WO2016173020A1 - 含有二(苯砜基)苯结构的共轭化合物及其制备方法和应用 - Google Patents

含有二(苯砜基)苯结构的共轭化合物及其制备方法和应用 Download PDF

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WO2016173020A1
WO2016173020A1 PCT/CN2015/079539 CN2015079539W WO2016173020A1 WO 2016173020 A1 WO2016173020 A1 WO 2016173020A1 CN 2015079539 W CN2015079539 W CN 2015079539W WO 2016173020 A1 WO2016173020 A1 WO 2016173020A1
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benzene
bis
phenylsulfone
compound containing
halogen
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English (en)
French (fr)
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李先杰
吴元均
苏仕健
刘坤坤
刘明
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深圳市华星光电技术有限公司
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Priority to US14/763,830 priority Critical patent/US9604941B2/en
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Definitions

  • the invention belongs to the technical field of electroluminescent materials, and particularly relates to a compound containing bis(phenylsulfone)benzene and a preparation method and application thereof.
  • OLEDs organic electroluminescent diodes
  • OLEDs organic electroluminescent diodes
  • Organic electroluminescence is mainly divided into fluorescence and phosphorescence, but according to the spin quantum statistics theory, the probability of singlet exciton and triplet exciton is 1:3, which is the theoretical limit of fluorescence from singlet exciton radiation transition It is 25%, and the theoretical limit of phosphorescence of triplet exciton radiation transition is 75%.
  • spin forbidden in conventional pure organic molecular compounds, triplet excitons cannot directly undergo radiative transition to emit light, and can only be de-excited to the ground state in the form of thermal radiation, resulting in the waste of most excitons and loss of energy. . How to use 75% of the energy of triplet excitons has become a top priority.
  • Adachi discovered that a class of compounds containing sulfone groups has a small singlet-triplet energy level difference, allowing excitons on the triplet state to pass through the anti-gap to the singlet state, and then emit fluorescence through a radiation transition, making The theoretical limit of all fluorescence greatly exceeds 25%.
  • the device prepared by using this type of sulfone group-containing compound as the light-emitting unit doped in the host material bis(2-(diphenylphosphooxy)phenyl)ether (DPEPO) has obtained an external quantum efficiency of up to 9.9%, which is greatly improved.
  • the primary purpose of the present invention is to provide a conjugated compound containing a bis(phenylsulfone) benzene structure, which has a higher fluorescence quantum yield and is beneficial to improve electrophoresis The luminous efficiency of the light-emitting device.
  • Another object of the present invention is to provide a method for preparing the above-mentioned conjugated compound containing a bis(phenylsulfone)benzene structure, which is simple, easy to operate, and has a high yield of the target product.
  • Another object of the present invention is to provide the application of the above-mentioned conjugated compound containing bis(phenylsulfone)benzene structure in organic light-emitting diode devices by applying the conjugated compound containing bis(phenylsulfone)benzene structure to organic light emitting diode devices.
  • the light-emitting efficiency of the organic light-emitting diode device can be significantly improved.
  • a conjugated compound containing bis(phenylsulfone)benzene structure with a chemical structure of one of the general structural formulas shown below:
  • the benzene ring in the middle is connected to the adjacent sulfone group, Ar unit or N(Ar) 2 unit by a covalent bond at any position;
  • the Ar unit has a conjugated structure and is a vinylene group, an ethynylene group, an aromatic ring composed of carbon and hydrogen atoms, an aromatic heterocyclic ring composed of carbon, nitrogen, and hydrogen atoms, an aromatic heterocyclic ring composed of carbon, nitrogen, oxygen, and hydrogen atoms, and carbon sulfur.
  • the benzene ring in the middle is connected to the adjacent sulfone group in a meta or para position, and the benzene ring on both sides of the sulfone group is covalently connected to the adjacent Ar unit or N(Ar) 2 unit at its para position.
  • the bond is connected, which has a chemical structure of one of the general structural formulas shown below:
  • the preparation method of the above-mentioned conjugated compound containing bis(phenylsulfone)benzene structure includes the following steps:
  • Step 10 Synthesize halogen-substituted bis(phenylsulfone)benzene precursor
  • Step 20 The synthesized halogen-substituted bis(phenylsulfone)benzene precursor and the borate compound of Ar unit are subjected to a SUZUKI coupling reaction (Suzuki reaction) in the presence of a catalyst to prepare a bis(phenylsulfone) group.
  • a SUZUKI coupling reaction Sudzuki reaction
  • the reaction equation is as follows:
  • step 20' the synthesized halogen-substituted bis(phenylsulfone) benzene precursor and the NH(Ar) 2 compound containing secondary amine atoms are subjected to the Buchwald-Hartwig coupling reaction (Buchwald-Hartwig reaction ) Or copper-catalyzed amination reaction of halogenated aromatic hydrocarbons to prepare conjugated compounds containing bis(phenylsulfone)benzene structure.
  • the reaction equation is as follows:
  • the step 10 specifically includes the following steps:
  • Step 11 Dissolve the halogenated thiophenol and dichlorodicyano-p-benzoquinone (DDQ) in a solvent, and heat the reaction to obtain a halogenated diphenyl disulfide;
  • Step 12 Dissolve halogenated diphenyl disulfide, dihalogenated benzene, catalyst, and alkali in a solvent, and heat the reaction to obtain halogen-substituted bis(phenylthio)benzene;
  • Step 13 Dissolve halogen-substituted bis(phenylsulfonyl)benzene in a solvent, add an oxidizing agent, and heat to react to obtain halogen-substituted bis(phenylsulfone)benzene;
  • the step 20 specifically includes dissolving halogen-substituted bis(phenylsulfone)benzene, Ar unit borate, catalyst, and alkali in a solvent, and heating the reaction to obtain a conjugated compound containing a bis(phenylsulfone)benzene structure. .
  • the step 20' specifically includes dissolving halogen-substituted bis(phenylsulfone)benzene, NH(Ar) 2 compound containing secondary amine atoms, catalyst, and alkali in a solvent, and heating the reaction to obtain a bis(phenylsulfone) Conjugated compound of benzene structure.
  • the molar ratio of halogenated thiophenol and dichlorodicyano-p-benzoquinone used in the step 11 is 2:1.
  • the molar ratio of halogenated diphenyl persulfide, dihalogenated benzene, catalyst, and base used in the step 12 is (1 to 1.2): 1: (0.02 to 0.05): (2 to 6).
  • the molar ratio of the halogen-substituted bis(phenylthio)benzene and the oxidant used in the step 13 is 1:(5-8).
  • the molar ratio of halogen-substituted bis(phenylsulfone)benzene, Ar unit borate, catalyst, and base used in the step 20 is 1: (2.2 ⁇ 3): (0.02 ⁇ 0.05): (3 ⁇ 6) .
  • the molar ratio of the halogen-substituted bis(phenylsulfone)benzene, the NH(Ar) 2 compound containing a secondary amine atom, the catalyst, and the base used in the step 20' is 1:(2.2 ⁇ 3):(0.05 ⁇ 0.1) : (3 ⁇ 6).
  • the halogenated thiophenol is at least one of o-bromothiophenol, m-bromothiophenol, and p-bromothiophenol.
  • the dihalobenzene is at least one of m-diiodobenzene and p-diiodobenzene;
  • the catalyst is at least one of cuprous sulfide, cuprous iodide and cuprous oxide;
  • the oxidant is at least one of hydrogen peroxide, potassium permanganate, and pyridinium chlorochromate.
  • the catalyst is at least one of tetrakis(triphenylphosphorus)palladium, tetrakis(triphenylphosphorus)palladium dichloride, tris(dibenzylideneacetone)dipalladium and tricyclohexylphosphorus Kind.
  • the catalyst in the step 20' is one of palladium acetate, tri-tert-butylphosphine, and 1,1'-bis(diphenylphosphine)ferrocene.
  • the alkali is at least one of potassium carbonate, sodium carbonate and potassium phosphate.
  • the solvent is toluene, ethanol, 1,4-dioxane, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, N,N-dioxane, At least one of methylformamide and 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone.
  • An organic electroluminescent diode device comprising a substrate, an anode, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode which are sequentially arranged from bottom to top, wherein the light emitting
  • the material of the layer is a host material doped with a conjugated compound containing a bis(phenylsulfone) benzene structure as described above, and the host material is bis(orthophenoxyphenyl) ether.
  • the substrate is a glass substrate
  • the material of the anode is indium tin oxide
  • the cathode is a double-layer composite structure composed of a lithium fluoride layer and an aluminum layer.
  • the material of the hole transport layer is N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, and the electron blocking
  • the material of the layer is 4,4',4”-tris(9-carbazole) triphenylamine, and the material of the hole blocking layer is 9-4-tert-butylphenyl-3,6-di-trityl Silyl-9H-carbazole
  • the material of the electron transport layer is 1,3,5-tris(1-phenyl-1-H-benzimidazole-2-)benzene.
  • the mechanism of the present invention is: the conjugated compound containing the bis(phenylsulfone)benzene structure of the present invention takes the bis(phenylsulfone)benzene as the core, and utilizes the electrophilicity of the sulfone group to obtain a class of intramolecular charge transfer Molecules; and use the barrier effect of the sulfone group on the conjugate system to control the effective conjugation strength of the entire molecule, so that the molecule has a high triplet energy, thereby reducing the singlet-triplet energy level difference, and the triplet excitation
  • the electrons can pass through the anti-gap to the singlet state, and then emit fluorescence through the radiation transition, so as to improve the utilization efficiency of excitons, and finally achieve the purpose of improving the performance of the device.
  • the present invention has the following advantages and beneficial effects:
  • the conjugated compound containing bis(phenylsulfone)benzene structure of the present invention is a newly synthesized product with bis(phenylsulfone)benzene as the nucleus, which is novel and creative.
  • the present invention provides a method for preparing conjugated compounds containing bis(phenylsulfone)benzene structure.
  • the conjugated compound containing the bis(phenylsulfone)benzene structure of the present invention can adjust the structure by connecting different units to achieve emission of different wavelengths.
  • the conjugated compound containing the bis(phenylsulfone)benzene structure of the present invention has a higher fluorescence quantum yield, which is beneficial to realize a high luminous efficiency of the device.
  • the conjugated compound containing the bis(phenylsulfone)benzene structure of the present invention has a lower singlet-triplet energy level difference, which is beneficial to improve the exciton utilization rate in the device and break through the traditional fluorescent materials5 % Efficiency limit of external quantum theory.
  • Figure 1 is a solid thin film ultraviolet-visible light absorption spectrum of a conjugated compound containing a bis(phenylsulfone)benzene structure prepared in Examples 15 and 16 of the present invention
  • FIG. 3 is a graph showing the voltage-current density-brightness relationship of organic light-emitting diode devices prepared by using the conjugated compound containing the bis(phenylsulfone)benzene structure as the light-emitting layer material prepared in Examples 15 and 16 of the present invention;
  • Fig. 5 is an electroluminescence spectrum diagram of an organic light-emitting diode device prepared by using the conjugated compound containing a bis(phenylsulfone)benzene structure as the light-emitting layer material prepared in Examples 15 and 16 of the present invention.
  • dichlorodicyano-p-benzoquinone (0.1 mol, To 22.7g) was added to 500ml of dichloromethane, and then m-bromothiophenol (0.20mol, 37.8g) was added and stirred for one hour. The mixture was then poured into 1 L of water, and the product was extracted with dichloromethane. The organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the silica gel column was used for separation and purification to obtain a yellow solid (33.4 g, yield 89%).
  • DDQ dichlorodicyano-p-benzoquinone
  • 1,4-bis[(4-bromobenzene)sulfur]benzene (30 mmol, 13.5 g) was added to 200 ml of acetic acid. After heating to 100°C, add 30% mass concentration of hydrogen peroxide aqueous solution (180mmol, about 19mL), stir for 18 hours, then pour the mixture into To 500 ml water, and extract the product with dichloromethane. The organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the silica gel column was used for separation and purification to obtain a white solid (14.5 g, 94%).
  • 1,3-bis[(4-bromobenzene)sulfur]benzene (30 mmol, 13.5 g) was added to 200 ml of acetic acid. After heating to 100°C, a 30% mass concentration of hydrogen peroxide aqueous solution (180 mmol, about 19 mL) was added, and after stirring for 18 hours, the mixture was poured into 500 mL of water, and the product was extracted with dichloromethane. The organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the silica gel column was used for separation and purification to obtain a white solid (13.8 g, 89%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the white solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (1.8 g, yield 72%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the white solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (1.7 g, yield 68%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and a white solid was obtained by separation and purification with a silica gel column, which was then dried and sublimated under vacuum to obtain a high-purity product (1.6 g, yield 62%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the white solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (1.9 g, yield 74%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the white solid was separated and purified by a silica gel column, and then dried and sublimated under vacuum to obtain a high-purity product (1.8 g, yield 71%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and a white solid was obtained by separation and purification with a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (2.5 g, yield 59%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the white solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (2.2 g, yield 52%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and a white solid was obtained by separation and purification with a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (2.4 g, yield 52%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the white solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (2.7 g, yield 59%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and a light yellow solid was obtained by separation and purification with a silica gel chromatography column, which was then dried and sublimated under vacuum to obtain a high-purity product (2.2g, yield 63%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and a light yellow solid was obtained by separation and purification with a silica gel chromatography column, which was then dried and sublimated under vacuum to obtain a high-purity product (2.2g, yield 63%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the white solid was separated and purified by a silica gel column, and then dried and sublimated under vacuum to obtain a high-purity product (2.4 g, yield 62%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the white solid was separated and purified by a silica gel column, and then dried and sublimated under vacuum to obtain a high-purity product (2.2g, yield 57%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the yellow solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (2.2 g, yield 61%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the yellow solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (2.0 g, yield 56%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the yellow solid was separated and purified by a silica gel column, and then dried and sublimated under vacuum to obtain a high-purity product (2.4 g, yield 63%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the yellow solid was separated and purified by a silica gel column, and then dried and sublimated under vacuum to obtain a high-purity product (2.2 g, yield 59%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the yellow solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (2.4 g, yield 55%).
  • the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed after separation, and the yellow solid was separated and purified by a silica gel column. After drying, it was sublimated under vacuum to obtain a high-purity product (2.3g, yield 52%).
  • the electromechanical light-emitting diode device includes a substrate, an anode, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and a cathode arranged from bottom to top, wherein the substrate is glass
  • the anode material is indium tin oxide (ITO)
  • the substrate and the anode together form ITO glass
  • the ITO glass is ultrasonically cleaned and then treated with oxygen plasma (Oxygen Plasma), the square of the ITO glass
  • the resistance is 10 ⁇ /cm 2 .
  • the material of the hole transport layer is N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), so
  • the material of the electron blocking layer is 4,4',4"-tris(9-carbazole)triphenylamine (TCTA), and the material of the hole blocking layer is 9-4-tert-butylphenyl-3,6 -Di-tritylsilyl-9H-carbazole (CzSi)
  • the material of the light-emitting layer is doped with the host material bis(ortho-diphenylphosphoroxyphenyl) ether (DPEPO) respectively.
  • Example 15 and Example 16 The obtained conjugated compounds 1-5, 2-5 containing bis(phenylsulfone)benzene structure, and the material of the electron transport layer is 1,3,5-tris(1-phenyl-1-H-benzo Imidazole-2-)benzene (TPBI);
  • the cathode is a double-layer composite structure composed of a lithium fluoride (LiF) layer and an aluminum (Al) layer.
  • LiF lithium fluoride
  • Al aluminum
  • CE stands for lumen efficiency
  • EQE stands for external quantum efficiency
  • PE stands for power efficiency
  • OLED organic light-emitting diode
  • the conjugated compound containing the bis(phenylsulfone)benzene structure of the present invention has a higher fluorescence quantum yield, and the organic light-emitting diode is used as the light-emitting layer. (OLED) devices have higher luminous efficiency.
  • the conjugated compound containing bis(phenylsulfone)benzene structure prepared by the present invention has fluorescence and can be used to make light-emitting layer, but also has certain conductivity, so it can also be used for making organic electroluminescent diodes. Electron transport layer.

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Abstract

一种含二(苯砜基)苯结构的共轭化合物及其制备方法，和用于制作有机电致发光二极管的发光层或电子传输层的用途。该化合物具有如下所示结构通式之一的化学结构：式A 或式B。

Description

含有二(苯砜基)苯结构的共轭化合物及其制备方法和应用 技术领域
本发明属于电致发光材料技术领域，特别涉及一种含有二(苯砜基)苯的化合物及其制备方法和应用。
背景技术
近二十年来，有机电致发光二极管(OLED)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。
有机电致发光主要分为荧光和磷光，但根据自旋量子统计理论，单重态激子和三重态激子的概率为1:3，即来自单重态激子辐射跃迁的荧光的理论极限为25％，三重态激子辐射跃迁的磷光的理论极限为75％。而由于自旋禁阻，在常规的纯有机分子化合物中，三重态激子无法直接进行辐射跃迁发光，只能以热辐射的形式退激发至基态，造成大部分激子的浪费和能量的损失。如何利用75％的三线态激子的能量成为当务之急。2012年Adachi发现一类含有砜基的化合物拥有较小的单重态-三重态能级差，使得三重态上的激子得以通过反隙间穿越至单重态，再通过辐射跃迁发出荧光，使得所有荧光的理论极限大大超过25％。以这类含有砜基的化合物作为发光单元掺杂在主体材料二(2-(二苯基磷氧)苯基)醚(DPEPO)中所制备的器件获得了高达9.9％的外量子效率，大大超过了传统的有机荧光化合物所能达到的水平。从此，人们对拥有较小的单重态-三重态能级差的电致发光化合物产生了浓厚的兴趣，而其中，含有砜基的化合物在其中又占有相当重要的地位。
而要实现较小的单重态-三重态能级差，对材料的设计有着严格的要求，其中包括对共轭长度以及给电子单元和吸电子单元相互作用的控制。目前为止，只有极少数材料能够在电致发光器件中实现三重态激子反穿越至单重态激子的转换。传统的有机发光分子，通常给电子单元和吸电子单元相互作用过强，分子的共轭程度过大，导致三重态能级较低，难以实现较小 的单重态-三重态能级差。因此，需要开发新的结构单元来控制分子间电荷转移在合理的程度上。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种含有二(苯砜基)苯结构的共轭化合物，该化合物具有较高的荧光量子产率，有利于提高电致发光器件的发光效率。
本发明另一目的在于提供一种上述含有二(苯砜基)苯结构的共轭化合物的制备方法，该方法简单，易于操作，且获得目标产物的产率较高。
本发明再一目的在于提供上述含有二(苯砜基)苯结构的共轭化合物在有机发光二极管器件中的应用，通过将所述含有二(苯砜基)苯结构的共轭化合物应用于有机发光二极管器件中的发光层中，可显著提高有机发光二极管器件的发光效率。
本发明的目的通过下述方案实现：
一种含有二(苯砜基)苯结构的共轭化合物，具有如下所示结构通式之一的化学结构：
式A
Figure PCTCN2015079539-appb-000001
式B
Figure PCTCN2015079539-appb-000002
以上式A与式B中，中间的苯环在其任意位置与相邻的砜基、Ar单元或者N(Ar)2单元以共价键相连；
所述的Ar单元具有共轭结构，为乙烯撑基、乙炔撑基、碳氢原子构成的芳香环、碳氮氢原子构成的芳香杂环、碳氮氧氢原子构成的芳香杂环、碳硫氢原子构成的芳香杂环、碳硅氢原子构成的芳香杂环、碳氮硫氢原子构成的芳香杂环、及碳硅硫氢原子构成的芳香杂环中的一种或多种的组合。
优选地，中间的苯环与相邻的砜基以间位，或者对位形式连接，砜基两侧的苯环与相邻的Ar单元或者N(Ar)2单元在其对位以共价键相连，其具有如下所示结构通式之一的化学结构：
式C
Figure PCTCN2015079539-appb-000003
式D
Figure PCTCN2015079539-appb-000004
式E
Figure PCTCN2015079539-appb-000005
式F
Figure PCTCN2015079539-appb-000006
上述含二(苯砜基)苯结构的共轭化合物的制备方法，包括以下步骤：
步骤10、合成卤素取代的二(苯砜基)苯前驱体；
步骤20、将所合成的卤素取代的二(苯砜基)苯前驱体与Ar单元的硼酸酯化合物在催化剂的存在下通过SUZUKI偶联反应(铃木反应)，制备得到含二(苯砜基)苯结构的共轭化合物，反应方程式如下：
Figure PCTCN2015079539-appb-000007
或者步骤20’、将所合成卤素取代的二(苯砜基)苯前驱体与含有仲胺原子的NH(Ar)2化合物通过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，制备得到含二(苯砜基)苯结构的共轭化合物，反应方程式如下：
Figure PCTCN2015079539-appb-000008
所述步骤10中具体包括以下步骤：
步骤11、把卤代苯硫酚、二氯二氰基对苯醌(DDQ)溶于溶剂中，加热反应，得到卤代二苯二硫醚；
步骤12、把卤代二苯二硫醚、二卤代苯、催化剂、碱溶于溶剂中，加热反应，得到卤素取代的二(苯硫基)苯；
步骤13、把卤素取代的二(苯硫基)苯溶于溶剂中，加入氧化剂，加热反应，得到卤素取代的二(苯砜基)苯；
所述步骤20具体为把卤素取代的二(苯砜基)苯、Ar单元的硼酸酯、催化剂、碱溶于溶剂中，加热反应，得到含有二(苯砜基)苯结构的共轭化合物。
所述步骤20’具体为把卤素取代的二(苯砜基)苯、含有仲胺原子的NH(Ar)2化合物、催化剂、碱溶于溶剂中，加热反应，得到含有二(苯砜基)苯结构的共轭化合物。
所述步骤11中所用卤代苯硫酚、二氯二氰基对苯醌的摩尔比为2：1。
所述步骤12中所用卤代二苯过硫醚、二卤代苯、催化剂、碱的摩尔比为(1～1.2)：1：(0.02～0.05)：(2～6)。
所述步骤13中所用卤素取代的二(苯硫基)苯、氧化剂的摩尔比为1：(5～8)。
所述步骤20中所用卤素取代的二(苯砜基)苯、Ar单元的硼酸酯、催化剂、碱的摩尔比为1：(2.2～3)：(0.02～0.05)：(3～6)。
所述步骤20’中所用卤素取代的二(苯砜基)苯、含有仲胺原子的NH(Ar)2化合物、催化剂、碱的摩尔比为1：(2.2～3)：(0.05～0.1)：(3～6)。
所述步骤11中，所述卤代苯硫酚为邻溴苯硫酚、间溴苯硫酚和对溴苯硫酚中的至少一种。
所述步骤12中，所述二卤代苯为间二碘苯和对二碘苯中的至少一种；所述催化剂为硫化亚铜、碘化亚铜和氧化亚铜中的至少一种；
所述步骤13中，所述氧化剂为过氧化氢、高锰酸钾、氯铬酸吡啶鎓盐中的至少一种。
所述步骤20中，所述催化剂为四(三苯基磷)钯、四(三苯基磷)二氯化钯、三(二亚苄基丙酮)二钯和三环己基磷中的至少一种。
所述步骤20’中所述催化剂为醋酸钯、三叔丁基膦、1,1'-双(二苯基膦)二茂铁中的一种。
所述步骤12、20、及20’中，所述碱为碳酸钾、碳酸钠和磷酸钾中的至少一种。
所述步骤11、12、13、20、及20’中，所述溶剂为甲苯、乙醇、1,4-二氧六环、四氢呋喃、二甲基亚砜、二氯甲烷、N，N-二甲基甲酰胺和1,3-二甲基-3,4,5,6-四氢-2-嘧啶酮中的至少一种。
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、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、及阴极，其中，所述发光层的材料为主体材料掺杂如上所述的含有二(苯砜基)苯结构的共轭化合物，所述主体材料为二(邻二苯磷氧基苯)醚。
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。
所述空穴传输层的材料为N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺，所述电子阻挡层的材料为4,4’,4”-三(9-咔唑)三苯胺，所述空穴阻挡层的材料为9-4-叔丁基苯基-3,6-二-三苯甲硅烷基-9H-咔唑，所述电子传输层的材料为1,3,5-三(1-苯基-1-H-苯并咪唑-2-)苯。
本发明的机理为：本发明的含有二(苯砜基)苯结构的共轭化合物以二(苯砜基)苯为核，利用砜基的亲电性，获得一类具有分子内电荷转移的分子；并利用砜基对共轭系统的阻隔作用，控制整个分子的有效共轭强度，使得分子具有高的三重态能量，从而减小单重态-三重态能级差，而三重态上的激子得以通过反隙间穿越至单重态，再通过辐射跃迁发出荧光，以提高激子的利用效率，最终达到提高器件性能的目的。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明所述的含有二(苯砜基)苯结构的共轭化合物以二(苯砜基)苯为核，为全新合成的产物，具有新颖性和创造性。
(2)本发明提供了一种制备含有二(苯砜基)苯结构的共轭化合物的方法路径。
(3)本发明所述的含有二(苯砜基)苯结构的共轭化合物可通过连接不同的单元来调节结构，实现不同波长的发射光。
(4)本发明所述的含有二(苯砜基)苯结构的共轭化合物具有较高的荧光量子产率，有利于实现高的器件发光效率。
(5)本发明所述的含有二(苯砜基)苯结构的共轭化合物具有较低的单重态-三重态能级差，有利于提高器件中的激子利用率，突破传统荧光材料5％的外量子理论效率极限。
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
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为本发明实施例15、16制备得到的含有二(苯砜基)苯结构的共轭化合物的固体薄膜紫外-可见光吸收光谱图；
图2为本发明实施例15、16制备得到的含有二(苯砜基)苯结构的共轭化合物的固体薄膜荧光光谱图；
图3为本发明实施例15、16制备得到的含有二(苯砜基)苯结构的共轭化合物作为发光层材料制备的有机发光二极管器件的电压-电流密度-亮度关系曲线图；
图4为本发明实施例15、16制备得到的含有二(苯砜基)苯结构的共轭化合物作为发光层材料制备的有机发光二极管器件的电流密度-外量子效率关系曲线图；
图5为本发明实施例15、16制备得到的含有二(苯砜基)苯结构的共轭化合物作为发光层材料制备的有机发光二极管器件的电致发光光谱图。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述，但本发明的实施方式不限于此。
实施例1：
双(4-溴苯)二硫醚的制备，反应式如下：
Figure PCTCN2015079539-appb-000009
在1升单口烧瓶中，在室温下将二氯二氰基对苯醌(DDQ)(0.1mol，22.7g)加入到500毫升的二氯甲烷中，然后再加入对溴苯硫酚(0.20mol，37.8g)，搅拌一小时。然后将混合液倒入1L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黄色固体(34.6g，产率92％)。
实施例2：
双(3-溴苯)二硫醚的制备，反应式如下：
Figure PCTCN2015079539-appb-000010
在1升单口烧瓶中，在室温下将二氯二氰基对苯醌(DDQ)(0.1mol， 22.7g)加入到500毫升的二氯甲烷中，然后再加入间溴苯硫酚(0.20mol,37.8g)，搅拌一小时。然后将混合液倒入1L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黄色固体(33.4g，产率89％)。
实施例3：
1，4-二[(4-溴苯)硫]苯的制备，反应式如下：
Figure PCTCN2015079539-appb-000011
在250毫升三口烧瓶中，在室温下将双(4-溴苯)二硫醚(50mmol，18.8g)和对二碘苯(50mmol，16.5g)加入到150毫升的二甲基亚砜，然后再加入碘化亚铜(5mmol，1.0g)和碳酸钾(150mmol，20.7g)。在氩气气氛下加热至120℃反应24小时。然后将混合液倒入500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(14.5g，64％)。
实施例4：
1，3-二[(4-溴苯)硫]苯的制备，反应式如下：
Figure PCTCN2015079539-appb-000012
在250毫升三口烧瓶中，将双(4-溴苯)二硫醚(50mmol，18.8g)和间二碘苯(50mmol，16.5g)加入到150毫升的二甲基亚砜，然后再加入碘化亚铜(5mmol，1.0g)和碳酸钾(150mmol，20.7g)。在氩气气氛下加热至120℃反应24小时。然后将混合液倒入500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(13.3g，58％)。
实施例5：
1，4-二[(4-溴苯)砜基]苯的制备，反应式如下：
Figure PCTCN2015079539-appb-000013
在500毫升三口烧瓶中，在下将1，4-二[(4-溴苯)硫]苯(30mmol，13.5g)加入到200毫升的醋酸中。加热至100℃后，再加入质量浓度为30％的过氧化氢水溶液(180mmol，约19mL)，搅拌18个小时后，然后将混合液倒入 500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(14.5g，94％)。
实施例6：
1，3-二[(4-溴苯)砜基]苯的制备，反应式如下：
Figure PCTCN2015079539-appb-000014
在500毫升三口烧瓶中，在下将1，3-二[(4-溴苯)硫]苯(30mmol，13.5g)加入到200毫升的醋酸中。加热至100℃后，再加入质量浓度为30％的过氧化氢水溶液(180mmol，约19mL)，搅拌18个小时后，然后将混合液倒入500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(13.8g，89％)。
实施例7：
含有二(苯砜基)苯结构的共轭化合物1-1的制备，反应式如下：
Figure PCTCN2015079539-appb-000015
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和苯硼酸(12mmol，1.5g)，30毫升甲苯和15毫升四氢呋喃，再加入30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(1.8g，产率72％)。
实施例8：
含有二(苯砜基)苯结构的共轭化合物2-1的制备，反应式如下：
Figure PCTCN2015079539-appb-000016
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)和苯硼酸(12mmol，1.5g)，30毫升甲苯和15毫升四氢呋喃，再加入30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(1.7g，产率67％)。
实施例9：
含有二(苯砜基)苯结构的共轭化合物1-2的制备，反应式如下：
Figure PCTCN2015079539-appb-000017
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和3-吡啶硼酸(12mmol，1.5g)，30毫升甲苯和15毫升四氢呋喃，再加入30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(1.7g，产率68％)。
实施例10：
含有二(苯砜基)苯结构的共轭化合物2-2的制备，反应式如下：
Figure PCTCN2015079539-appb-000018
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)和3-吡啶硼酸(12mmol，1.5g)，30毫升甲苯和15毫升四氢呋喃，再加入30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(1.6g，产率62％)。
实施例11：
含有二(苯砜基)苯结构的共轭化合物1-3的制备，反应式如下：
Figure PCTCN2015079539-appb-000019
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和4-吡啶硼酸(12mmol，1.5g)，30毫升甲苯和15毫升四氢呋喃，再 加入30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(1.9g，产率74％)。
实施例12：
含有二(苯砜基)苯结构的共轭化合物2-3的制备，反应式如下：
Figure PCTCN2015079539-appb-000020
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)和4-吡啶硼酸(12mmol，1.5g)，30毫升甲苯和15毫升四氢呋喃，再加入30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(1.8g，产率71％)。
实施例13：
含有二(苯砜基)苯结构的共轭化合物1-4的制备，反应式如下：
Figure PCTCN2015079539-appb-000021
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)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(12mmol，4.4g)，30毫升甲苯和15毫升四氢呋喃，再加入30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(2.5g，产率59％)。
实施例14：
含有二(苯砜基)苯结构的共轭化合物2-4的制备，反应式如下：
Figure PCTCN2015079539-appb-000022
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)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(12mmol，4.4g)，30毫升甲苯和15毫升四氢呋喃，再加入30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(2.2g，产率52％)。
实施例15：
含有二(苯砜基)苯结构的共轭化合物1-5化合物的制备，反应式如下：
Figure PCTCN2015079539-appb-000023
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和3，6-二叔丁基咔唑(11mmol，3.1g)，20毫升1,3-二甲基-3,4,5,6-四氢-2-嘧啶酮作为溶剂，碘化亚铜0.2克，18冠6醚0.1克，和1.5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(2.4g，产率52％)。
实施例16：
含有二(苯砜基)苯结构的共轭化合物2-5的制备，反应式如下：
Figure PCTCN2015079539-appb-000024
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol， 2.6g)和3，6-二叔丁基咔唑(11mmol，3.1g)，20毫升1,3-二甲基-3,4,5,6-四氢-2-嘧啶酮作为溶剂，碘化亚铜0.2克，18冠6醚0.1克，和1.5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(2.7g，产率59％)。
实施例17：
含有二(苯砜基)苯结构的共轭化合物1-6的制备，反应式如下：
Figure PCTCN2015079539-appb-000025
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和二苯胺(12mmol，2.0g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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淡黄色固体，再经过干燥后于真空下升华得到高纯度产物(2.2g，产率63％)。
实施例18：
含有二(苯砜基)苯结构的共轭化合物2-6的制备，反应式如下：
Figure PCTCN2015079539-appb-000026
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)和二苯胺(12mmol，2.0g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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淡黄色固体，再经过干燥后于真空下升华得到高纯度产物(2.2g，产率63％)。
实施例19：
含有二(苯砜基)苯结构的共轭化合物1-7的制备，反应式如下：
Figure PCTCN2015079539-appb-000027
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和9，9-二甲基吖啶(12mmol，2.5g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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(2.4g，产率62％)。
实施例20：
含有二(苯砜基)苯结构的共轭化合物2-7的制备，反应式如下：
Figure PCTCN2015079539-appb-000028
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)和9，9-二甲基吖啶(12mmol，2.5g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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(2.2g，产率57％)。
实施例21：
含有二(苯砜基)苯结构的共轭化合物1-8的制备，反应式如下：
Figure PCTCN2015079539-appb-000029
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和吩恶嗪(12mmol，2.2g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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黄色固体，再经过干燥后于真空下升华得到高纯度产物(2.2g，产率61％)。
实施例22：
含有二(苯砜基)苯结构的共轭化合物2-8的制备，反应式如下：
Figure PCTCN2015079539-appb-000030
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)和吩恶嗪(12mmol，2.2g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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黄色固体，再经过干燥后于真空下升华得到高纯度产物(2.0g，产率56％)。
实施例23：
含有二(苯砜基)苯结构的共轭化合物1-9的制备，反应式如下：
Figure PCTCN2015079539-appb-000031
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和吩噻嗪(12mmol，2.4g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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黄色固体，再经过干燥后于真空下升华得到高纯度产物(2.4g，产率63％)。
实施例24：
含有二(苯砜基)苯结构的共轭化合物2-9的制备，反应式如下：
Figure PCTCN2015079539-appb-000032
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)和吩噻嗪(12mmol，2.4g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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黄色固体，再经过干燥后于真空下升华得到高纯度产物(2.2g，产率59％)。
实施例25：
含有二(苯砜基)苯结构的共轭化合物1-10的制备，反应式如下：
Figure PCTCN2015079539-appb-000033
在氩气气氛下向反应瓶中加入1，4-二[(4-溴苯)砜基]苯(5mmol，2.6g)和5-苯-9-氢-吩嗪(12mmol，3.1g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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黄色固体，再经过干燥后于真空下升华得到高纯度产物(2.4g，产率55％)。
实施例26：
含有二(苯砜基)苯结构的共轭化合物2-10的制备，反应式如下：
Figure PCTCN2015079539-appb-000034
在氩气气氛下向反应瓶中加入1，3-二[(4-溴苯)砜基]苯(5mmol，2.6g)和5-苯-9-氢-吩嗪(12mmol，3.1g)，100毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)，和1.5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黄色固体，再经过干燥后于真空下升华得到高纯度产物(2.3g，产率52％)。
将实施例15、实施例16得到的含有二(苯砜基)苯结构的共轭化合物1-5、2-5用于制备有机发光二极管(OLED)器件，并进行性能测试：
所述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、空穴传输层、电子阻挡层、发光层、空穴阻挡层、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(Oxygen Plasma)处理，所述ITO玻璃的方块电阻为10Ω/cm2。所述空穴传输层的材料为N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(NPB)，所述电子阻挡层的材料为4,4’,4”-三(9-咔唑)三苯胺(TCTA)，所述空穴阻挡层的材料为9-4-叔丁基苯基-3,6-二-三苯甲硅烷基-9H-咔唑(CzSi)，所述发光层的材料分别采用主体材料二(邻二苯磷氧基苯)醚(DPEPO)掺杂实施例15、实施例16得到的含有二(苯砜基)苯结构的共轭化合物1-5、2-5，所述电子传输层的材料为1,3,5-三(1-苯基-1-H-苯并咪唑-2-)苯(TPBI)；所述阴极为氟化锂(LiF)层与铝(Al)层构成的双层复合结构。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，结果如下表所示。
表1基于化合物1-5、2-5为发光层材料的有机电致发光器件的性能列表
Figure PCTCN2015079539-appb-000035
其中CE代表流明效率，EQE代表外量子效率，PE为功率效率。
实施例15和实施例16制备的含有二(苯砜基)苯结构的共轭化合物1-5、2-5作为发光层材料制备的有机发光二极管(OLED)器件的电压-电流密度-亮度关系曲线如图3所示；其电流密度-外量子效率关系曲线如图4所示；其电致发光光谱如图5所示。
从表1及附图3-5中的结果可以看出，本发明的含有二(苯砜基)苯结构的共轭化合物具有较高的荧光量子产率，以其为发光层的有机发光二极管(OLED)器件具有较高的发光效率。特别是基于化合物1-5的OLED器件，其外量子效率在1cd/m2亮度下达到了10.2％，远远超过了传统荧光器件5％的理论极限，这说明本发明制备的含有二(苯砜基)苯结构的共轭化 合物能够使得三重态上的激子得以通过反隙间穿越至单重态，再通过辐射跃迁发出荧光，从而获得高的器件发光效率。
本发明制备的含有二(苯砜基)苯结构的共轭化合物，除具有荧光性，可用于制作发光层之外，还具有一定的导电性，因此还可应用于制作有机电致发光二极管的电子传输层。
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，其它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. 一种含有二(苯砜基)苯结构的共轭化合物，具有如下所示结构通式之一的化学结构：
    Figure PCTCN2015079539-appb-100001
    以上式A与式B中，中间的苯环在其任意位置与相邻的砜基、Ar单元或者N(Ar)2单元以共价键相连；
    所述Ar单元具有共轭结构，为乙烯撑基、乙炔撑基、碳氢原子构成的芳香环、碳氮氢原子构成的芳香杂环、碳氮氧氢原子构成的芳香杂环、碳硫氢原子构成的芳香杂环、碳硅氢原子构成的芳香杂环、碳氮硫氢原子构成的芳香杂环、及碳硅硫氢原子构成的芳香杂环中的一种或多种的组合。
  2. 如权利要求1所述的含有二(苯砜基)苯结构的共轭化合物，其中，中间苯环与相邻的砜基以间位、或者对位形式共价键连接，砜基两侧的苯环与相邻的Ar单元或者N(Ar)2单元以对位形式共价键相连，其具有如下所示结构通式之一的化学结构：
    Figure PCTCN2015079539-appb-100002
    Figure PCTCN2015079539-appb-100003
  3. 一种如权利要求1所述的含有二(苯砜基)苯结构的共轭化合物的制备方法，包括以下步骤：
    步骤10、合成卤素取代的二(苯砜基)苯前驱体；
    步骤20、将合成的卤素取代的二(苯砜基)苯前驱体与Ar单元的硼酸酯化合物在催化剂的存在下通过Suzuki偶联反应，制备得到含二(苯砜基)苯结构的共轭化合物，反应方程式如下：
    Figure PCTCN2015079539-appb-100004
    或者，
    步骤20’、将合成的卤素取代的二(苯砜基)苯前驱体与含有仲胺原子的NH(Ar)2化合物通过Buchwald-Hartwig偶联或者铜催化卤代芳烃氨基化反应，制备得到含二(苯砜基)苯结构的共轭化合物，反应方程式如下：
    Figure PCTCN2015079539-appb-100005
  4. 如权利要求3所述的含有二(苯砜基)苯结构的共轭化合物的制备方法，其中，所述步骤10中具体包括以下步骤：
    步骤11、把卤代苯硫酚、二氯二氰基对苯醌(DDQ)溶于溶剂中，加热反应，得到卤代二苯二硫醚；
    步骤12、把卤代二苯二硫醚、二卤代苯、催化剂、碱溶于溶剂中，加热反应，得到卤素取代的二(苯硫基)苯；
    步骤13、把卤素取代的二(苯硫基)苯溶于溶剂中，加入氧化剂，加热反应，得到卤素取代的二(苯砜基)苯。
  5. 如权利要求4所述的含有二(苯砜基)苯结构的共轭化合物的制备 方法，其中，所述步骤20具体为将所合成卤素取代的二(苯砜基)苯、Ar单元的硼酸酯、催化剂、碱溶于溶剂中，加热反应，得到含有二(苯砜基)苯结构的共轭化合物；
    所述步骤20’具体为将所合成的卤素取代的二(苯砜基)苯、含有仲胺原子的NH(Ar)2化合物、催化剂、碱溶于溶剂中，加热反应，得到含有二(苯砜基)苯结构的共轭化合物。
  6. 如权利要求5所述的含有二(苯砜基)苯结构的共轭化合物的制备方法，其中：
    所述步骤11中，所用卤代苯硫酚、二氯二氰基对苯醌的摩尔比为2：1；
    所述步骤12中，所用卤代二苯过硫醚、二卤代苯、催化剂、碱的摩尔比为(1～1.2)：1：(0.02～0.05)：(2～6)；
    所述步骤13中，所用卤素取代的二(苯硫基)苯、氧化剂的摩尔比为1：(5～8)；
    所述步骤20中，所用卤素取代的二(苯砜基)苯、Ar单元的硼酸酯、催化剂、碱的摩尔比为1：(2.2～3)：(0.02～0.05)：(3～6)；
    所述步骤20’中，所用卤素取代的二(苯砜基)苯、含有仲胺原子的NH(Ar)2化合物、催化剂、碱的摩尔比为1：(2.2～3)：(0.05～0.1)：(3～6)。
  7. 如权利要求5所述的含有二(苯砜基)苯结构的共轭化合物的制备方法，其中：
    所述步骤11中，所述卤代苯硫酚为邻溴苯硫酚、间溴苯硫酚和对溴苯硫酚中的至少一种；
    所述步骤12中，所述二卤代苯为间二碘苯和对二碘苯中的至少一种，所述催化剂为硫化亚铜、碘化亚铜和氧化亚铜中的至少一种；
    所述步骤13中，所述氧化剂为过氧化氢、高锰酸钾和氯铬酸吡啶鎓盐中的至少一种；
    所述步骤20中，所述催化剂为四(三苯基磷)钯、四(三苯基磷)二氯化钯、三(二亚苄基丙酮)二钯和三环己基磷中的至少一种；
    所述步骤20’中，所述催化剂为醋酸钯、三叔丁基膦和1,1'-双(二苯基膦)二茂铁中的一种；
    所述步骤12、20、及20’中，所述碱为碳酸钾、碳酸钠和磷酸钾中的至少一种；
    所述步骤11、12、13、20、及20’中，所述溶剂为甲苯、乙醇、1,4-二氧六环、四氢呋喃、二甲基亚砜、二氯甲烷、N，N-二甲基甲酰胺和1,3-二甲基-3,4,5,6-四氢-2-嘧啶酮中的至少一种。
  8. 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、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、及阴极，其特征在于，所述发光层的材料为主体材料掺杂如权利要求1所述的含有二(苯砜基)苯结构的共轭化合物，所述主体材料为二(邻二苯磷氧基苯)醚。
  9. 如权利要求8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8所述的有机电致发光二极管器件，其中，所述空穴传输层的材料为N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺，所述电子阻挡层的材料为4,4’,4”-三(9-咔唑)三苯胺，所述空穴阻挡层的材料为9-4-叔丁基苯基-3,6-二-三苯甲硅烷基-9H-咔唑，所述电子传输层的材料为1,3,5-三(1-苯基-1-H-苯并咪唑-2-)苯。
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