WO2016173019A1 - 含有吩恶噻结构的共轭化合物及其制备方法与有机电致发光二极管器件 - Google Patents

含有吩恶噻结构的共轭化合物及其制备方法与有机电致发光二极管器件 Download PDF

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WO2016173019A1
WO2016173019A1 PCT/CN2015/079538 CN2015079538W WO2016173019A1 WO 2016173019 A1 WO2016173019 A1 WO 2016173019A1 CN 2015079538 W CN2015079538 W CN 2015079538W WO 2016173019 A1 WO2016173019 A1 WO 2016173019A1
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thiophene structure
conjugated
conjugated compound
compound containing
mmol
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李先杰
吴元均
苏仕健
刘明
刘坤坤
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深圳市华星光电技术有限公司
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Priority to US14/763,827 priority Critical patent/US9634260B2/en
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Definitions

  • the invention belongs to the technical field of electroluminescent materials, and in particular relates to a conjugated compound containing a thiophene structure, a preparation method thereof and an organic electroluminescent diode device.
  • OLED Organic Light-Emitting Diode
  • the research began in the 1950s. Until 1987, Dr. Deng Qingyun of Kodak Company of the United States adopted the sandwich device structure in US 4,356,429.
  • the OLED device was developed with a luminance of 1000 cd/m 2 driven by a 10 V DC voltage. OLED has achieved epoch-making development. In the past two decades, OLED devices using novel illuminants, especially organic-heavy metal complex phosphorescent emitters, have achieved great success.
  • the classical blue organic fluorescent material can be divided into n-type molecules and p-type molecules in molecular structure. They either appear as electrons in the device work or appear as hole-bearing, so it is difficult to implement carriers. The balance leads to low current efficiency and quantum efficiency of the device.
  • Simple design of Donor-Acceptor (DA) type molecules although it is possible to achieve bipolar transmission, to achieve the purpose of balancing carriers, but due to the intramolecular charge transfer between the electron donor unit and the electrophilic unit, the compound The band gap is narrowed, resulting in a red shift of the luminescence peak, making it difficult to obtain an ideal blue luminescence.
  • DA Donor-Acceptor
  • the object of the present invention is to provide a conjugated compound containing a thiophene structure, which is an organic small molecule, has a single structure, has a determined molecular weight, is fluorescent, and has good solubility and film forming properties.
  • a light-emitting layer material of an organic electroluminescent diode As a light-emitting layer material of an organic electroluminescent diode.
  • Another object of the present invention is to provide a process for producing a conjugated compound containing a thiophene structure, which is easy to handle, has a simple purification step, and has a high yield of a target product.
  • Another object of the present invention is to provide an organic electroluminescent diode device, wherein the conjugated compound containing a thiophene structure is used as a light-emitting layer material in an organic photoelectric device such as an organic light-emitting diode, thereby improving luminous efficiency and stability of the device. Sex.
  • the present invention provides a conjugated compound containing a thiophene structure, which has a chemical structure of one of the structural formulae shown below:
  • R 1 to R 8 is an electron donating conjugated aromatic unit, an alkyl-substituted conjugated aromatic unit, an alkoxy-substituted conjugated aromatic unit, or an alkyl group.
  • a conjugated aromatic unit substituted simultaneously with an alkoxy group which is an aromatic ring composed of a vinylene group, an acetylene group, a hydrocarbon atom, an aromatic heterocyclic ring composed of a carbon nitrogen hydrogen atom, and a carbon nitrogen
  • the present invention also provides a method for preparing a conjugated compound containing a thiophene structure as described above, first preparing an intermediate containing a thiophene structure, and then coextending an intermediate containing a thiophene structure with a rich electron
  • the conjugated aromatic unit compound is prepared by a Suzuki coupling reaction (Suzuki reaction), a Buchwald-Hartwig coupling reaction (Buchwald-Hartwig reaction) or a copper-catalyzed halogenated aromatic amination reaction.
  • a conjugated compound of a thia structure is prepared by a Suzuki coupling reaction (Suzuki reaction), a Buchwald-Hartwig coupling reaction (Buchwald-Hartwig reaction) or a copper-catalyzed halogenated aromatic amination reaction.
  • the intermediate containing a thiophene structure is a compound M1, M2, M3 or M4, and the structural formulas of the compounds M1, M2, M3 and M4 are as follows:
  • the preparation method of the intermediate M1 containing the thiophene structure is specifically: adding 3 g of 2-hydroxy-benzenethiol and 120 mL of anhydrous N,N-dimethylformamide to a 250 mL three-necked flask, and stirring in an Ar atmosphere. Under gas protection, 5.47 g of potassium t-butoxide was slowly added, and after stirring for 0.5 hours, 7.01 g of 2,5-dibromonitrobenzene was added, and after stirring for 20 minutes, it was heated to reflux overnight, and most of the anhydrous was removed by a rotary evaporator. After N,N-dimethylformamide, extracted with deionized water and dichloromethane, and separated by silica gel column to give intermediate M1 as a white solid;
  • the preparation method of the intermediate M2 containing the thiophene structure is specifically: adding 4.2 g of the intermediate M1 and 50 mL of glacial acetic acid into a 100 mL three-necked flask, stirring, adding 10 mL of 30% hydrogen peroxide, heating under reflux overnight, cooling and adding Ethanol, suction filtration and drying gave intermediate M2 as a white solid.
  • the preparation method of the intermediate M3 containing the thiophene structure is specifically: adding 5 g of 5-bromo-2-hydroxy-benzenethiol and 120 mL of anhydrous N,N-dimethylformamide in a 250 mL three-necked flask, in Ar After stirring in an atmosphere, 5.47 g of potassium t-butoxide was slowly added under a gas atmosphere, and after stirring for 0.5 hour, 7.01 g of 2,5-dibromonitrobenzene was added, and after stirring for 20 minutes, it was heated to reflux overnight, and removed by a rotary evaporator. After a large portion of anhydrous N,N-dimethylformamide, extracted with deionized water and dichloromethane, and separated by silica gel chromatography to give intermediate M3 as a white solid;
  • the preparation method of the intermediate M4 containing the thiophene structure is specifically: adding 4.6 g of the intermediate M3 and 50 mL of glacial acetic acid into a 100 mL three-necked flask, stirring, adding 10 mL of 30% hydrogen peroxide, heating under reflux overnight, cooling and adding Ethanol, suction filtration and drying gave intermediate M4 as a white solid.
  • the compound containing an electron-rich conjugated aromatic unit is nitrogen nitromethyl vinyl urea, 9,10-dihydro-9,9-dimethyl acridine, N,N-diphenyl-4-(4) ,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline, bis(4-t-butylphenyl)amine, phenothiazine, 9-phenyl -3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole, phenoxazine or nitrogen nitroformylurea.
  • the present invention also provides an organic electroluminescent diode device comprising a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode, which are sequentially disposed from bottom to top, wherein the light emitting
  • the layer contains the conjugated compound containing a thiophene structure according to claim 1.
  • the luminescent layer is formed by vacuum evaporation or solution coating.
  • the substrate is a glass substrate
  • the material of the anode is indium tin oxide
  • the cathode is a two-layer composite structure composed of a lithium fluoride layer and an aluminum layer.
  • the material of the hole injection layer is HAT-CN
  • the material of the hole transport layer is NPB and TCTA
  • the material of the electron transport layer is TPBI
  • the structural formula of the compounds HAT-CN, NPB, TCTA and TPBI They are:
  • the present invention has the following advantages and benefits:
  • the conjugated compound containing a thiophene structure of the present invention has a single structure, a molecular weight is determined, is easy to be purified, has good reproducibility of multiple times of synthesis, and is convenient for studying a structure-performance relationship;
  • the conjugated compound containing a thiophene structure is a small molecule material having a lower sublimation temperature and a decomposition temperature, and the film morphology is stable;
  • the electricity absorption of the thiophene unit can be adjusted, thereby achieving effective regulation of intramolecular charge transfer, molecular energy level, and carrier transport performance.
  • FIG. 2 is a graph showing a current density-voltage-luminance relationship of an organic electroluminescent diode device containing a thiophene structure-containing conjugated compound P3 as a light-emitting layer material prepared in Example 5 of the present invention
  • Figure 3 is a graph showing the luminance-current efficiency/power efficiency of an organic electroluminescent diode device containing a thiophene structure-containing conjugated compound P3 as a light-emitting layer material prepared in Example 5 of the present invention.
  • M2 M1 and 50 mL of glacial acetic acid were added to a 100 mL three-necked flask. After stirring, 10 mL of 30% hydrogen peroxide was added, and the mixture was heated to reflux overnight. After cooling, ethanol was added, filtered, and dried to give a white solid M2 (4.57 g), yield 97%. .
  • M4 M3 and 50 mL of glacial acetic acid were added to a 100 mL three-necked flask. After stirring, 10 mL of 30% hydrogen peroxide was added, and the mixture was heated to reflux overnight. After cooling, ethanol was added, suction filtration, and drying to obtain a white solid. M4 (4.50 g), yield 97%.
  • OLED organic electroluminescent diode
  • the organic electroluminescent diode device includes a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode, which are sequentially disposed from bottom to top, wherein the substrate is a glass substrate.
  • the material of the anode is indium tin oxide (ITO).
  • ITO indium tin oxide
  • the substrate and the anode together constitute an ITO glass. After the ultrasonic cleaning, the ITO glass is treated with oxygen-plasma, and the sheet resistance of the ITO glass is 10 ⁇ /cm 2 .
  • the material of the hole injecting layer is HAT-CN, the material of the hole transporting layer is NPB and TCTA, the material of the light emitting layer is the compound P3 prepared in Example 5, and the material of the electron transporting layer is TPBI.
  • the cathode is a two-layer structure composed of a lithium fluoride (LiF) layer and an aluminum (Al) layer.
  • NPB N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine
  • TCTA 4,4',4" Tris(oxazol-9-yl)triphenylamine
  • TPBI refers to 1,3,5-tris(1-phenyl-1-H-benzo[d]imidazol-2-)benzene.
  • CE lumen efficiency
  • EQE external quantum efficiency
  • CIE CIE XYZ color space

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Abstract

本发明涉及一种含有吩恶噻结构的共轭化合物及其制备方法与有机电致发光二极管器件，所述含有吩恶噻结构的共轭化合物具有如下所示的结构通式之一的化学结构。本发明通过选择多种含有富电子共轭芳香单元的化合物与含有吩恶噻基团的中间体通过Suzuki偶联反应、Buchwald-Hartwig偶联反应或者铜催化卤代芳烃氨基化反应，获得含有吩恶噻结构的共轭化合物。本发明所制备的新型化合物，具有荧光性，因此可应用于发光层材料制作有机电致发光二极管。

Description

含有吩恶噻结构的共轭化合物及其制备方法与有机电致发光二极管器件 技术领域
本发明属于电致发光材料技术领域，特别涉及一种含有吩恶噻结构的共轭化合物及其制备方法和有机电致发光二极管器件。
背景技术
有机电致发光二极管(OLED,Organic Light-Emitting Diode)因具有高效、低电压驱动，易于大面积制备及全色显示等优点具有广阔的应用前景，得到人们的广泛关注。该研究始于上个世纪50年代，直到1987年美国柯达公司的邓青云博士等在专利US4356429中采用三明治器件结构，研制出的OLED器件在10V直流电压驱动下发光亮度达到1000cd/m2，使OLED获得了划时代的发展。在过去的二十年里，采用新型发光体，尤其是有机-重金属配合物磷光发射体的OLED器件取得了不小的成功。然而，由于较难获得能带隙磷光体，目前能够满足高效纯蓝色发光(yCIE<0.15，yCIE+xCIE<0.30)的磷光发射体数量十分稀少，并且相对于绿色和红色磷光材料，要选择针对蓝色磷光的具有高三线态能的主体材料也具有相当的挑战性。此外，蓝色磷光器件寿命上的不稳定也很大程度上限制了它的实际应用。因此，发展高效、稳定的蓝色荧光发光体仍然十分必要。考虑到多方面的因素，采用蓝色荧光材料可以使OLED全彩显示或者白光照明的实用化生产降低成本以及简化制造工序。但是以往经典的蓝色有机荧光材料从分子结构上可以划分为n-型分子，p-型分子，他们在器件工作中要么表现为电子主导，要么表现为空穴主导，因而难以实现载流子的平衡，从而导致器件电流效率和量子效率偏低。而简单的设计Donor-Acceptor(D-A)型分子，虽然可能实现双极性传输，达到平衡载流子的目的，但是由于给电子单元和亲电子单元之间的分子内电荷转移作用，会使得化合物的带隙变窄，导致发光峰红移，难以获得理想的蓝色发光。要克服这一困难，必须选择具有合适强度给电性的给体和亲电性的受体组合成分子，把分子内电荷转移控制在一定的程度内，才能获得性能好，色纯度高的蓝色有机荧光材料。
截止目前，用于有机光电器件的绝大多数的蒸镀分子的骨架为硫氧 芴、磷氧、三苯胺等单元为核，而以吩恶噻为核的有机发光小分子却鲜有报道。
至今有机发光二极管已经取得了长足的进展，通过荧光磷光杂化，我们可以获得器件结构简单效率很高的白光器件。而这种荧光磷光杂化器件的效率很大程度上依赖于荧光的效率，因此发展高效的荧光材料依然具有举足轻重的意义。基于此，我们开发了一系列具有新颖结构且易于合成的荧光发光材料。
发明内容
本发明的目的在于提供一种含有吩恶噻结构的共轭化合物，该类化合物为有机小分子，结构单一，分子量确定，具有荧光性，且具有较好的溶解性及成膜性，因此可作为有机电致发光二极管的发光层材料。
本发明另一目的在于提供一种含有吩恶噻结构的共轭化合物的制备方法，该方法易于操作，纯化步骤简单，且获得目标产物的产率较高。
本发明又一目的在于提供一种有机电致发光二极管器件，将该含有吩恶噻结构的共轭化合物作为发光层材料应用于有机发光二极管等有机光电器件中，从而提高器件的发光效率及稳定性。
为实现上述发明目的，本发明提供一种含有吩恶噻结构的共轭化合物，具有如下所示的结构通式之一的化学结构：
式一
Figure PCTCN2015079538-appb-000001
式二
Figure PCTCN2015079538-appb-000002
以上式一与式二中，R1-R8中至少有一个为具有给电子性的共轭芳香单元、烷基取代的共轭芳香单元、烷氧基取代的共轭芳香单元、或烷基和烷氧基同时取代的共轭芳香单元，所述共轭芳香单元为由乙烯撑基、乙炔撑 基、碳氢原子构成的芳香环、由碳氮氢原子构成的芳香杂环、由碳氮氧氢原子构成的芳香杂环、由碳硫氢原子构成的芳香杂环和由碳硅氢原子构成的芳香杂环中的一种或多种的组合。
本发明还提供一种如上所述的含有吩恶噻结构的共轭化合物的制备方法，首先制备出含有吩恶噻结构的中间体，然后将含有吩恶噻结构的中间体与含有富电子共轭芳香单元的化合物通过Suzuki偶联反应(铃木反应)、Buchwald-Hartwig偶联反应(布赫瓦尔德-哈特维希反应)或者铜催化卤代芳烃氨基化反应来制备得到所述含有吩恶噻结构的共轭化合物。
所述含有吩恶噻结构的中间体为化合物M1、M2、M3或M4，所述化合物M1、M2、M3和M4的结构式分别如下：
Figure PCTCN2015079538-appb-000003
Figure PCTCN2015079538-appb-000004
所述含有吩恶噻结构的中间体M1，M2的制备方法及反应式如下：
Figure PCTCN2015079538-appb-000005
所述含有吩恶噻结构的中间体M1的制备方法具体为：在250mL三口瓶中加入3g 2-羟基-苯硫醇和120mL无水N,N-二甲基甲酰胺，在Ar气氛中搅拌，在气体保护下，缓慢加入5.47g叔丁醇钾，搅拌0.5小时后，加入7.01g 2,5-二溴硝基苯，搅拌20分钟后，加热回流过夜，通过旋转蒸发仪除去大部分无水N,N-二甲基甲酰胺后，用去离子水和二氯甲烷萃取，过硅胶色谱柱分离，得到白色固体状的中间体M1；
所述含有吩恶噻结构的中间体M2的制备方法具体为：在100mL三口瓶中加入4.2g中间体M1和50mL冰醋酸，搅拌后，加入10mL的30％双氧水，加热回流过夜，冷却后加入乙醇，抽滤，干燥得到白色固体状的中间体M2。
所述含有吩恶噻结构的中间体M3，M4的制备方法及反应式如下：
Figure PCTCN2015079538-appb-000006
所述含有吩恶噻结构的中间体M3的制备方法具体为：在250mL三口瓶中加入5g 5-溴-2-羟基-苯硫醇和120mL无水N,N-二甲基甲酰胺，在Ar气氛中搅拌，在气体保护下，缓慢加入5.47g叔丁醇钾，搅拌0.5小时后，加入7.01g 2,5-二溴硝基苯，搅拌20分钟后，加热回流过夜，通过旋转蒸发仪除去大部分无水N,N-二甲基甲酰胺后，用去离子水和二氯甲烷萃取，过硅胶色谱柱分离，得到白色固体状的中间体M3；
所述含有吩恶噻结构的中间体M4的制备方法具体为：在100mL三口瓶中加入4.6g中间体M3和50mL冰醋酸，搅拌后，加入10mL的30％双氧水，加热回流过夜，冷却后加入乙醇，抽滤，干燥得到白色固体状的中间体M4。
所述含有富电子共轭芳香单元的化合物为氮氮二甲基乙烯基脲、9,10-二氢-9,9-二甲基吖啶、N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)苯胺、双(4-叔丁基苯基)胺、吩噻嗪、9-苯基-3-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)咔唑、吩恶嗪或氮氮二甲基乙烯基脲。
本发明还提供一种有机电致发光二极管器件，包括从下到上依次设置的基板、阳极、空穴注入层、空穴传输层、发光层、电子传输层、及阴极，其中，所述发光层中含有如权利要求1所述的含有吩恶噻结构的共轭化合物。
所述发光层采用真空蒸镀或者溶液涂覆的方法形成。
所述基板为玻璃基板，所述阳极的材料为氧化铟锡，所述阴极为氟化锂层与铝层构成的双层复合结构。
所述空穴注入层的材料为HAT-CN，所述空穴传输层的材料为NPB和TCTA，所述电子传输层的材料为TPBI，所述化合物HAT-CN，NPB，TCTA和TPBI的结构式分别为：
Figure PCTCN2015079538-appb-000007
Figure PCTCN2015079538-appb-000008
相比于已有材料和技术，本发明具有如下优点和有益效果：
(1)本发明的含有吩恶噻结构的共轭化合物，结构单一，分子量确定，便于提纯，多次合成再现性好，且便于研究结构-性能的关系；
(2)该含有吩恶噻结构的共轭化合物为小分子材料，具有较低的升华温度和分解温度，薄膜形态稳定；
(3)通过改变吩恶噻结构上连接的取代基的化学结构可以有效地调控该化合物的共轭长度和发光的颜色；
(4)通过改变具有芳香结构的取代基上的修饰基团，可进一步改善该化合物的物理特性以及基于其的光电器件性能；
(5)通过改变吩恶噻结构中硫原子的价态，可调整吩恶噻单元的吸电性，从而实现对分子内电荷转移、分子能级、以及载流子传输性能的有效调控。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。
附图中，
图1为本发明具体实施例5中所制备的含有吩恶噻结构的共轭化合物P3在二氯甲烷溶液中的吸收和发射光谱；
图2为本发明具体实施例5中所制备的含有吩恶噻结构的共轭化合物P3作为发光层材料的有机电致发光二极管器件的电流密度-电压-亮度关系曲线图；
图3为本发明具体实施例5中所制备的含有吩恶噻结构的共轭化合物P3作为发光层材料的有机电致发光二极管器件的亮度-电流效率/功率效率关系曲线图。
具体实施方式
本发明中所用的未注明的一些原料均为市售商品。一些化合物的制备方法将在实施案例中描述。下面结合具体实施例对本发明作进一步具体详细描述，但本发明的实施方式不限于此。
实施例1：
含有吩恶噻结构的中间体M1，M2的制备，反应式如下：
Figure PCTCN2015079538-appb-000009
M1：在250mL三口瓶中加入2-羟基-苯硫醇(3g,23.8mmol)和120mL无水N,N-二甲基甲酰胺，在Ar气氛中搅拌。在气体保护下，缓慢加入叔丁醇钾(5.47g,48.7mmol)。搅拌0.5小时后，加入2,5-二溴硝基苯(7.01g,25mmol)，搅拌20分钟后，加热回流过夜。通过旋转蒸发仪除去大部分无水N,N-二甲基甲酰胺后，用去离子水和二氯甲烷萃取，过硅胶色谱柱分离，得到白色固体M1(4.2g)，产率63％。
M2：在100mL三口瓶中加入M1和50mL冰醋酸，搅拌后，加入10mL的30％双氧水，加热回流过夜，冷却后加入乙醇，抽滤，干燥得到白色固体M2(4.57g)，产率97％。
实施例2：
含有吩恶噻结构的中间体M3，M4的制备，反应式如下：
Figure PCTCN2015079538-appb-000010
M3：在250mL三口瓶中加入5-溴-2-羟基-苯硫醇(5g,23.8mmol)和120mL无水N,N-二甲基甲酰胺，在Ar气氛中搅拌。在气体保护下，缓慢加入叔丁醇钾(5.47g,48.7mmol)。搅拌0.5小时后，加入2,5-二溴硝基苯(7.01g,25mmol)，搅拌20分钟后，加热回流过夜。通过旋转蒸发仪除去大部分无水N,N-二甲基甲酰胺后，用去离子水和二氯甲烷萃取，过硅胶色谱柱分离，得到白色固体M3(4.6g)，产率66％。
M4：在100mL三口瓶中加入M3和50mL冰醋酸，搅拌后，加入10mL的30％双氧水，加热回流过夜，冷却后加入乙醇，抽滤，干燥得到白色固 体M4(4.50g)，产率97％。
实施例3：
含有吩恶噻结构的共轭化合物P1的制备，反应式如下：
Figure PCTCN2015079538-appb-000011
在氮气气氛下，往100mL烧瓶中加入M1(1.06g,3.5mmol)，15mL氮氮二甲基乙烯基脲，碘化亚铜(0.56g)，碳酸钾(1.40g)，3,6-二叔丁基咔唑(1.17g,1.2equ)，18-冠醚-6(0.21g)，在160℃下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(0.995g，产率57％)。
实施例4：
含有吩恶噻结构的共轭化合物P2的制备，反应式如下：
Figure PCTCN2015079538-appb-000012
在氮气气氛下，往100mL烧瓶中加入M2(1.08g,3.5mmol)，15mL氮氮二甲基乙烯基脲，碘化亚铜(0.56g)，碳酸钾(1.40g)，3,6-二叔丁基咔唑(1.17g,1.2equ)，18-冠醚-6(0.21g)，在160℃下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(0.997g，产率56％)。
实施例5：
含有吩恶噻结构的共轭化合物P3的制备，反应式如下：
Figure PCTCN2015079538-appb-000013
在氮气气氛下，往100mL烧瓶中加入M3(1.26g,3.5mmol)，15mL氮氮二甲基乙烯基脲，碘化亚铜(0.56g)，碳酸钾(1.40g)，3,6-二叔丁基咔唑(2.34g,1.2equ)，18-冠醚-6(0.21g)，在160℃下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(1.47g，产率57％)。
实施例6：
含有吩恶噻结构的共轭化合物P4的制备，反应式如下：
Figure PCTCN2015079538-appb-000014
在氮气气氛下，往100mL烧瓶中加入M4(1.28g,3.5mmol)，15mL氮氮二甲基乙烯基脲，碘化亚铜(0.56g)，碳酸钾(1.40g)，3,6-二叔丁基咔唑(2.34g,1.2equ)，18-冠醚-6(0.21g)，在160℃下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(1.49g，产率55％)。
实施例7：
含有吩恶噻结构的共轭化合物P5的制备，反应式如下：
Figure PCTCN2015079538-appb-000015
在氩气气氛下向反应瓶中加入M1(1.04g,3.5mmol)和9,10-二氢-9,9-二甲基吖啶(3.5mmol，0.71g)，作为溶剂的100mL甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时。冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.24g，产率86％)。
实施例8：
含有吩恶噻结构的共轭化合物P6的制备，反应式如下：
Figure PCTCN2015079538-appb-000016
在氩气气氛下向反应瓶中加入M2(1.08g,3.5mmol)和9,10-二氢-9,9-二甲基吖啶(3.5mmol，0.71g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时。冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.29g，产率84％)。
实施例9：
含有吩恶噻结构的共轭化合物P7的制备，反应式如下：
Figure PCTCN2015079538-appb-000017
在氮气气氛下，往100ml烧瓶中加入M3(1.25g,3.5mmol)，9,10-二氢-9,9-二甲基吖啶(7mmol，1.4g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(2.01g，产率85％)。
实施例10：
含有吩恶噻结构的共轭化合物P8的制备，反应式如下：
Figure PCTCN2015079538-appb-000018
在氮气气氛下，往100mL烧瓶中加入M4(1.28g,3.5mmol)，9,10-二氢-9,9-二甲基吖啶(7mmol，1.4g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(2.0g，产率87％)。
实施例11：
含有吩恶噻结构的共轭化合物P9的制备，反应式如下：
Figure PCTCN2015079538-appb-000019
将M1(1.05g,3.5mmol)和N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)苯胺(1.3g 3.5mmol)加入到250mL单口烧瓶中，加入120ml甲苯、40ml乙醇和30ml 2M的碳酸钾水溶液，然后加入100mg的三苯基膦零价钯，通气半小时，置换出反应体系中的氧气，通气完毕密封，90-100℃加热反应18-24小时，降温，二氯甲烷萃取，有机相干燥，过短柱，石油醚:二氯甲烷＝1:1过柱，得白色固体1.48g，产率91％。
实施例12：
含有吩恶噻结构的共轭化合物P10的制备，反应式如下：
Figure PCTCN2015079538-appb-000020
将M2(1.08g,3.5mmol)和N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)苯胺(1.3g 3.5mmol)加入到250mL单口烧瓶中，加入120ml甲苯、40ml乙醇和30ml 2M的碳酸钾水溶液，然后加入100mg的三苯基膦零价钯，通气半小时，置换出反应体系中的氧气，通气完毕密封，90-100℃加热反应18-24小时，降温，二氯甲烷萃取，有机相干燥，过短柱，石油醚:二氯甲烷＝1:1过柱，得白色固体1.51g，产率90％。
实施例13：
含有吩恶噻结构的共轭化合物P11的制备，反应式如下：
Figure PCTCN2015079538-appb-000021
将M3(1.25g,3.5mmol)和N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)苯胺(2.6g,7mmol)加入到250mL单口烧瓶中，加入120mL甲苯、40ml乙醇和30ml 2M的碳酸钾水溶液，然后加入100mg的三苯基膦零价钯，通气半小时，置换出反应体系中的氧气，通气完毕密封，90-100℃加热反应18-24小时，降温，二氯甲烷萃取，有机相干燥，过短柱，石油醚:二氯甲烷＝1:1过柱，得白色固体2.10g，产率91％。
实施例14
含有吩恶噻结构的共轭化合物P12的制备，反应式如下：
Figure PCTCN2015079538-appb-000022
将M4(1.28g,3.5mmol)和N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)苯胺(2.6g,7mmol)加入到250mL单口烧瓶中，加入120ml甲苯、40mL乙醇和30ml 2M的碳酸钾水溶液，然后加入100mg的三苯基膦零价钯，通气半小时，置换出反应体系中的氧气，通气完毕密封，90-100℃加热反应18-24小时，降温，二氯甲烷萃取，有机相干燥，过短柱，石油醚:二氯甲烷＝1:1过柱，得白色固体2.15g，产率92％。
实施例15：
含有吩恶噻结构的共轭化合物P13的制备，反应式如下：
Figure PCTCN2015079538-appb-000023
在氩气气氛下向反应瓶中加入M1(1.05g,3.5mmol)，双(4-叔丁基苯基)胺(3.5mmol，1.0g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.50g，产率85％)。
实施例16：
含有吩恶噻结构的共轭化合物P14的制备，反应式如下：
Figure PCTCN2015079538-appb-000024
在氩气气氛下向反应瓶中加入M2(1.08g,3.5mmol)，双(4-叔丁基苯基)胺(3.5mmol，1.0g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔 丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.50g，产率85％)。
实施例17：
含有吩恶噻结构的共轭化合物P15的制备，反应式如下：
Figure PCTCN2015079538-appb-000025
在氩气气氛下向反应瓶中加入M3(1.20g,3.5mmol)，双(4-叔丁基苯基)胺(7mmol，2.0g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(2.9g，产率85％)。
实施例18：
含有吩恶噻结构的共轭化合物P16的制备，反应式如下：
Figure PCTCN2015079538-appb-000026
在氩气气氛下向反应瓶中加入M4(1.28g,3.5mmol)，双(4-叔丁基苯基)胺(7mmol，2.0g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(2.94g，产率83％)。
实施例19：
含有吩恶噻结构的共轭化合物P17的制备，反应式如下：
Figure PCTCN2015079538-appb-000027
在氩气气氛下向反应瓶中加入M1(1.05g,3.5mmol),吩噻嗪(3.5mmol，0.70g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.21g，产率84％)。
实施例20：
含有吩恶噻结构的共轭化合物P18的制备，反应式如下：
Figure PCTCN2015079538-appb-000028
在氩气气氛下向反应瓶中加入M2(1.08g,3.5mmol),吩噻嗪(3.5mmol，0.70g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.21g，产率84％)。
实施例21：
含有吩恶噻结构的共轭化合物P19的制备，反应式如下：
Figure PCTCN2015079538-appb-000029
在氩气气氛下向反应瓶中加入M3(1.20g,3.5mmol),吩噻嗪(7mmol，1.40g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.89g，产率84％)。
实施例22：
含有吩恶噻结构的共轭化合物P20的制备，反应式如下：
Figure PCTCN2015079538-appb-000030
在氩气气氛下向反应瓶中加入M4(1.08g,3.5mmol),吩噻嗪(7mmol，1.40g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.94g，产率85％)。
实施例23：
含有吩恶噻结构的共轭化合物P21的制备，反应式如下：
Figure PCTCN2015079538-appb-000031
在氩气气氛下向反应瓶中加入M1(1.05g,3.5mmol)和9-苯基-3-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)咔唑(3.5mmol，1.3g)，30毫升甲苯和15毫升四氢呋喃，再加入20毫升重量浓度为10％的碳酸钠水溶液，50毫克四(三苯基磷)合钯，加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.42g，产率86％)。
实施例24：
含有吩恶噻结构的共轭化合物P22的制备，反应式如下：
Figure PCTCN2015079538-appb-000032
在氩气气氛下向反应瓶中加入M2(1.08g,3.5mmol)和9-苯基-3-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)咔唑(3.5mmol，1.3g)，30毫升甲苯和15毫升四氢呋喃，再加入20毫升重量浓度为10％的碳酸钠水溶液，50毫克四(三苯基磷)合钯，加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.40g，产率85％)。
实施例25：
含有吩恶噻结构的共轭化合物P23的制备，反应式如下：
Figure PCTCN2015079538-appb-000033
在氩气气氛下向反应瓶中加入M3(1.25g,3.5mmol),9-苯基-3-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)咔唑(7mmol，2.6g),30毫升甲苯和15毫升四氢呋喃，再加入20毫升重量浓度为10％的碳酸钠水溶液，50毫克四(三苯基磷)合钯，加热回流下搅拌反应24小时。冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(2.00g，产率85％)。
实施例26：
含有吩恶噻结构的共轭化合物P24的制备，反应式如下：
Figure PCTCN2015079538-appb-000034
在氩气气氛下向反应瓶中加入M4(1.28g,3.5mmol),9-苯基-3-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)咔唑(7mmol，2.6g),30毫升甲苯和15毫升四氢呋喃，再加入20毫升重量浓度为10％的碳酸钠水溶液，50毫克四(三苯基磷)合钯，加热回流下搅拌反应24小时。冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(2.06g，产率86％)。
实施例27：
含有吩恶噻结构的共轭化合物P25的制备，反应式如下：
Figure PCTCN2015079538-appb-000035
在氩气气氛下向反应瓶中加入M1(1.05g,3.5mmol)，吩恶嗪(3.5mmol，0.68g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.21g，产率84％)。
实施例28：
含有吩恶噻结构的共轭化合物P26的制备，反应式如下：
Figure PCTCN2015079538-appb-000036
在氩气气氛下向反应瓶中加入M2(1.05g,3.5mmol),吩恶嗪(3.5mmol，0.68g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.21g，产率84％)。
实施例29：
含有吩恶噻结构的共轭化合物P27的制备，反应式如下：
Figure PCTCN2015079538-appb-000037
在氩气气氛下向反应瓶中加入M3(1.25g,3.5mmol),吩恶嗪(7mmol，1.36g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.65g，产率84％)。
实施例30：
含有吩恶噻结构的共轭化合物P28的制备，反应式如下：
Figure PCTCN2015079538-appb-000038
在氩气气氛下向反应瓶中加入M4(1.28g,3.5mmol),吩恶嗪(7mmol，1.36g)，作为溶剂的100毫升甲苯，60毫克醋酸钯，三叔丁基磷(0.5mmol，0.11g)和0.75克碳酸钾。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体，再经过干燥后于真空下升华得到高纯度产物(1.68g，产率83％)。
实施例31：
含有吩恶噻结构的共轭化合物P29的制备，反应式如下：
Figure PCTCN2015079538-appb-000039
在氮气气氛下，往100mL烧瓶中加入M1(1.05g,3.5mmol)，15mL氮氮二甲基乙烯基脲，碘化亚铜(0.56g)，碳酸钾(1.40g)，9-氢-3-9’-双咔唑(3.6mmol，1.2g)，18-冠醚-6(0.21g)，在160℃下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(0.997g，产率56％)。
实施例32：
含有吩恶噻结构的共轭化合物P30的制备，反应式如下：
Figure PCTCN2015079538-appb-000040
在氮气气氛下，往100mL烧瓶中加入M2(1.08g,3.5mmol)，15mL氮氮二甲基乙烯基脲，碘化亚铜(0.56g)，碳酸钾(1.40g)，9-氢-3-9’-双咔唑(3.6mmol，1.2g)，18-冠醚-6(0.21g)，在160℃下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(1.00g，产率57％)。
实施例33：
含有吩恶噻结构的共轭化合物P31的制备，反应式如下：
Figure PCTCN2015079538-appb-000041
在氮气气氛下，往100mL烧瓶中加入M3(1.25g,3.5mmol)，15mL氮氮二甲基乙烯基脲，碘化亚铜(0.56g)，碳酸钾(1.40g)，9-氢-3-9’-双咔唑(7.2mmol，2.4g)，18-冠醚-6(0.21g)，在160℃下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(1.63g，产率56％)。
实施例34：
含有吩恶噻结构的共轭化合物P32的制备，反应式如下：
Figure PCTCN2015079538-appb-000042
在氮气气氛下，往100mL烧瓶中加入M4(1.28g,3.5mmol)，15mL氮氮二甲基乙烯基脲，碘化亚铜(0.56g)，碳酸钾(1.40g)，9-氢-3-9’-双咔唑(7.2mmol，2.4g)，18-冠醚-6(0.21g)，在160℃下搅拌反应24小时。用二氯甲烷萃取，分液，合并有机相，用无水硫酸镁干燥，抽滤，所得的滤液在减压下除去溶剂，柱分离得到白色产物，再经过干燥后于真空下升华得到高纯度产物(1.70g，产率55％)。
实施例35：
有机电致发光二极管(OLED)器件的制备：
所述有机电致发光二极管器件包括从下到上依次设置的基板、阳极、空穴注入层、空穴传输层、发光层、电子传输层、及阴极，其中，所述基板为玻璃基板，所述阳极的材料为氧化铟锡(ITO)，所述基板与阳极共同构成ITO玻璃，所述ITO玻璃经过超声波清洗后，用氧-等离子体处理，ITO玻璃的方块电阻为10Ω/cm2。所述空穴注入层的材料为HAT-CN，所述空穴 传输层的材料为NPB和TCTA，所述发光层的材料为实施例5所制备的化合物P3，所述电子传输层的材料为TPBI。所述阴极为氟化锂(LiF)层与铝(Al)层构成的双层结构。
其中，NPB指N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺，TCTA指4,4',4”-三(咔唑-9-基)三苯胺，TPBI指1,3,5-三(1-苯基-1-H-苯并[d]咪唑-2-)苯。
所述化合物HAT-CN，NPB，TCTA和TPBI的结构式分别为：
Figure PCTCN2015079538-appb-000043
在阳极和阴极之间施加正偏压，在不同电流下测试器件的特性，测试结果如下表1所示。
表1 基于化合物P3为发光层材料的有机电致发光器件的性能列表
Figure PCTCN2015079538-appb-000044
其中CE代表流明效率，EQE代表外量子效率，CIE为CIE XYZ色彩 空间。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种含有吩恶噻结构的共轭化合物，具有如下所示的结构通式之一的化学结构：
    式一
    Figure PCTCN2015079538-appb-100001
    式二
    Figure PCTCN2015079538-appb-100002
    以上式一与式二中，R1-R8中至少有一个为具有给电子性的共轭芳香单元、烷基取代的共轭芳香单元、烷氧基取代的共轭单元、或烷基和烷氧基同时取代的共轭芳香单元，所述共轭芳香单元为由乙烯撑基、乙炔撑基、碳氢原子构成的芳香环、由碳氮氢原子构成的芳香杂环、由碳氮氧氢原子构成的芳香杂环、由碳硫氢原子构成的芳香杂环和由碳硅氢原子构成的芳香杂环中的一种或多种的组合。
  2. 一种如权利要求1所述的含有吩恶噻结构的共轭化合物的制备方法，首先制备出含有吩恶噻结构的中间体，然后将含有吩恶噻结构的中间体与含有富电子共轭芳香单元的化合物通过Suzuki偶联反应、Buchwald-Hartwig偶联反应或者铜催化卤代芳烃氨基化反应来制备得到所述含有吩恶噻结构的共轭化合物。
  3. 如权利要求2所述的含有吩恶噻结构的共轭化合物的制备方法，其中，所述含有吩恶噻结构的中间体为化合物M1、M2、M3或M4，所述化合物M1、M2、M3和M4的结构式分别如下：
    Figure PCTCN2015079538-appb-100003
  4. 如权利要求3所述的含有吩恶噻结构的共轭化合物的制备方法，其中，所述含有吩恶噻结构的中间体M1，M2的制备方法及反应式如下：
    Figure PCTCN2015079538-appb-100004
    所述含有吩恶噻结构的中间体M1的制备方法具体为：在250mL三口瓶中加入3g 2-羟基-苯硫醇和120mL无水N,N-二甲基甲酰胺，在Ar气氛中搅拌，在气体保护下，缓慢加入5.47g叔丁醇钾，搅拌0.5小时后，加入7.01g 2,5-二溴硝基苯，搅拌20分钟后，加热回流过夜，通过旋转蒸发仪除去大部分无水N,N-二甲基甲酰胺后，用去离子水和二氯甲烷萃取，过硅胶色谱柱分离，得到白色固体状的中间体M1；
    所述含有吩恶噻结构的中间体M2的制备方法具体为：在100mL三口瓶中加入4.2g中间体M1和50mL冰醋酸，搅拌后，加入10mL的30％双氧水，加热回流过夜，冷却后加入乙醇，抽滤，干燥得到白色固体状的中间体M2。
  5. 如权利要求3所述的含有吩恶噻结构的共轭化合物的制备方法，其中，所述含有吩恶噻结构的中间体M3，M4的制备方法及反应式如下：
    Figure PCTCN2015079538-appb-100005
    所述含有吩恶噻结构的中间体M3的制备方法具体为：在250mL三口 瓶中加入5g 5-溴-2-羟基-苯硫醇和120mL无水N,N-二甲基甲酰胺，在Ar气氛中搅拌，在气体保护下，缓慢加入5.47g叔丁醇钾，搅拌0.5小时后，加入7.01g 2,5-二溴硝基苯，搅拌20分钟后，加热回流过夜，通过旋转蒸发仪除去大部分无水N,N-二甲基甲酰胺后，用去离子水和二氯甲烷萃取，过硅胶色谱柱分离，得到白色固体状的中间体M3；
    所述含有吩恶噻结构的中间体M4的制备方法具体为：在100mL三口瓶中加入4.6g中间体M3和50mL冰醋酸，搅拌后，加入10mL的30％双氧水，加热回流过夜，冷却后加入乙醇，抽滤，干燥得到白色固体状的中间体M4。
  6. 如权利要求2所述的含有吩恶噻结构的共轭化合物的制备方法，其中，所述含有富电子共轭芳香单元的化合物为氮氮二甲基乙烯基脲、9,10-二氢-9,9-二甲基吖啶、N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)苯胺、双(4-叔丁基苯基)胺、吩噻嗪、9-苯基-3-(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)咔唑、吩恶嗪或氮氮二甲基乙烯基脲。
  7. 一种有机电致发光二极管器件，包括从下到上依次设置的基板、阳极、空穴注入层、空穴传输层、发光层、电子传输层、及阴极，其特征在于，所述发光层中含有如权利要求1所述的含有吩恶噻结构的共轭化合物。
  8. 如权利要求7所述的有机电致发光二极管器件，其中，所述发光层采用真空蒸镀或者溶液涂覆的方法形成。
  9. 如权利要求7所述的有机电致发光二极管器件，其中，所述基板为玻璃基板，所述阳极的材料为氧化铟锡，所述阴极为氟化锂层与铝层构成的双层复合结构。
  10. 如权利要求7所述的有机电致发光二极管器件，其中，所述空穴注入层的材料为HAT-CN，所述空穴传输层的材料为NPB和TCTA，所述电子传输层的材料为TPBI，所述化合物HAT-CN，NPB，TCTA和TPBI的结构式分别为：
    Figure PCTCN2015079538-appb-100006
    Figure PCTCN2015079538-appb-100007
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106749098A (zh) * 2016-12-07 2017-05-31 大连万福制药有限公司 一种以氧气为氧化剂制备盐酸二氧丙嗪的绿色工艺
US20180159050A1 (en) * 2016-12-07 2018-06-07 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101863942B1 (ko) * 2015-08-28 2018-07-06 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함한 유기 발광 소자
CN105968104A (zh) * 2016-07-20 2016-09-28 深圳市华星光电技术有限公司 发光材料及其制备方法与使用该发光材料的有机发光二极管
CN106188024A (zh) * 2016-07-20 2016-12-07 深圳市华星光电技术有限公司 发光材料及其制备方法与使用该发光材料的有机发光二极管
KR102600472B1 (ko) * 2016-09-13 2023-11-13 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함한 유기 발광 소자
CN106831744A (zh) * 2016-12-30 2017-06-13 上海天马有机发光显示技术有限公司 一种有机电致发光材料以及有机光电装置
KR102512719B1 (ko) * 2017-11-07 2023-03-23 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함한 유기 발광 소자
CN110354894B (zh) * 2019-07-22 2022-03-04 三峡大学 CuOX/OMS-2催化剂的制备方法及在合成吩恶噻衍生物上的应用
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CN112979626B (zh) * 2020-12-17 2023-04-18 上海和辉光电股份有限公司 一种用于有机发光的化合物及其应用
CN114874228A (zh) * 2021-02-05 2022-08-09 上海和辉光电股份有限公司 一种有机电致发光化合物及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006114966A1 (ja) * 2005-04-18 2006-11-02 Konica Minolta Holdings, Inc. 有機エレクトロルミネッセンス素子、表示装置及び照明装置
CN101560136A (zh) * 2008-04-02 2009-10-21 葛来西雅帝史派有限公司 新颖的有机电致发光化合物和使用该化合物的有机电致发光器件
JP2009260276A (ja) * 2008-03-10 2009-11-05 Fujifilm Corp 有機電界発光素子
WO2010150593A1 (ja) * 2009-06-24 2010-12-29 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子、表示装置、照明装置及び縮合多環式複素環化合物
WO2011081451A2 (ko) * 2009-12-30 2011-07-07 주식회사 두산 트리페닐렌계 화합물 및 이를 포함하는 유기 전계 발광 소자
WO2014030822A1 (ko) * 2012-08-21 2014-02-27 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882231A (en) * 1971-06-29 1975-05-06 Richardson Merrell Inc Antiviral compositions containing bis-basic ketones of phenoxathins and methods of inhibiting viral infections therewith
US4031147A (en) * 1975-08-01 1977-06-21 Hooker Chemicals & Plastics Corporation Process for directed chlorination of alkylbenzenes
US4190609A (en) * 1976-10-04 1980-02-26 Hooker Chemicals & Plastics Corp. Process for the directed chlorination of xylenes
US4069264A (en) * 1976-10-04 1978-01-17 Hooker Chemicals & Plastics Corporation Process for directed chlorination of alkylbenzenes
US4069263A (en) * 1977-01-03 1978-01-17 Hooker Chemicals & Plastics Corporation Process for directed chlorination of alkylbenzenes
US4289916A (en) * 1979-06-28 1981-09-15 Ihara Chemical Industry Co., Ltd. Process for producing p-chloroalkylbenzene
DE3432095A1 (de) * 1984-08-31 1986-03-06 Hoechst Ag, 6230 Frankfurt Verfahren zur kernchlorierung von toluol
DE3916664A1 (de) * 1989-05-23 1991-01-03 Bayer Ag Verfahren zur herstellung von 2-chlor-4-nitro-alkylbenzol
US5036067A (en) * 1990-03-14 1991-07-30 Merck & Co., Inc. Dibenzoheterocyclic hydroxamic acids and hydroxy ureas as inhibitors of 5-lipoxygenase
US5077374A (en) * 1990-04-20 1991-12-31 Phillips Petroleum Company Aromatic sulfide polymers and method of preparation
GB0204467D0 (en) * 2002-02-26 2002-04-10 Coates Brothers Plc Novel fused ring compounds, and their use as cationic photoinitiators
DE10242224A1 (de) * 2002-09-12 2004-03-25 Clariant Gmbh Verfahren zur Kernchlorierung von ortho-Xylol
DE10343606A1 (de) * 2003-09-20 2005-04-14 Covion Organic Semiconductors Gmbh Weiß emittierende Copolymere, deren Darstellung und Verwendung
WO2010080977A2 (en) * 2009-01-09 2010-07-15 Cenerx Biopharma, Inc. Oral sustained release antidepressant formulation
JP2012514648A (ja) * 2009-01-09 2012-06-28 セネレックス バイオファーマ，インコーポレーテッド 経口腸溶性抗うつ薬製剤
JP2010186106A (ja) * 2009-02-13 2010-08-26 Toshiba Corp ホログラム記録媒体
JP5761199B2 (ja) * 2010-10-22 2015-08-12 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子
US9142785B2 (en) * 2011-09-12 2015-09-22 Nippon Steel & Sumikin Chemical Co., Ltd. Organic electroluminescent element
CN104393181B (zh) * 2014-10-30 2017-02-01 中国科学院长春应用化学研究所 一种红色有机电致发光器件及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006114966A1 (ja) * 2005-04-18 2006-11-02 Konica Minolta Holdings, Inc. 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2009260276A (ja) * 2008-03-10 2009-11-05 Fujifilm Corp 有機電界発光素子
CN101560136A (zh) * 2008-04-02 2009-10-21 葛来西雅帝史派有限公司 新颖的有机电致发光化合物和使用该化合物的有机电致发光器件
WO2010150593A1 (ja) * 2009-06-24 2010-12-29 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子、表示装置、照明装置及び縮合多環式複素環化合物
WO2011081451A2 (ko) * 2009-12-30 2011-07-07 주식회사 두산 트리페닐렌계 화합물 및 이를 포함하는 유기 전계 발광 소자
WO2014030822A1 (ko) * 2012-08-21 2014-02-27 제일모직 주식회사 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106749098A (zh) * 2016-12-07 2017-05-31 大连万福制药有限公司 一种以氧气为氧化剂制备盐酸二氧丙嗪的绿色工艺
US20180159050A1 (en) * 2016-12-07 2018-06-07 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
US10892423B2 (en) * 2016-12-07 2021-01-12 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same

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