发光材料传输空穴的速度要比传输电子的速度快。这就使得电子和空穴在发光层中的数量不平衡，导致器件发光时远离发光层，接近电极，这样就需要较高的驱动电压，也降低了器件的效率和器件的使用寿命。最近的有机电致发光器件尽管已经得到逐渐改良，但仍要求在发光效率，驱动电压，寿命等方面更为优异的材料，因此，需要开发具有良好热稳定性和性能优良的电子传输材料。
三(8-羟基喹啉)铝，TBPi,Bphen,包括其它唑类，菲罗啉等化合物已经作为电子传输材料应用在有机电致发光器件。1989年Adachi报道了噁唑类化合物PBD(2-(4-biphenyl)-5-(4-tert-buylphenyl)-1,3,4-0xadiazole作为电子传输材料用于双层式OLED上(Appl.Phys.Lett.,1989,55,1489),然而，PBD的玻璃化温度约为60度，器件工作时会结晶，造成器件寿命缩短。专利US5646948公开了咪唑类化合物1,3,5—tris(N-phenyl-benzimidizol-2-yl)(TPBI)作为电子传输材料应用在有机电致发光器件上。专利CN112279844公开了芴并唑类化合物跟三嗪连接用作绿光主体材料，并且没有考虑公开化合物及在其它位置接三嗪作为电子传输材料的性能。专利KR20200100972公开了唑类衍生物连接芳香胺用作光提取层材料，没有考虑所公开化合物的用作电子传输材料性能。专利WO2010126270公开了苯并唑类基团接三嗪作 为电子传输材料应用在有机电致发光器件上，但是没有显示其它基团并唑类化合物的性质。专利CN107311955A公开了茚并4，7-位的苯并唑系列化合物，并没意识到在5，6位上引入不同基团的化合物的优势。
随着OLED的要求越来越高，还需要开发具有优异的热稳定性，成膜性和电子传输性能的电子传输材料。本发明研究一种唑类的有机化合物，以及作为电子传输材料在有机电致发光器件上面的应用，合成出的器件具有优异的器件性能。
发明内容：
本发明正是针对上述问题，提供了一种含有唑类的有机化合物及其应用。
为了实现上述目的，本发明采用如下技术方案，在化合物中引入唑类衍生物，并通过化学键或者芳香基团连接三嗪和吡啶基，可以增强材料的稳定性，提高化合物的电子传输性能，其结构如结构式I所示，
结构式I中，Ar1-Ar3为C6-C30取代或者未取代的芳基，C3-C30取代或者未取代的杂芳基中的一种；
Z1-Z3中一个以上为N,其余为CH；
L为单键，C6-C30取代或者未取代的芳基，C3-C30取代或者未取 代的杂芳基中的一种；
A为CR101R102，亚乙基，亚乙烯基，亚苯基，O，S，SO2，Se或者NR103；R101-R103为C1-C20的取代或未取代的烷基，C3-C20的取代或未取代的环烷基，C6-C30的取代或者未取代的芳基，C3-C30的取代或者未取代的杂芳基中的一种；R101和R102可以通过化学键连接；
B为-NR104，-O-或者-S-；R104为C1-C20的取代或未取代的烷基，C3-C20的取代或未取代的环烷基，C6-C30的取代或者未取代的芳基，C3-C30的取代或者未取代的杂芳基中的一种。
优选地，Ar1-Ar3为苯基，甲苯基，联苯基，萘基，菲基，蒽基，苝基，荧蒽基，芘基，苯基萘基，萘基苯基，二苯基苯基，9，9-二甲基芴基，9，9-二苯基芴基，9，9-螺二芴基，苯并呋喃基，苯并噻吩基，二苯并呋喃基，二苯并噻吩基，苯并菲基，螺[芴-9,9'-氧杂蒽]，吡啶基，苄基苯基，吡啶基苯基，吲哚基，咔唑吲哚基，芴咔唑基、咪唑基，噁唑基，噻唑基，噻二唑基，喹啉基，异喹啉基，喹唑啉基，喹喔啉基，氮杂二苯并呋喃基，氮杂二苯并噻吩基中的一种，以上芳基和杂芳基还可以进一步为C1-C12的烷基取代。
L优选为单键，苯基，萘基，联苯基，蒽基，9，9-二甲基芴基，9，9-二苯基芴基，9，9-螺二芴基，苯并呋喃基或者二苯并噻吩基；
R101-R104为甲基，乙基，异丙基，丙基，丁基，苯基，联苯基，萘基或者甲苯基。
进一步优选地，含唑类化合物为下列结构式1-96的化合物:



上述含唑类化合物可应用于合成有机电致发光器件，所述的有机电致发光器件包括阳极、阴极和有机层；有机层包含发光层、空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层以上。
所述的有机层中至少有一层含有结构式Ⅰ所示的含唑类化合物。
优选地，所述的有机层的发光层中含有结构式Ⅰ所示的含唑类化合物。
优选地，所述的有机层电子传输层或者电子注入层中含有结构式Ⅰ所示的含唑类化合物。
优选地，所述的有机层中空穴阻挡层含有结构式Ⅰ所示的含唑类化合物。
优选地，所述的有机层的总厚度为1-1000nm；进一步优选地，所述的有机层的总厚度为50-500nm。
本发明的有机电致发光器件中有机层的每一层，可以通过真空蒸镀法、分子束蒸镀法、溶于溶剂的浸涂法、旋涂法、棒涂法或者喷墨打印等方式合成，对于金属电极可以使用蒸镀法或者溅射法进行合成。
含有结构式Ⅰ所示的含唑类化合物还可被用于生产有机太阳能电池、有机薄膜晶体管、有机光检测器、有机场效应晶体管、有机集成电路和有机光感受器。
本发明的有益效果：
本发明提供了一种含有唑类的有机化合物和应用，唑类的引入跟三嗪基团相连接，有益于提升材料的热稳定性和电子迁移率。采用该有机电致发光化合物制作的有机电致发光器件能够降低驱动电压、提高发光效率、色纯度优异、延长器件寿命的效果。
附图说明：
图1为本发明的一种有机电致发光器件结构示意图。
具体实施方式：
实施例1化合物1的合成
1、中间体1-1的合成
将3,7-二溴-9,9-二甲基-9H-芴-2-胺(15.0g，40.86mmol)和DCM(150mL)加入到烧瓶中，再加入三乙胺(14.9g，147.11mmol)，降温至0-5℃，缓慢滴加苯甲酰氯(18.4g，130.76mmol)，加完搅拌1h，加水(150mL)淬灭反应，分液，有机相浓缩至近干，有固体析出，加入石油醚(50mL)搅拌，析出大量固体，过滤，石油醚淋洗，滤饼烘干，得到16g白色固体，产率80％。1H NMR(400MHz,CDCl3)δ:9.73(s,1H),7.94-7.98(m,2H),7.83(s,1H),7.63-7.68(m,2H),7.49-7.58(m,5H),1.57(s,6H).
2、中间体1-2的合成
将中间体1-1(14.75g，31.3mmol)，碳酸铯(12.24g，37.56mmol)，1,10-邻菲罗啉(0.9g，5.01mmol)，碘化亚铜(0.45g，2.35mmol) 加入到单口烧瓶中，再加入DMF(120mL)和二甲苯(60mL)。回流反应8h后，停止反应，过滤，滤液减压蒸馏除去大部分溶剂，加水搅拌析出固体，过滤，乙醇淋洗，烘干，得到白色固体9.3g，产率76％。1H NMR(400MHz,CDCl3)δ:7.87-7.91(m,2H),7.82-7.84(m,1H),7.75(s,1H),7.45-7.55(m,6H),1.57(s,6H).
3、中间体1-3的合成
将中间体1-2(8.0g，20.5mmol)，联硼酸频哪酯(6.77g，26.65mmol)，醋酸钾(6.0g，61.49mmol)和无水甲苯(80mL)加入到三口烧瓶中，氮气保护下，加入Pd(PPh3)2Cl2(0.16g)，回流反应5h，趁热过率，甲苯淋洗，滤液浓缩至近干，加入石油醚搅拌(20mL)，析出大量固体，过滤，石油醚淋洗，烘干，得到7.8g灰白色产物，产率87％。1HNMR(400MHz,CDCl3)δ:7.94-7.98(m,2H),7.85(s,1H),7.71-7.74(m,1H),7.54(s,1H),7.44-7.52(m,4H),7.41-7.43(m,1H),1.56(s,6H),1.24(s,12H).
4、化合物1的合成
将中间体1-3(0.86g，1.97mmol)，2-氯-4,6-二苯基-1,3,5-三嗪(0.5g，1.87mmol)和碳酸钾(0.51g，3.69mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.65g淡黄绿色固体，产率64％。1H NMR(400MHz,CDCl3)δ:8.21-8.24(m,4H),7.96-8.03(m,2H),7.86-7.94(m,3H),7.79(m,1H),7.56(m,1H),7.39-7.47(m,9H), 1.57(s,6H).
实施例2化合物9的合成
将2-氯-4-(二苯并[b,d]呋喃-3-基)-6-苯基-1,3,5-三嗪(0.5g，1.40mmol)，中间体1-3(0.64g，1.46mmol)和碳酸钾(0.29g，2.10mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.54g淡黄绿色固体，产率61％。1H NMR(400MHz,CDCl3):8.12-8.20(m,4H),7.90-8.06(m,6H),7.78-7.82(m,2H),7.56-7.59(m,2H),7.48-7.52(m,1H),7.36-7.46(m,7H),1.58(s,6H).
实施例3化合物22的合成
将2-氯-4-(9,9’-螺二芴-2-基)-6-苯基-1,3,5-三嗪(0.5g，0.99mmol)，中间体1-3(0.45g，1.03mmol)和碳酸钾(0.27g，1.95mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水 (3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.51g淡黄绿色固体，产率57％。1H NMR(400MHz,CDCl3)δ:8.19-8.23(m,2H),7.91-8.02(m,5H),7.78-7.87(m,7H),7.55(s,1H),7.33-7.46(m,9H),7.25-7.29(m,3H),7.01-7.08(m,3H),1.60(s,6H).
实施例4化合物26的合成
将2-[(1,1’-联苯)-4-基]-4-氯-6-苯基-1,3,5-三嗪(0.5g，1.45mmol)，中间体1-3(0.67g，1.53mmol)和碳酸钾(0.40g，2.89mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.59g淡黄绿色固体，产率65％。1H NMR(400MHz,CDCl3)δ:8.16-8.20(m,2H),7.90-8.02(m,6H),7.78-7.82(m,2H),7.56-7.65(m,5H),7.35-7.45(m,9H),1.58(s,6H).
实施例5化合物30的合成
将3’-(4-氯-6-苯基-1,3,5-三嗪-2-基)-(1,1’-联苯)-4-甲腈(0.5g，1.36mmol)，中间体1-3(0.62g，1.42mmol)和碳酸钾(0.37g，2.68mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.52g淡黄绿色固体，产率59％。1H NMR(400MHz,CDCl3)δ:8.16-8.24(m,4H),7.90-8.02(m,4H),7.66-7.82(m,7H),7.50-7.56(m,2H),7.35-7.45(m,6H),1.58(s,6H).
实施例6化合物37的合成
将2-氯-4-苯基-6-(螺芴-9,9’-氧杂蒽-2-基)-1,3,5-三嗪(0.5g，0.96mmol)，中间体1-3(0.44g，1.01mmol)和碳酸钾(0.26g，1.88mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.63g淡黄 绿色固体，产率69％。1H NMR(400MHz,CDCl3)δ:8.19-8.23(m,2H),7.99-8.05(m,2H),7.91-7.94(m,3H),7.77-7.85(m,5H),7.55(s,1H),7.34-7.46(m,7H),7.22-7.27(m,3H),7.09-7.17(m,4H),6.90-7.00(m,3H),1.60(s,6H).
实施例7化合物41的合成
1、中间体41-1的合成
将3,7-二溴-9,9-二苯基-9H-芴-2-胺(15.0g，30.54mmol)和DCM(150mL)加入到烧瓶中，再加入三乙胺(10.8g，106.73mmol)，降温至0-5℃，缓慢滴加苯甲酰氯(12.9g，91.77mmol)，加完搅拌1h，加水(150mL)淬灭反应，分液，有机相浓缩至近干，有固体析出，加入石油醚(50mL)搅拌，析出大量固体，过滤，石油醚淋洗，滤 饼烘干，得到15g白色固体，产率82％。1H NMR(400MHz,CDCl3)δ:9.92(s,1H),7.94-7.97(m,2H),7.86(s,1H),7.75-7.78(m,1H),7.49-7.53(m,3H),7.38-7.47(m,3H),7.24-7.31(m,6H),7.14-7.19(m,4H).
2、中间体41-2的合成
将中间体41-1(14.0g，23.52mmol)，碳酸铯(9.2g，28.24mmol)，1,10-邻菲罗啉(0.85g，4.72mmol)，碘化亚铜(0.45g，2.36mmol)加入到单口烧瓶中，再加入DMF(120mL)和二甲苯(60mL)。回流反应8h后，停止反应，过滤，滤液减压蒸馏除去大部分溶剂，加水搅拌析出固体，过滤，乙醇淋洗，烘干，得到白色固体8.5g，产率70％。1H NMR(400MHz,CDCl3)δ:7.94-7.98(m,2H),7.89-7.91(m,1H),7.81(s,1H),7.60-7.62(m,1H),7.41-7.51(m,5H),7.27-7.31(m,6H),7.18-7.22(m,4H).
3、中间体41-3的合成
将中间体41-2(8.0g，15.55mmol)，联硼酸频哪酯(4.7g，18.51mmol)，醋酸钾(4.6g，46.87mmol)和无水甲苯(80mL)加入到三口烧瓶中，氮气保护下，加入Pd(PPh3)2Cl2(0.16g)，回流反应5h，趁热过率，甲苯淋洗，滤液浓缩至近干，加入石油醚搅拌(20mL)，析出大量固体，过滤，石油醚淋洗，烘干，得到7.9g灰白色产物，产率90％。1H NMR(400MHz,CDCl3)δ:7.88-7.94(m,3H),7.71-7.73(m,1H),7.40-7.49(m,5H),7.25-7.35(m,7H),7.17-7.21(m,4H),1.24(m,12H).
4、化合物41的合成
将中间体41-3(0.86g，1.53mmol)，2-[(1,1’-联苯)-4基]-4-氯-6-苯基-1,3,5-三嗪(0.5g，1.45mmol)和碳酸钾(0.40g，2.89mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.72g淡黄绿色固体，产率66％。1H NMR(400MHz,CDCl3)δ:8.19-8.23(m,2H),7.82-8.02(m,8H),7.57-7.67(m,4H),7.33-7.46(m,10H),7.21-7.32(m,6H),7.12-7.16(m,4H).
实施例8化合物56的合成
1、中间体56-1的合成
将2,7-二溴二苯并[b,d]呋喃-3-胺(15.0g，43.99mmol)和DCM (150mL)加入到烧瓶中，再加入三乙胺(15.6g，154.17mmol)，降温至0-5℃，缓慢滴加苯甲酰氯(18.6g，132.32mmol)，加完搅拌1h，加水(150mL)淬灭反应，分液，有机相浓缩至近干，有固体析出，加入石油醚(50mL)搅拌，析出大量固体，过滤，石油醚淋洗，滤饼烘干，得到13.7g白色固体，产率70％。1H NMR(400MHz,CDCl3)δ:9.79(s,1H),8.03(s,1H),7.93-7.98(m,3H),7.80-7.83(m,1H),7.49-7.58(m,5H).
2、中间体56-2的合成
将中间体56-1(13.0g，29.21mmol)，碳酸铯(11.4g，34.99mmol)，1,10-邻菲罗啉(1.05g，5.83mmol)，碘化亚铜(0.56g，2.94mmol)加入到单口烧瓶中，再加入DMF(120mL)和二甲苯(60mL)。回流反应8h后，停止反应，过滤，滤液减压蒸馏除去大部分溶剂，加水搅拌析出固体，过滤，乙醇淋洗，烘干，得到白色固体8.1g，产率76％。1H NMR(400MHz,CDCl3)δ:7.87-7.96(m,4H),7.70(s,1H),7.44-7.53(m,5H).
3、中间体56-3的合成
将中间体56-2(8.0g，21.97mmol)，联硼酸频哪酯(6.7g，26.38mmol)，醋酸钾(6.5g，66.23mmol)和无水甲苯(80mL)加入到三口烧瓶中，氮气保护下，加入Pd(PPh3)2Cl2(0.16g)，回流反应5h，趁热过率，甲苯淋洗，滤液浓缩至近干，加入石油醚搅拌(20mL)，析出大量固体，过滤，石油醚淋洗，烘干，得到7.8g灰白色产物，产率86％。1H NMR(400MHz,CDCl3)δ:8.05(s,1H),7.79-7.91(m, 5H),7.63-7.66(m,1H),7.45-7.52(m,3H),1.24(m,12H).
4、化合物56的合成
将中间体56-3(0.63g，1.53mmol)，2-[(1,1’-联苯)-4基]-4-氯-6-苯基-1,3,5-三嗪(0.5g，1.45mmol)和碳酸钾(0.40g，2.89mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.53g淡黄绿色固体，产率61％。1H NMR(400MHz,CDCl3)δ:8.15-8.25(m,4H),8.09-8.12(m,1H),7.97-8.00(m,3H),7.87-7.91(m,2H),7.81(s,1H),7.60-7.67(m,4H),7.36-7.49(m,9H).
实施例9化合物62的合成
1、中间体62-1的合成
将2,7-二溴二苯并[b,d]噻吩-3-胺(15.0g，42.01mmol)和DCM(150mL)加入到烧瓶中，再加入三乙胺(14.9g，147.25mmol)，降温至0-5℃，缓慢滴加苯甲酰氯(17.7g，125.92mmol)，加完搅拌1h，加水(150mL)淬灭反应，分液，有机相浓缩至近干，有固体析出，加入石油醚(50mL)搅拌，析出大量固体，过滤，石油醚淋洗，滤饼烘干，得到16.3g白色固体，产率84％。1H NMR(400MHz,CDCl3)δ:9.71(s,1H),8.49(s,1H),8.07(s,1H),7.88-7.98(m,4H),7.46-7.58(m,4H).
2、中间体62-2的合成
将中间体62-1(15.0g，32.53mmol)，碳酸铯(12.7g，38.98mmol)，1,10-邻菲罗啉(1.17g，6.49mmol)，碘化亚铜(0.62g，3.26mmol)加入到单口烧瓶中，再加入DMF(120mL)和二甲苯(60mL)。回流反应8h后，停止反应，过滤，滤液减压蒸馏除去大部分溶剂，加水搅拌析出固体，过滤，乙醇淋洗，烘干，得到白色固体9.9g，产率80％。1H NMR(400MHz,CDCl3)δ:8.29(s,1H),8.16(s,1H),7.86-8.01(m,4H),7.45-7.53(m,4H).
3、中间体62-3的合成
将中间体62-2(8.0g，21.04mmol)，联硼酸频哪酯(6.4g，25.20mmol)，醋酸钾(6.2g，63.18mmol)和无水甲苯(80mL)加入到三口烧瓶中，氮气保护下，加入Pd(PPh3)2Cl2(0.16g)，回流反应5h，趁热过率，甲苯淋洗，滤液浓缩至近干，加入石油醚搅拌(20mL)，析出大量固体，过滤，石油醚淋洗，烘干，得到8.1g灰白色产物， 产率90％。1H NMR(400MHz,CDCl3)δ:8.39(s,1H),8.22-8.29(m,2H),7.85-7.98(m,3H),7.67-7.70(m,1H),7.45-7.52(m,3H),1.24(m,12H).
4、化合物62的合成
将中间体62-3(0.65g，1.52mmol)，2-[(1,1’-联苯)-4基]-4-氯-6-苯基-1,3,5-三嗪(0.5g，1.45mmol)和碳酸钾(0.40g，2.89mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.64g淡黄绿色固体，产率72％。1H NMR(400MHz,CDCl3)δ:8.70-8.71(m,1H),8.35(s,1H),8.16-8.21(m,4H),7.91-8.09(m,5H),7.60-7.65(m,4H),7.36-7.47(m,9H).
实施例10化合物79的合成
将中间体1-3(0.59g，1.35mmol)，2-(3-溴苯基)-4,6-二苯基-1,3,5-三嗪(0.5g，1.29mmol)和碳酸钾(0.36g，2.60mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.54g淡黄绿色固体，产率67％。1H NMR(400MHz,CDCl3)δ:8.16-8.23(m,5H),8.11-8.13(m, 1H),7.90-7.94(m,2H),7.71-7.79(m,3H),7.49-7.57(m,3H),7.36-7.47(m,10H),1.57(s,6H).
实施例11化合物82的合成
将中间体1-3(0.49g，1.12mmol)，2-[(1,1’-联苯)-4-基]-4-(3-溴苯基)-6-苯基-1,3,5-三嗪(0.5g，1.08mmol)和碳酸钾(0.30g，2.17mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)，氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.47g淡黄绿色固体，产率62％。1H NMR(400MHz,CDCl3)δ:8.16-8.23(m,3H),8.11-8.13(m,1H),7.89-8.00(m,4H),7.71-7.79(m,3H),7.54-7.65(m,6H),7.48-7.52(m,2H),7.33-7.46(m,9H),1.56(s,6H).
实施例12化合物91的合成
将中间体56-3(0.56g，1.36mmol)，2-(3-溴苯基)-4,6-二苯基-1,3,5-三嗪(0.5g，1.29mmol)和碳酸钾(0.36g，2.60mmol)加入到三口烧瓶中，再加入甲苯(5mL)，四氢呋喃(3mL)和去离子水(3mL)， 氮气保护下加入Pd(PPh3)2Cl2(0.01g)，回流反应5h后，分液，有机相浓缩干，粗品柱色谱分离，烘干，得到0.55g淡黄绿色固体，产率72％。1H NMR(400MHz,CDCl3)δ:8.34(t,J＝1.6Hz,1H),8.19-8.23(m,5H),7.98-8.02(m,2H),7.87-7.91(m,2H),7.81(s,1H),7.64-7.66(m,1H),7.50-7.59(m,2H),7.38-7.46(m,10H).
以下通过实施例对本发明化合物的效果进行详细说明。
有机电致发光器件的制备，结构示意图见图1，具体器件结构如下：玻璃/阳极(ITO)/空穴注入层(HIL)/空穴传输层(HTL)/电子阻挡层(EBL)/发光层(EML，主体材料BH:蓝色发光材料BD)/电子传输层(ETL,电子传输材料:8-羟基喹啉锂)/电子注入层(EIL)/阴极(Mg:Ag,10:1)。具体器件结构见图1。
实施例13
器件制备方法：
使用实施例1制备的化合物1制备OLED。
将透明导电ITO玻璃基板110(上面带有阳极120)(中国南玻集团股份有限公司)在商用清洗剂中超声处理，在去离子水中冲洗，再依次经过乙醇，丙酮和去离子水洗净，在洁净环境下烘烤至完全除去水分，用紫外光合臭氧清洗，再用氧等离子处理30秒。
把上述带有阳极的玻璃基片至于真空腔内，抽真空，在ITO上面蒸镀HIL(5nm)作为空穴注入层130，蒸镀速率为0.1nm/s。
在空穴注入层上面蒸镀化合物HT，形成80nm厚的空穴传输层140，蒸镀速率为0.1nm/s，
在空虚传输层上面蒸镀EB，形成10nm厚的电子阻挡层150。蒸镀速率为0.1nm/s。
在空穴阻挡层上蒸镀30nm厚的发光层160，其中，BH为主体发光材料，而以2％重量比的BD作为掺杂客体材料，蒸镀速率为0.1nm/s。
在发光层上蒸镀30nm厚的50％重量比化合物1和50％重量比LiQ作为电子传输层170。蒸镀速率为0.1nm/s，
在电子传输层上蒸镀1nm厚的LiQ作为电子注入层180。
在电子注入层蒸镀100nm厚掺杂比为10：1的镁银作为器件阴极190。
实施例14-24
与实施例13的区别仅在于，将化合物1换成本发明其它化合物作为电子传输材料。
对比例1
与实施例13的区别仅在于，将化合物1换成化合物TPBI作为电子传输材料。
器件中所述结构式如下：

上述有机材料都是现有的已知材料，由市场采购获得。
表1器件结构

器件性能的测试：
所制备的器件用Photo Research PR655光谱仪测得在10mA/cm2电流密度下的工作电压，效率，发射波长，以及测量在15mA/cm2电流 密度下亮度变成初始亮度95％的时间(T95)，具体表2所示。
表2器件性能参数
从表2可以看出，利用本发明电子传输材料制备的有机电致发光器件，电压降低了，电压降低0.3-0.4V，电流效率提升，在15mA/cm2的电流密度下T95从51小时提升到76-119小时，寿命大幅提高。本发明的化合物显示出了良好的性能，这是由于唑类跟三嗪连接，有利于增加材料的稳定性和提升共轭，提高材料的电子迁移率，增强器件空穴和电子的平衡，可以有效地把电子传输到发光层，进而提升器件的性能。
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思做出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技 术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。

Claims (10)

  1. 一种含有唑类的有机化合物，其特征在于，其结构如结构式I所示，
    结构式I中，Ar1-Ar3为C6-C30取代或者未取代的芳基，C3-C30取代或者未取代的杂芳基中的一种；
    Z1-Z3中一个以上为N,其余为CH；
    L为单键，C6-C30取代或者未取代的芳基，C3-C30取代或者未取代的杂芳基中的一种；
    A为CR101R102，亚乙基，亚乙烯基，亚苯基，O，S，SO2，Se或者NR103；R101-R103为C1-C20的取代或未取代的烷基，C3-C20的取代或未取代的环烷基，C6-C30的取代或者未取代的芳基，C3-C30的取代或者未取代的杂芳基中的一种；R101和R102可以通过化学键连接；
    B为-NR104，-O-或者-S-；R104为C1-C20的取代或未取代的烷基，C3-C20的取代或未取代的环烷基，C6-C30的取代或者未取代的芳基，C3-C30的取代或者未取代的杂芳基中的一种。
  2. 根据权利要求1所述的含有唑类的有机化合物，其特征在于，Ar1-Ar3为苯基，甲苯基，联苯基，萘基，菲基，蒽基，苝基，荧蒽基，芘基，苯基萘基，萘基苯基，二苯基苯基，9，9-二甲基芴基，9， 9-二苯基芴基，9，9-螺二芴基，苯并呋喃基，苯并噻吩基，二苯并呋喃基，二苯并噻吩基，苯并菲基，螺[芴-9,9'-氧杂蒽]，吡啶基，苄基苯基，吡啶基苯基，吲哚基，咔唑吲哚基，芴咔唑基、咪唑基，噁唑基，噻唑基，噻二唑基，喹啉基，异喹啉基，喹唑啉基，喹喔啉基，氮杂二苯并呋喃基，氮杂二苯并噻吩基中的一种，以上芳基和杂芳基还可以进一步为C1-C12的烷基取代。
  3. 根据权利要求1所述的含有唑类的有机化合物，其特征在于，L为单键，苯基，萘基，联苯基，蒽基，9，9-二甲基芴基，9，9-二苯基芴基，9，9-螺二芴基，苯并呋喃基或者二苯并噻吩基。
  4. 根据权利要求1所述的含有唑类的有机化合物，其特征在于，R101-R104为甲基，乙基，异丙基，丙基，丁基，苯基，联苯基，萘基或者甲苯基。
  5. 一种权利要求1所述的含有唑类的有机化合物的应用，其特征在于，其可用于合成有机电致发光器件，所述的有机电致发光器件包括阳极、阴极和有机层；有机层包含发光层、空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层以上。
  6. 根据权利要求5所述的含有唑类的有机化合物的应用，其特征在于，所述的有机层中至少有一层含有结构式Ⅰ所示的含唑类化合物。
  7. 根据权利要求6所述的含有唑类的有机化合物的应用，其特征在于，所述的有机层的发光层中含有结构式Ⅰ所示的含唑类化合物。
  8. 根据权利要求6所述的含有唑类的有机化合物的应用，其特征在于，所述的有机层电子传输层或者电子注入层中含有结构式Ⅰ所示的含唑类化合物。
  9. 根据权利要求6所述的含有唑类的有机化合物的应用，其特征在于，所述的有机层中空穴阻挡层含有结构式Ⅰ所示的含唑类化合物。
  10. 根据权利要求5所述的含有唑类的有机化合物的应用，其特征在于，含有结构式Ⅰ所示的含唑类化合物还可被用于生产有机太阳能电池、有机薄膜晶体管、有机光检测器、有机场效应晶体管、有机集成电路和有机光感受器。
PCT/CN2023/088564 2022-04-18 2023-04-17 一种含有唑类的有机化合物及其应用 WO2023202502A1 (zh)

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CN114702484A (zh) * 2022-04-18 2022-07-05 上海传勤新材料有限公司 一种含有唑类的有机化合物及其应用

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