CN109438430B - 一种间苯二酚杯芳烃化合物及制备方法与应用 - Google Patents
一种间苯二酚杯芳烃化合物及制备方法与应用 Download PDFInfo
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- CN109438430B CN109438430B CN201811514367.XA CN201811514367A CN109438430B CN 109438430 B CN109438430 B CN 109438430B CN 201811514367 A CN201811514367 A CN 201811514367A CN 109438430 B CN109438430 B CN 109438430B
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- calixarene compound
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- -1 Calixarene compound Chemical class 0.000 title claims description 33
- 238000002360 preparation method Methods 0.000 title description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
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- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 239000003480 eluent Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
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- 239000000741 silica gel Substances 0.000 claims description 13
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- 229960001755 resorcinol Drugs 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- XXFUZSHTIOFGNV-UHFFFAOYSA-N 1-bromoprop-1-yne Chemical compound CC#CBr XXFUZSHTIOFGNV-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 5
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 claims description 5
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- 238000002156 mixing Methods 0.000 claims description 4
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- YVGKLVZOQWYWTI-UHFFFAOYSA-N calixresorc[4]arene Chemical compound C1C(C(=CC=2O)O)=CC=2CC(C(=CC=2O)O)=CC=2CC(=C2)C(O)=CC(O)=C2CC2=CC1=C(O)C=C2O YVGKLVZOQWYWTI-UHFFFAOYSA-N 0.000 abstract 3
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- QOAXUJYWVFZSDY-UHFFFAOYSA-N dichloromethane;ethyl acetate;oxolane Chemical compound ClCCl.C1CCOC1.CCOC(C)=O QOAXUJYWVFZSDY-UHFFFAOYSA-N 0.000 description 1
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- TWOKQHDORBJKRS-UHFFFAOYSA-N n'-[2-[2-(ethylamino)ethylamino]ethyl]ethane-1,2-diamine Chemical compound CCNCCNCCNCCN TWOKQHDORBJKRS-UHFFFAOYSA-N 0.000 description 1
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- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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Abstract
本发明提供了一种以间苯二酚杯芳烃（Calix[4]resorcinarene,CRA）为核的星形发光材料及其在有机电致发光器件中的应用，该类化合物合成方法简单、反应条件温和且产率较高。特别是核体CRA有八个高反应活性位点，可以挂接八个功能基团，相应的功能化合物具有较好的成膜性、溶解性和较高的热稳定性。本发明化合物作为发光层材料应用于有机电致发光器件，可以获得优异的器件性能。
Description
技术领域
本发明属于有机光电材料技术领域，尤其涉及一种间苯二酚杯芳烃化合物及制备方法与应用。
背景技术
OLED是采用有机物作为发光材料的器件。具有驱动电压低、发光亮度和发光效率高、响应速度快、视角宽、生产工艺简单等优点，越来越多地用于显示器来取代传统的液晶显示器。
传统的底发射型OLED是由附着在玻璃基底上的透明阳极氧化铟锡(Indium TinOxide,ITO)，有机功能层(多层)和反射阴极Al(或其它阴极材料)组成的。另外，将反射阴极更换为具有一定透明度的电极材料，则可获得顶发射型OLED或者透明OLED。
在电激发条件下，空穴和电子分别从正极和负极注入到发光层，发光分子吸收能量受激发跃迁到高能级而形成单重态和三重态激子，激子再通过辐射发出可见光。传统的荧光材料只能利用单重态激子进行辐射发光，理论最大内量子效率仅为25％。磷光材料通过引入贵金属，可以同时利用单重态和三重态激子进行辐射发光，理论最大内量子效率为100％，不过存在贵金属的稀缺、成本高、对环境污染等缺点。基于这种需要，热活化延迟荧光(Thermally Activated Delayed Fluorescence,TADF)是OLED器件中使用的最有前途的激子收集机制，它依赖于小的单重态三重态能级差ΔEST，让三重态激子通过反向系间窜跃(Reverse Intersystem Crossing,RISC)到单重态发光，不利用贵金属，也能达到最大内量子效率100％，成为下一代OLED显示屏的关键性技术。
目前树枝状TADF材料的主要设计策略是在TADF发光单元的外围键接不同的主体分子。这种分子设计策略虽然取得了较好的效果，但也具有一定的局限性，比如：(1)TADF成分与主体成分之间比例要受TADF核体上反应位点数量的限制；(2)对于一些非对称TADF分子，难以引入多个反应位点；(3)许多TADF发光小分子只能通过真空蒸镀的方法制作器件，成本较高。
发明内容
本发明的目的在于提供一种间苯二酚杯芳烃化合物及制备方法与应用。
为实现上述目的，本发明采取的技术方案是：
一种间苯二酚杯芳烃化合物，所述化合物的结构如通式(1)所示：
其中，A1-A8为八个活性位点与功能成分反应后形成的官能团，R1-R8为有机发光二极管(Organic Light-Emitting Diode,OLED)发光材料。
A1-A8为1,4-二取代-1,2,3-三氮唑基团，其结构为
R1-R8选自以下任一种基团：
所述的间苯二酚杯芳烃化合物在有机电致发光材料中的应用。
所述间苯二酚杯芳烃化合物为OLED发光层。
一种含有所述的间苯二酚杯芳烃化合物的有机电致发光器件。
所述的有机电致发光器件，其结构为：ITO/PEDOT:PSS/Poly-TPD/PVK/发光层/TmPyPB/LiF/Al；所述发光层为间苯二酚杯芳烃化合物与mCP的混合物；其中，间苯二酚杯芳烃化合物与mCP二者的混合百分比含量分别为5-10wt％和90-95wt％。
利用溶液法制备所述的间苯二酚杯芳烃化合物的方法，包括以下步骤：
其中，Ri为有机发光二极管发光材料。
Ri选自以下任一种基团：
步骤1)的具体步骤为：将间苯二酚杯芳烃，K2CO3溶解在丙酮中，逐渐加入溴丙炔，室温回流反应，再加入溴丙炔回流，加入饱和食盐水，再加入盐酸中和，乙醚萃取得到有机相，旋蒸、干燥，最后以氯仿为淋洗剂，过硅胶色谱柱提纯，得到白色固体产物即为间苯二酚杯芳烃核体CRA-core；步骤2)的具体步骤为：在N2保护下，加入CRA-core、中间体Ri-N3和N,N,N',N,'N”-五甲基二亚乙基三胺、CuBr和DMF，室温搅拌反应后，通入空气，缓慢加入1,4,7,10-四氮杂环十二烷室温搅拌后终止反应，分离提纯即得为目标产物。
与现有技术相比，本发明的积极效果是：
本发明以间苯二酚杯芳烃为核，通过对经典的TADF发光分子进行功能化处理，键接在核体的八个活性位点上，具有较好的成膜性、溶解性和较高的热稳定性。根据这些优点，可以利用溶液法制备OLED器件，相比于传统的真空蒸镀的方法，该方法具有制备的方法简单，成本低廉、适用范围广等优点。通过该方法，利用本发明化合物作为发光层材料应用于OLED器件制作，可以获得优异的器件性能，具有良好的产业化前景。
附图说明
图1为本发明化合物应用的器件结构示意图；
其中，101透明导电玻璃基底，102为氧化铟锡(Indium tin oxide,ITO)阳极层，103为空穴注入层，104为空穴传输层，105为电子阻挡层，106为发光层，107为电子传输层，108为电子注入层，109为阴极金属层；
图2为化合物1、中间体1-7和CRA-core的红外光谱图；
图3为化合物2、中间体2-8和CRA-core的红外光谱图；
图4为中间体1-2的核磁共振氢谱图；
图5为中间体1-5的核磁共振氢谱图；
图6为中间体1-7的核磁共振氢谱图；
图7为化合物1的核磁共振氢谱表图；
图8为中间体2-1的核磁共振氢谱图；
图9为中间体2-2的核磁共振氢谱图；
图10为中间体2-3的核磁共振氢谱图；
图11为中间体2-4的核磁共振氢谱图；
图12为中间体2-5的核磁共振氢谱图；
图13为中间体2-6的核磁共振氢谱图；
图14为中间体2-7的核磁共振氢谱图；
图15为中间体2-8的核磁共振氢谱图；
图16为化合物2的核磁共振氢谱图；
图17为实施例1器件的电流密度-电压-亮度曲线；
图18为实施例2器件的电流密度-电压-亮度曲线。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
一种间苯二酚杯芳烃化合物(记为化合物1)，所述化合物的结构如通式(1)所示：
A1-A8为1,4-二取代-1,2,3-三氮唑基团，其结构为
R1-R8为以下基团：
其采用以下步骤制得：
1)间苯二酚杯芳烃核体(CRA-core)的制备：
将间苯二酚杯芳烃(2.2g，4mmol)，K2CO3(10.0g)溶解在丙酮(125mL)中，逐渐加入溴丙炔(5mL，45mmol)，室温回流反应24h，再加入溴丙炔(5mL，45mmol)，回流24h，加入饱和食盐水(100mL)，再加入2M盐酸中和，乙醚萃取得到有机相，旋蒸、干燥。最后以氯仿为淋洗剂，过硅胶色谱柱提纯，得到白色固体产物1.4g，即为间苯二酚杯芳烃核体CRA-core，收率40％。
表征：1H NMR(400MHz,CDCl3,δppm):6.72(s,4H),6.60(s,4H),4.62(q,4H),4.42(s,16H),2.48(s,8H),1.44(d,12H).13C NMR(101MHz,CDCl3,δppm):153.90(s),129.60(s),125.55(s),101.44(s),79.72(s),75.00(s),57.46(s),30.61(s),20.11(s).FT-IR(KBr),υ(cm-1):3282(CH≡C-),2121(C≡C)。其红外表征如图2所示，核磁共振氢谱如图3所示。
2)中间体1-1的制备：
将2-苯基-4,6-二氯三嗪(2.9g，13mmol)、对甲氧基苯硼酸(1.7g，11mmol)和碳酸钾(3.6g，26mmol)加入到100mL Schlenk瓶内，抽真空，充氮气3次，在N2气氛下加入四(三苯基膦)钯(0)(577.9mg，0.6mmol)、40mL四氢呋喃(THF)和8mL蒸馏水，60℃下搅拌反应12h。反应结束后，冷却至室温。用二氯甲烷萃取，收集有机相。以石油醚/氯仿＝1/1(v/v)为淋洗剂，过硅胶色谱柱提纯，用旋转蒸发仪除去溶剂，干燥后得到白色粉末状产物，即为中间体1-1，实际产量2.3g，收率60％。
表征：1H NMR(400MHz,CDCl3,δppm):8.67-8.57(m,4H,Ar-H),7.65(s,1H,Ar-H),7.57(s,2H,Ar-H),7.06(d,2H,Ar-H),3.95(s,3H,-OCH3)。
3)中间体1-2的制备：
将中间体1-1(1.9g，6.4mmol)和4-氨基苯硼酸频哪醇酯(1.7g，7.8mmol)加入100mL Schlenk瓶，抽真空，充氮气3次，N2气氛下加入四(三苯基膦)钯(0)(369.7g，0.3mmol)和50mL四氢呋喃(THF)、10mL甲苯。室温下搅拌10min，再向其中加入10mL碳酸钾(1.8g，12.8mmol)水溶液，回流搅拌反应48h。冷却至室温后，乙酸乙酯萃取，并收集有机相。加入无水MgSO4进行干燥，抽滤，浓缩试剂，得到褐色固体。将其用氯仿冲洗后，抽滤，得到白色粉末状样品，即为中间体1-2。实际产量1.9g，收率83％。
表征：1HNMR(400MHz,CDCl3,δppm):8.75(dd,4H,Ar-H),8.63(d,2H,Ar-H),7.66-7.52(m,3H,Ar-H),7.08(d,2H,Ar-H),6.83(d,2H,Ar-H),3.95(s,3H,-OCH3)。
4)中间体1-3的制备：
将Schlenk瓶抽真空，充氮气3次，在N2环境下将中间体1-2(1.7g，4.7mmol)的HBr溶液20mL冷却至(0～5℃)，加入到Schlenk瓶内。随后，将3mL冷却的亚硝酸钠(648.5mg，9.4mmol)水溶液，缓慢滴加至反应溶液中，在冰浴中搅拌1h。向冷却后的反应溶液中缓慢加入CuBr(404.5mg，2.8mmol)的HBr(47％)溶液，然后在室温下搅拌20min。之后加热至115℃，回流过夜。反应结束后，自然冷却至室温，将反应溶液在冰水中冷却，并用1M NaHCO3溶液进行中和。加入氯仿萃取，后并用无水MgSO4干燥有机相，过滤，用旋转蒸发仪除去溶剂，以氯仿为淋洗剂过硅胶色谱柱提纯，得到黄色粉末状产物，即为中间体1-3。实际产量1.1g，收率53％。
表征：1H NMR(400MHz,CDCl3,δppm)：8.81-8.64(m,4H,Ar-H),8.60(d,2H,Ar-H),7.69(d,2H,Ar-H),7.66-7.52(m,3H,Ar-H),7.06(t,2H,Ar-H),6.98(d,2H,Ar-H),3.93(s,3H,-OCH3)。
5)中间体1-4的制备：
将中间体1-3(917.5mg，2.2mmol)、吩恶嗪(567.5mg，3.1mmol)和K2CO3(910.9mg，6.6mmol)加入Schlenk管，抽真空，充N2三次，加入10mL精制甲苯，室温搅拌10min。向其中缓慢加入乙酸钯(II)(24.7mg，0.1mmol)、三叔丁基膦(0.02mL，0.02mmol)甲苯溶液，回流搅拌反应24h。反应结束后，自然冷却至室温，用氯仿萃取，并收集有机层。用无水MgSO4搅拌干燥2h，抽滤，浓缩溶剂。以氯仿/石油醚＝1/4(v/v)为淋洗剂，过硅胶色谱柱提纯，得到黄色粉末状产物，即为中间体1-4。实际产量1.1g，收率91％。
表征：1H NMR(400MHz,CDCl3,δppm):8.99(d,2H,Ar-H),8.82-8.76(m,4H,Ar-H),7.66-7.56(m,5H,Ar-H),7.21-7.01(m,2H,Ar-H),6.70(dd,6H,Ar-H),6.07(dt,2H,Ar-H),4.02-3.89(S,3H,-OCH3)。
6)中间体1-5的制备：
将中间体1-4(987.9mg，1.9mmol)溶解于20mL精制二氯甲烷，缓慢加入三溴化硼(BBr3)(0.6mL，5.7mmol)，40℃下回流搅拌8h。反应结束后，冷却至室温，在0℃下缓慢加入5％盐酸猝灭反应，之后用1M NaOH溶液中和。用乙酸乙酯萃取，无水MgSO4搅拌干燥2h，抽滤。以二氯甲烷为淋洗剂，过硅胶色谱柱提纯，用旋转蒸发仪除去溶剂，得到黄色粉末状固体，即为中间体1-5，实际产量819.6mg，收率81％。
表征：1H NMR(400MHz,CDCl3,δppm):8.99(d,2H,Ar-H),8.82-8.76(m,4H,Ar-H),7.66-7.56(m,5H,Ar-H),7.13(m,2H,Ar-H),6.70(dd,6H,Ar-H),6.07(dt,2H,Ar-H)。
7)中间体1-6的制备：
将中间体1-5(809.9mg，1.6mmol)、1,6-二溴己烷(585.5mg，2.4mmol)和K2CO3(884.5mg，6.4mmol)加入圆底烧瓶，向反应瓶内加入25mL丙酮，60℃下回流搅拌过夜。反应结束后，冷却至室温，抽滤，浓缩有机相。以二氯甲烷/石油醚＝1/3(v/v)为淋洗剂，过硅胶色谱柱提纯，得到黄色粉末状固体，即为中间体1-6。实际产量826.5mg，收率76％。
表征：1H NMR(400MHz,CDCl3,δppm):9.05-8.92(m,2H,Ar-H),8.87-8.70(m,4H,Ar-H),7.72-7.50(m,5H,Ar-H),7.17-7.02(m,2H,Ar-H),6.70(dd,6H,Ar-H),6.06(dt,2H,Ar-H),4.13(t,2H,-OCH2-),3.47(t,2H,-CH2-),2.03-1.81(m,4H,-CH2-),1.58(dd,4H,-CH2-)。
8)中间体1-7的制备：
将Schlenk瓶抽真空，充氮气3次，N2气氛下加入中间体1-6(472.9mg，0.7mmol)、NaN3(179.6mg，2.8mmol)和5mL DMF，60℃下搅拌过夜。反应完全后，停止加热，冷却至室温。将产物溶于乙酸乙酯，用蒸馏水洗涤有机相，无水MgSO4干燥2h，浓缩试剂。以二氯甲烷/石油醚＝1/2(v/v)为淋洗剂，过硅胶色谱柱提纯，用旋转蒸发仪除去溶剂，得到黄色粉末状产物，即为中间体1-7。实际产量493.1mg，收率86％。
表征：1H NMR(400MHz,CDCl3,δppm):9.07-8.95(m,2H,Ar-H),8.84-8.74(m,4H,Ar-H),7.69-7.54(m,5H,Ar-H),7.13-7.06(m,2H,Ar-H),6.81-6.60(m,6H,Ar-H),6.06(dt,2H,Ar-H),4.13(t,2H,-OCH2-),3.34(t,2H,-CH2-),1.89(dd,2H,-CH2-),1.70(dt,2H,-CH2-),1.60-1.49(m,4H,-CH2-).FT-IR(KBr),υ(cm-1):2090cm-1(-N3).HR MS(EI)m/z:[M]+calcdfor C39H33N5O2631.270；found,631.2872。其红外表征如图2所示。
9)化合物1的制备：
将Schlenk反应瓶抽真空，充氮气3次，在N2保护下加入CRA-core(34.1mg，0.04mmol)、中间体1-7(256.7mg，0.4mmol)和N,N,N',N,'N”-五甲基二亚乙基三胺(PMDETA)(104.2mg，0.6mmol)、CuBr(134.2mg，0.6mmol)和5mL DMF，室温搅拌反应14h。通入空气2h，缓慢加入1,4,7,10-四氮杂环十二烷(68.9mg，0.4mmol)搅拌4h后，用氯仿萃取，收集有机相，用蒸馏水洗涤至水相无色透明后进行柱层析。用乙酸乙酯将得到的固体产物进行索式提取，干燥得到黄色粉末状产物，即为化合物1。实际产量215.9mg，收率91％。
表征：1H NMR(400MHz,CDCl3,δppm)：8.91(s,16H,Ar-H),8.80-8.59(m,33H,Ar-H),7.53(s,48H,Ar-H),7.00(d,20H,Ar-H),6.76-6.54(m,48H,Ar-H),6.05(d,16H,Ar-H),4.66(s,8H,-CH-),4.34(s,12H,-CH3),4.01(s,12H,-CH2-),3.78(dd,12H,-CH2-),2.08-1.71(m,46H,-CH2-),1.61-1.48(m,18H,-CH2-).FT-IR(KBr),υ(cm-1):2936cm-1、2864cm-1(-C-H).EA:Anal.Calcd.For C368H312N56O24:C74.88,H5.33,N 13.29％.Found:C 74.89,H 5.51,N13.26％。其红外表征如图2所示。
实施例2
一种间苯二酚杯芳烃化合物(记为化合物2)，所述化合物的结构如通式(1)所示：
A1-A8为1,4-二取代-1,2,3-三氮唑基团，其结构为
R1-R8为以下基团：
采用以下步骤制得：
1)间苯二酚杯芳烃核体(CRA-core)的制备同实施例1中步骤1)；
2)中间体2-1的制备：
将98％硫酸引流入量筒中，量取50mL，再将量筒中的浓硫酸引流入100mL圆底烧瓶中，取化合物硫代水杨酸(5.04g，32.5mmol)分批加入反应瓶，取溴苯(10.52g，67mmol)逐滴加入混合液，室温(25-30℃)搅拌24h，之后在115℃的油浴里搅拌1h。终止反应，冷却至室温。粗产物用2M NaOH中和至混合液呈中性，再用氯仿及饱和食盐水洗涤多次，合并有机相，无水MgSO4干燥过夜，过滤后用旋转蒸发仪除去溶剂。以氯仿/石油醚＝3/2(v/v)为淋洗剂，过硅胶色谱柱提纯，得到淡黄色固体，即为中间体2-1，实际产量5.54g，收率75％。
表征：1H NMR(400MHz,CDCl3,δppm):8.75(d,J＝2.1Hz,1H，ArH),8.62(d,J＝8.1Hz,1H,ArH),7.72(dd,J＝8.6,2.1Hz,1H,ArH),7.68-7.62(m,1H,ArH),7.59(d,J＝8.0Hz,1H,ArH),7.54-7.45(m,2H,ArH)。
3)中间体2-2的制备：
取中间体2-1(5.21g，15.45mmol)，冰醋酸(143mL)，30％的过氧化氢(46.03g，1.35mmol)加入到单口圆底烧瓶中，连接冷凝管。置于油浴锅中，升温至120℃，恒温搅拌2h。反应终止，冷却至室温。取粗产物逐滴加入冰水中，将沉淀物用水洗涤并真空抽滤，收集到干净表面皿放入干燥箱干燥。得到淡黄色固体。即为中间体2-2，实际产量5.63g，收率98.7％。
表征：1H NMR(400MHz,CDCl3，δppm):8.50(d,J＝1.8Hz,1H),8.35(dt,J＝33.9,17.0Hz,1H,ArH),8.20(d,J＝7.8Hz,1H,ArH),8.04(dt,J＝8.4,5.1Hz,2H,ArH),7.93(td,J＝7.7,1.2Hz,1H,ArH),7.84(td,J＝7.7,1.1Hz,1H,ArH)。
4)中间体2-3的制备：
取化合物I-TPA(4.40g，12.04mmol)和精制DMF(31mL)加入100mL圆底烧瓶中室温搅拌30min至化合物I-TPA完全溶解，分批将N-溴代丁二酰亚胺(2.84g，16mmol)加入到体系中，室温搅拌5h。反应终止后，再用二氯甲烷稀释并用饱和食盐水萃取至水相澄清，合并有机相，浓缩至无液滴滴出，以氯仿/石油醚＝1/4(v/v)为淋洗剂，过硅胶色谱柱提纯，烘干得白色油状产物，即为中间体2-3，实际产量4.70g，收率75％。
表征：1H NMR(400MHz,CDCl3，δppm):7.37-7.29(m,1H，ArH),7.27(dd,J＝12.2,4.6Hz,1H，ArH),7.15-7.04(m,1H，ArH),7.02(t,J＝7.3Hz,1H，ArH),6.96-6.85(m,1H，ArH),3.84(s,1H，-OCH3)。
5)中间体2-4的制备：
先将100mL Schlenk瓶充氮脱气三次，取中间体2-3(2.87g，8.50mmol)，双(频哪醇合)二硼(4.38g，17.0mmol)和乙酸钾(3.36g，34.0mmol)置于50mL二氧六环中。接着加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯(PdCl2(dppf))(0.35g，0.40mmol)，置于100℃油浴，恒温搅拌12h。反应完成后，用二氯甲烷稀释产物并用饱和食盐水洗涤三次，以乙酸乙酯/石油醚＝1/20(v/v)为淋洗剂，过硅胶色谱柱提纯，得无色透明油状产物，即为中间体2-4，实际产量2.84g，收率75％。
表征：1H NMR(400MHz,CDCl3,δppm):7.63(d,J＝8.5Hz,2H,ArH),7.31-7.14(m,2H,ArH),7.11-7.02(m,5H,ArH),6.97(t,J＝8.2Hz,3H,ArH),6.88-6.80(m,2H,ArH),3.77(d,J＝23.4Hz,3H,-OCH3),1.34(d,J＝9.4Hz,12H,-CCH3)。
6)中间体2-5的制备：
取中间体2-2(2.46g，8.17mmol)、四(三苯膦)钯(0.17g，0.13mmol)、K2CO3(2mmol/mL,40mL)和四氢呋喃(60mL)在氮气下加入到250mL Schlenk瓶中。再取中间体3-4(2.71g，6.76mmol)加入反应瓶中并加热到110℃，恒温搅拌7h。终止反应后，冷却至室温后，用二氯甲烷稀释并用饱和食盐水洗涤有机相。用无水MgSO4干燥，过滤除去溶剂，浓缩。以乙酸乙酯：石油醚＝1:10(v/v)为淋洗剂，过硅胶色谱柱提纯，得到橙红色固体粉末，即为中间体2-5，实际产量1.81g，收率79％。
表征：1H NMR(400MHz,CDCl3,δppm):8.49(t,J＝6.7Hz,1H,ArH),8.36(dd,J＝7.9,1.2Hz,1H,ArH),8.24-8.10(m,1H,ArH),8.07-7.95(m,1H,ArH),7.87(tt,J＝14.1,7.0Hz,1H,ArH),7.79(td,J＝7.7,1.2Hz,1H,ArH),7.60-7.46(m,1H,ArH),7.32-7.26(m,1H,ArH),7.16-6.96(m,2H,ArH),6.94-6.78(m,1H,ArH),3.83(s,1H,-OCH3)。
7)中间体2-6的制备：
取中间体2-5(1.59g，3.07mmol)加到冰乙酸(200mL)中待其溶解，再将40％的氢溴酸(75mL)逐滴加到搅拌着的混合液中，在110℃油浴中搅拌12h。反应终止，先冷却至室温，再用酸中和，用二氯甲烷稀释并用饱和食盐水洗涤，用无水MgSO4干燥，过滤除去溶剂，浓缩。以乙酸乙酯/石油醚＝1/2(v/v)为淋洗剂，过硅胶色谱柱提纯，得红色固体粉末产物，即为中间体2-6，实际产量0.92g，收率69％。
表征：1H NMR(400MHz,DMSO,δppm):9.51(s,1H,-OH),8.40(t,J＝7.5Hz,1H,ArH),8.33-8.18(m,2H,ArH),8.11-8.01(m,1H,ArH),7.98(t,J＝7.6Hz,1H,ArH),7.71(t,J＝10.2Hz,1H,ArH),7.33(t,J＝7.9Hz,1H,ArH),7.13-6.99(m,2H,ArH),6.97(d,J＝8.8Hz,1H,ArH),6.81(t,J＝9.7Hz,1H,ArH)。
8)中间体2-7的制备：
先将100mL Scheleck瓶充氮脱气三次，在N2氛围下，加入中间体2-6(0.89g，2.78mmol)和1，6-二溴己烷(7.51g，30.41mmol)，溶于14mL DMF，再取化合物碳酸铯(2.95g，8.94mmol)加入进反应瓶，80℃油浴恒温搅拌6h。反应结束后，用二氯甲烷稀释并用饱和食盐水洗涤三次，以二氯甲烷为淋洗剂，过硅胶色谱柱提纯，得红色固体产物，即为中间体2-7，实际产量0.60g，收率73％。
表征：1H NMR(400MHz,CDCl3,δppm):8.50(d,J＝1.8Hz,1H,ArH),8.36(dd,J＝7.8,1.0Hz,1H,ArH),8.27-8.05(m,1H,ArH),8.02(dd,J＝8.3,1.9Hz,1H,ArH),7.84(dtd,J＝35.3,7.6,1.3Hz,1H,ArH),7.53(d,J＝8.7Hz,1H,ArH),7.29(t,J＝6.4Hz,1H,ArH),7.17-7.06(m,1H,ArH),6.92-6.72(m,1H,ArH),3.97(t,J＝6.3Hz,2H,-OCH2-),3.68-3.32(m,2H,-CH2Br),2.00-1.73(m,4H,-CH2-),1.62-1.46(m,4H,-CH2-)。
9)中间体2-8的制备：
在25mL的Scheleck中加入化合物中间体2-7(0.71g，1.05mmol)和DMF(11mL)，待其溶解后，充氮脱气三次。在N2环境下加入化合物NaN3(0.42g，11.72mmol)，置于100℃油浴恒温搅拌，反应30h。反应结束后加入50mL冰水淬灭，并搅拌冷却至室温。反应液用二氯甲烷稀释并用饱和食盐水洗三次。有机相用无水MgSO4干燥，过滤，浓缩。以二氯甲烷为淋洗剂，过硅胶色谱柱提纯，得红色固体产物，即为中间体2-8，实际产量0.45g，收率95％。其核磁共振氢谱如图3所示，红外表征如图4所示。
表征：1H NMR(400MHz,CDCl3，δppm):8.50(d,J＝1.8Hz,1H,ArH),8.36(dd,J＝7.9,1.1Hz,1H,ArH),8.25-8.14(m,2H,ArH),8.02(dd,J＝8.3,1.9Hz,1H,ArH),7.84(dtd,J＝35.3,7.6,1.3Hz,2H,ArH),7.61-7.50(m,2H,ArH),7.36-7.28(m,1H,ArH),7.19-7.00(m,7H,ArH),6.94-6.84(m,2H,ArH),3.97(t,J＝6.4Hz,2H,-OCH2-),3.30(t,J＝6.9Hz,2H,-CH2-),1.91-1.76(m,2H,-CH2N3),1.74-1.62(m,2H,-CH2-),1.56-1.45(m,4H,-CH2-).FT-IR(KBr),υ(cm-1):2867,2939(-CH2-)；2101(-N3)；1137,1303(O＝S＝O)；C37H32N4O4S(EA)(％,found/calcd)：N 8.91/8.75,C70.68/69.92,H 5.13/5.19,S5.10/5.04；HR-MS C37H32N4O4S:m/z calcd for[M+H]+629.2144,found 629.2223。
10)化合物2的制备：
取中间体2-8(128.26mg，0.20mmol)、CRA-core(17.32mg，0.02mmol)加入Scheleck管，先用DMF(4mL)溶解。充氮脱气3次，加入PMDETA(64.12mg，0.32mmol)，加入溴化铜(25.35mg，0.16mmol)，室温搅拌15h后，加入40mL二氯甲烷稀释搅拌，再取化合物1，4，7，10-四氮杂十二烷(43.50mg，0.25mmol)，室温搅拌4h，加入大量水终止反应并用氯仿萃取，合并有机相，加无水MgSO4搅拌过夜，抽滤并除去有机试剂，以二氯甲烷-乙酸乙酯-四氢呋喃为淋洗剂，过硅胶色谱柱提纯，得红色固体粉末产物，即为化合物2，实际产量0.114g，收率95％。
表征：1H NMR(400MHz,CDCl3，δppm)8.48(s,1H，ArH),8.34(d,J＝7.7Hz,1H，ArH),8.18(t,J＝8.4Hz,2H，ArH),8.00(d,J＝7.9Hz,1H，ArH),7.88(t,J＝7.3Hz,1H，ArH),7.77(d,J＝15.1Hz,1H，ArH),7.51(d,J＝8.5Hz,2H，ArH),7.29-7.21(m,2H，ArH),7.08(d,J＝20.3Hz,7H，ArH),6.86(d,J＝8.9Hz,2H，ArH),5.19(d,J＝10.5Hz,1H，-CH2O-),4.65(d,J＝6.8Hz,1H，-CH2-),4.37(d,J＝41.8Hz,1H，-CHCH2-),3.94(t,J＝6.1Hz,2H，-CH2N-),2.01(d,J＝45.5Hz,2H，-CH2-),1.85-1.72(m,2H，ArH),1.61-1.37(m,6H，ArH).FT-IR(KBr),υ(cm-1):1552,1335(-NO2)；C352H304N32O40S(EA)(％,found/calcd)：N 7.62/7.17,C 71.92/67.76,H 5.21/4.88,S4.36/3.81；C352H304N32O40S MALDI-TOF MS:m/z calcd for[M+H]+5874.0503,found 5879.4。其核磁共振氢谱如图3所示，红外表征如图4所示。
在其他实施例中，R1-R8基团还可以选择以下基团中任一种均可实现本发明效果。
实施例3应用
使用实施例的化合物1、化合物2作为发光层制备OLED器件。
器件1的结构：ITO/PEDOT:PSS(40nm)/Poly-TPD(35nm)/PVK(5nm)/10wt％化合物1:mCP(30nm)/TmPyPB(40nm)/LiF(1nm)/Al(80nm)。
首先，将涂有ITO的导电玻璃分别在清洗剂、去离子水、丙酮和乙醇中超声清洗各30min，然后在氧等离子体中处理5min。
在ITO阳极层上旋涂40nm厚的PEDOT:PSS，作为空穴注入层，在120℃下干燥15min；以氯苯为溶剂，在空穴注入层上旋涂35nm厚的Poly-TPD，作为空穴传输层，在110℃下干燥10min；
以氯苯为溶剂，在空穴传输层上旋涂5nm厚的PVK，作为电子阻挡层，在110℃下干燥10min。
以四氢呋喃为溶剂，化合物1和mCP均溶解在其中，二者质量比为10:90，记为10wt％化合物1：mCP，旋涂在电子阻挡层PVK之上，作为发光层，厚度为30nm，在50℃下干燥10min；
在发光层之上，通过真空蒸镀的方法蒸镀TmPyPB作为电子传输层，厚度为40nm；
在电子传输层之上，通过真空蒸镀的方法蒸镀LiF作为电子注入层，厚度为1nm；
在电子注入层之上，通过真空蒸镀的方法蒸镀Al作为阴极，厚度为80nm。
按照上述步骤制作出的电致发光器件，测量其电流效率和亮度等参数，其结果见表1所示。
器件2的结构：ITO/PEDOT:PSS(40nm)/Poly-TPD(35nm)/PVK(5nm)/5wt％化合物2:mCP(30nm)/TmPyPB(40nm)/LiF(1nm)/Al(80nm)。
器件2的制作方法与器件1一样，不同之处在于，将化合物2作为发光层，测量其电流效率和亮度等参数，其结果见表1所示。
相关材料的分子结构式如下所示：
表1器件的性能
以上所述仅为本发明的实施例，并不是本发明的限制。本发明旨在提供一种以间苯二酚杯芳烃为核的有机电致发光材料，以本发明化合物作为功能层材料制作OLED器件，器件的结构和性能有进一步提升的空间，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (7)
1.一种间苯二酚杯芳烃化合物，其特征在于，所述化合物的结构如通式(1)所示：
其中，A1-A8为八个活性位点与功能成分反应后形成的官能团，R1-R8为有机发光二极管发光材料；A1-A8为1,4-二取代-1,2,3-三氮唑基团，其结构为
R1-R8选自以下任一种基团：
2.权利要求1所述的间苯二酚杯芳烃化合物在有机电致发光材料中的应用。
3.如权利要求2所述的间苯二酚杯芳烃化合物在有机电致发光材料中的应用，其特征在于，所述间苯二酚杯芳烃化合物为OLED发光层。
4.一种含有权利要求1所述的间苯二酚杯芳烃化合物的有机电致发光器件。
5.如权利要求4所述的有机电致发光器件，其特征在于，其结构为：
ITO/PEDOT:PSS/Poly-TPD/PVK/发光层/TmPyPB/LiF/Al；所述发光层为间苯二酚杯芳烃化合物与mCP的混合物；其中，间苯二酚杯芳烃化合物与mCP二者的混合百分比含量分别为5-10wt％和90-95wt％。
6.利用溶液法制备权利要求1所述的间苯二酚杯芳烃化合物的方法，其特征在于，包括以下步骤：
1)
2)
其中，Ri为有机发光二极管发光材料。
7.如权利要求6所述的制备间苯二酚杯芳烃化合物的方法，其特征在于，步骤1)的具体步骤为：将间苯二酚杯芳烃，K2CO3溶解在丙酮中，逐渐加入溴丙炔，室温回流反应，再加入溴丙炔回流，加入饱和食盐水，再加入盐酸中和，乙醚萃取得到有机相，旋蒸、干燥，最后以氯仿为淋洗剂，过硅胶色谱柱提纯，得到白色固体产物即为间苯二酚杯芳烃核体CRA-core；步骤2)的具体步骤为：在N2保护下，加入CRA-core、中间体Ri-N3和N,N,N',N,'N”-五甲基二亚乙基三胺、CuBr和DMF，室温搅拌反应后，通入空气，缓慢加入1,4,7,10-四氮杂环十二烷室温搅拌后终止反应，分离提纯即为目标产物。
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