CN107501164B - 一种含四苯基乙烯结构的双咔唑化合物及其制备和应用 - Google Patents
一种含四苯基乙烯结构的双咔唑化合物及其制备和应用 Download PDFInfo
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Abstract
本发明提供了一种含四苯基乙烯结构的双咔唑化合物及其制备和应用，该化合物的名称是：9,9'‑(5‑(2,2‑二苯基‑1‑(4‑苯甲基))乙烯基‑1,3‑亚苯基)双咔唑。制备方法是：首先制备3,5‑二(9‑咔唑基)苯基‑(4‑甲基苯基)甲酮；然后将3,5‑二(9‑咔唑基)苯基‑(4‑甲基苯基)甲酮与二苯甲烷反应得到9,9'‑(5‑(2,2‑二苯基‑1‑(4‑苯甲基))乙烯基‑1,3‑亚苯基)双咔唑。该化合物具有优良的热稳定性能、电化学稳定性能、电荷传输性能和发光性能，可用作蓝绿色有机电致发光材料。
Description
技术领域
本发明涉及含碳、氢、氮的杂环化合物，具体属于一种含四苯基乙烯结构的双咔唑化合物的制备方法，以及该化合物作为有机电致发光材料的应用。
背景技术
有机发光二极管(OLED)由于其在固态发光和平面显示上的广泛应用使得OLED成为学术界和商业的热点。通常，OLED器件需要通过传输层和发光层来吸收激子发光。但是传统的发光材料在用作发光层制备OLED时，通常会发生浓度猝灭效应(ACQ)，也即在溶液状态时发光较强，但在固态聚集下会由于分子间的π-π堆积作用使发光减弱。这种ACQ效应严重制约了OLED的发展。直到2001年，唐本忠等发现了一种与ACQ完全相反的现象：一些材料在溶液下发光微弱甚至不发光，但在固态薄膜下发光较强。这种现象被成为聚集诱导发光(AIE)。自AIE现象提出以来，唐本忠和其他研究学者开始对AIE过程的机理进行研究。他们采用了一系列从外部和内部调制的模型及理论研究证明了分子内旋转受限(RIR)是AIE现象的主要原因。基于RIR机理的AIE分子一般有通过单键与分子骨架连接的能够自由旋转的芳香环，稀溶液中分子会通过旋转芳香环的方式消耗掉分子从激发态返回到基态的能量；而聚集态下芳香环被固定，能量只能通过辐射跃迁发光的方式消耗。
基于上述报道的AIE的发光机理，许多课题组开始致力于设计合成AIE发光团。在这些AIE发光团中，四苯基乙烯(TPE)结构由于结构简单，易于合成，能够连接ACQ分子组成新的AIE分子而被受人们关注。此外，咔唑基团是典型的ACQ基团，但是富含电子，有利于电荷传输。并且咔唑分子还具有优良的热稳定性能，这对于延长OLED的使用寿命是十分有利的。基于上述分析，通过把具有AIE性能的TPE分子和具有ACQ性能的咔唑分子结合在一起，设计合成新的荧光分子，研究新分子的AIE效应及在OLED中的应用具有重要的价值。因此，我们在这里提供了一种含四苯基乙烯结构的双咔唑化合物及其制备、光学性质和应用。
发明内容
本发明的目的在于提供一种含四苯基乙烯结构的双咔唑化合物及其制备方法。
本发明的另一目的在于提供一种含四苯基乙烯结构的双咔唑化合物作为发光材料在有机电致发光器件中的应用。
本发明提供的一种含四苯基乙烯结构的双咔唑化合物，它是9,9'-(5-(2,2-二苯基-1-(4-苯甲基))乙烯基-1,3-亚苯基)双咔唑，简称DPPBC，结构式为：
本发明提供的制备含四苯基乙烯结构的双咔唑化合物的反应式如下：
化合物DPPBC的制备方法，包括如下步骤：
(1)按摩尔比1：2.2：3取9,9'-(5-溴-1,3-亚苯基)双咔唑，叔丁基锂和对甲基苯甲醛：在-78℃时，向溶有9,9'-(5-溴-1,3-亚苯基)双咔唑的THF溶液中加入叔丁基锂，在此温度下搅拌反应1h～2h，再在常温下搅拌反应5h～6h；再将混合物温度降至-78℃，向混合物中加入对甲基苯甲醛；反应物逐渐回升至室温，在室温下搅拌反应过夜；用冰水猝灭反应，停止搅拌，CH2Cl2萃取2～3次，水洗2～3次，合并有机层，用无水MgSO4干燥，旋干溶剂；然后经过柱色谱分离，得到白色固体的化合物3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮；
(2)按摩尔比1:1.5:1.8取3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮、二苯甲烷和正丁基锂，先将二苯甲烷加入到无水的THF溶剂中，然后在-78℃时，滴加正丁基锂，搅拌1.5h～2h；再把反应得到的混合物转移到溶有3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮的THF溶剂中，反应逐渐回升至室温，最后在室温下搅拌反应12h；反应终止后，反应混合物用CH2Cl2萃取；有机层用水洗涤，然后用无水MgSO4干燥，利用旋转蒸发仪旋出溶剂；将得到的固体溶于甲苯中，加入对甲苯磺酸用于脱水反应；在通氮气的情况下，搅拌回流反应18h～24h；停止反应，反应温度降至室温；将反应物旋干，先用卤水除去对甲苯磺酸，再用二氯甲烷进行萃取，收集有机层，旋干，将固体用水洗涤，然后抽干得到黄色固体，最后通过柱分离得到9,9'-(5-(2,2-二苯基-1-(4-苯甲基))乙烯基-1,3-亚苯基)双咔唑。
本发明所述的含四苯基乙烯结构的双咔唑化合物可用作蓝绿光有机电致发光材料。
本发明提供的包含发光层的有机电致发光器件，所述的发光层含有所述的含四苯基乙烯结构的双咔唑化合物。
我们制备的器件是蓝绿光有机电致发光器件，器件的结构为：ITO/HATCN(厚度20nm)/NPB(厚度40nm)/权利要求1所述的含四苯基乙烯结构的双咔唑化合物(厚度20nm)/TPBI(厚度40nm)/LiF(厚度1nm)/Al(厚度100nm)。
本发明提供的发光器件经测试表明：发光器件的启亮电压为3.6V，最大亮度为10290cd/m2，最大电流效率为4.075cd/A。说明该化合物是适宜于有机电致发光器件的性能优良的发光材料，具有广泛的应用前景。
与现有技术相比，本发明具有的优点和效果：
1.本发明合成的含四苯基乙烯结构的双咔唑化合物，具有热稳定性好，发光效率高、传输性能好的特点，可作为器件的发光材料。
2.本发明提供的含四苯基乙烯结构的双咔唑化合物的制备方法简便，合成步骤简单，产物产率及纯度高，操作易行。
3.本发明提供的含四苯基乙烯结构的双咔唑化合物可用作有机电致发光器件中的蓝绿色发光材料，具有广阔的应用前景。
附图说明
图1化合物DPPBC的紫外吸收光谱
图2化合物DPPBC的荧光光谱图
图3化合物DPPBC的AIE发光光谱
图4化合物DPPBC的固态荧光发光光谱
图5发光器件的电流密度-电压-亮度曲线
图6发光器件的电流效率-电流密度曲线
图7发光器件的电致发光光谱
具体实施方式
实施例1. 9,9'-(5-(2,2-二苯基-1-(4-苯甲基))乙烯基-1,3-亚苯基)双咔唑的制备，步骤如下：
(1)3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮的合成；
在-78℃时，向溶有5.3g(10.9mmol)9,9'-(5-溴-1,3-亚苯基)双咔唑的THF溶液中加入18.8mL叔丁基锂(1.3M,24.4mmol)，在此温度下搅拌反应1h，再在常温下搅拌反应5h；再将混合物温度降至-78℃，向混合物中加入3.9mL(32.7mmol)的对甲基苯甲醛；反应物逐渐回升至室温，在室温下搅拌反应过夜；用冰水猝灭反应，停止搅拌，CH2Cl2萃取3次，水洗3次，合并有机层，用无水MgSO4干燥，旋干溶剂；然后经过柱色谱分离，得到白色固体的化合物3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮1.9g，产率36.5％；
(2)9,9'-(5-(2,2-二苯基-1-(4-苯甲基))乙烯基-1,3-亚苯基)双咔唑的合成及表征；
先将0.57mL(2.9mmol)二苯甲烷加入到30mL无水的THF溶剂中，然后在-78℃时，滴加1.44mL(2.4M,3.45mmol)正丁基锂，搅拌1.5h；再把反应得到的混合物转移到溶有1g(1.9mmol)3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮的40mL的THF溶剂中，反应逐渐回升至室温，最后在室温下搅拌反应12h；反应终止后，反应混合物用CH2Cl2萃取；有机层用水洗涤，然后用无水MgSO4干燥；利用旋转蒸发仪旋出溶剂；将得到的固体溶于80mL甲苯中，加入0.8g的对甲苯磺酸用于脱水反应；在通氮气的情况下，搅拌回流反应24h；停止反应，反应温度降至室温；将反应物旋干，先用卤水除去对甲苯磺酸，再用二氯甲烷进行萃取，收集有机层，旋干，将固体用水洗涤3次，然后抽干得到黄色固体，最后通过柱分离得到9,9'-(5-(2,2-二苯基-1-(4-苯甲基))乙烯基-1,3-亚苯基)双咔唑0.9g，产率60％。
表征数据：1H NMR(600MHz,CDCl3),δ(ppm):8.14(d,J＝7.7z,2H),7.67–7.61(m,2H),7.57–7.52(m,2H),7.45(t,J＝7.7Hz,2H),7.36–7.29(m,4H),7.19(d,J＝7.1Hz,4H),7.16–7.05(m,8H),6.97(d,J＝7.3Hz,3H),6.77(d,J＝9.4Hz,2H),6.41–6.31(m,3H),1.94(s,3H).13C NMR(150MHz,CDCl3)δ(ppm):143.65,143.45,142.68,142.33,140.39,140.33,140.27,138.19,138.03,137.49,136.13,136.10,135.46,130.91,130.64,129.60,129.52,128.94,128.52,128.32,128.14,127.70,127.62,127.43,127.13,126.23,126.22,126.09,125.85,125.38,123.64,120.41,120.29,119.65,119.42,110.56,110.24,109.76,109.71,77.23,76.81,56.34,26.93,20.90.
实施例2.有机电致发光器件的结构、制备和性能：
我们制备的器件是蓝绿色有机电致发光器件，器件结构为：ITO/HATCN(厚度20nm)/NPB(厚度40nm)/化合物DPPBC(厚度20nm)/TPBI(厚度40nm)/LiF(厚度1nm)/Al(厚度100nm)。其中，HATCN作为空穴注入层，NPB作为空穴传输层；9,9'-(5-(2,2-二苯基-1-(4-苯甲基))乙烯基-1,3-亚苯基)双咔唑(化合物DPPBC)作为发光层；TPBI作为电子传输层。
器件的制备步骤：先用丙酮擦洗ITO玻璃，然后用清水冲洗，接着用清洗液超声清洗，最后用清水超声洗。洗净的基片用氮气吹干，最后用紫外线-臭氧处理以充分洗净表面。根据所设计的器件的结构按顺序依次在ITO基片上蒸镀20nm厚的HATCN作为空穴注入层、蒸镀40nm厚的NPB作为空穴传输层，蒸镀20nm厚的9,9'-(5-(2,2-二苯基-1-(4-苯甲基))乙烯基-1,3-亚苯基)双咔唑(化合物DPPBC)作为发光层，蒸镀40nm厚的TPBI作为电子传输层，蒸镀1nm厚的氟化锂作为电子注入层，蒸镀100nm厚的铝作为器件的阴极。整个蒸镀过程均在高真空下进行，有机层的蒸镀速度控制在0.2-0.5nm/s,金属铝层的蒸镀速度控制在0.5-1nm/s。
本发明提供的发光器件经测试表明：器件的启亮电压为3.6V，最大亮度为10290cd/m2，最大电流效率为4.075cd/A。发光器件的优良性能表明化合物DPPBC是适宜于有机电致发光器件的性能优良的发光材料，具有广泛的应用前景。
Claims (6)
1.一种含四苯基乙烯结构的双咔唑化合物，其特征在于，结构式为：
2.如权利要求1所述的一种含四苯基乙烯结构的双咔唑化合物的制备方法，其特征在于，包括如下步骤：
(1)制备(3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮；
(2)按摩尔比1:1.5:1.8取(3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮、二苯甲烷和正丁基锂，先将二苯甲烷加入到THF溶剂中，然后在-78℃时，滴加正丁基锂，搅拌1.5h～2h；再把反应得到的混合物转移到溶有(3,5-二(9-咔唑基)苯基-(4-甲基苯基)甲酮的THF溶液中，反应逐渐回升至室温，最后在室温下搅拌反应12h；反应终止后，反应混合物用CH2Cl2萃取；有机层用水洗涤，然后用无水MgSO4干燥，利用旋转蒸发仪旋出溶剂；将得到的固体溶于甲苯中，加入对甲苯磺酸；在通氮气的情况下，搅拌回流反应18h～24h；停止反应，反应温度降至室温；将反应物旋干，用二氯甲烷进行萃取，收集有机层，旋干，将固体用水洗涤，然后抽干得到黄色固体，最后通过柱分离得到9,9'-(5-(2,2-二苯基-1-(4-苯甲基))乙烯基-1,3-亚苯基)双咔唑。
3.如权利要求1所述的含四苯基乙烯结构的双咔唑化合物用作蓝绿色有机电致发光材料。
4.一种有机电致发光器件，包括发光层，其特征在于，所述的发光层含有如权利要求1所述的含四苯基乙烯结构的双咔唑化合物。
5.一种有机电致发光器件，其特征在于，器件的结构为：ITO/HATCN，厚度20nm/NPB，厚度40nm/权利要求1所述的含四苯基乙烯结构的双咔唑化合物，厚度20nm/TPBI，厚度40nm/LiF，厚度1nm/Al，厚度100nm。
6.如权利要求1所述的含四苯基乙烯结构的双咔唑化合物在有机电致发光器件中的应用。
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