CN112279816B - 一种电子传输材料及使用该种材料的有机电致发光器件 - Google Patents
一种电子传输材料及使用该种材料的有机电致发光器件 Download PDFInfo
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Abstract
Description
技术领域
本发明有机电致发光材料技术领域,具体涉及一种电子传输材料及使用该种材料的有机电致发光器件。
背景技术
随着科学技术的发展,电子显示设备在人类的日常生活中已是必不可少的工具,在人类与机器的互动过程中,电子显示设备扮演了举足轻重的角色;同时,随着新的显示技术的涌现,电子显示设备市场更是以迅雷不及掩耳的速度在发展。传统的CRT显示器,不仅笨重,而且体积比较庞大,这给使用者带来很大的不便,因此已逐渐被轻薄的等离子显示器PDP(Plasma Display Panel)和液晶显示器LCD(Liquid Crystal Display)所取代。在新崛起的平板显示技术中,OLED(Organic Light Emitting Diode,有机电致发光二极管)是最具市场前景的新技术。利用此元件与技术不仅可制成具有轻薄、易扭曲、低功耗等优点的电子显示设备,而且与传统电子显示设备相比较而言,这种显示器的可视角度宽、响应时间短,也克服了传统电子显示设备有影像残影的缺点,是平面显示器未来发展的趋势。
1963年Pope公开报道了有关于OLED的第一篇文章:当Anthracence晶体被数百伏特的电压通过时,可以很明显的看到Anthracence晶体发光的现象。但由于使用的电压很高以及发光效率很低的原因,在当时并没有受到研究学者的重视。随着技术不断进步,1987年Kodak公司的C.W.Tang等人以8-羟基喹啉铝(AIq3)为发光材料,采用真空蒸镀的方法制成了双层夹心结构OLED器件,启亮电压仅有几伏特,亮度最高可达1000cd/m2,标志OLED朝向实用化迈出了重要的一步,使其具有强大的商业应用潜力,从而引起了全球的瞩目,OLED也因此成为了研究热点。
载流子的平衡注入是提高OLED元件发光效率的关键因素,因此,就必需要解决如何才能使载流子在器件中实现平衡注入的问题。然而,很多发光材料的电子亲和势都是比较弱的,因此,大多数情况下,都是以空穴来作为主要载流子。根据载流子的不同可分为:电子传输材料和空穴传输材料,
电子传输层是有机电致发光器件中必不可少的组成部分,通常来说,电子传输材料都具有大的共轭结构的平面芳香族化合物,较好的电子接受能力,同时在一定的正向偏压下又可以有效的传递电子。目前可用的电子传输材料主要有8-羟基喹啉铝类化合物,恶二唑类化合物,咪唑类化合物,恶唑类化合物,***类化合物,含氮六元杂环类,全氟化类电子传输材料,有机硅类电子传输材料等。
目前,在有机电致发光器件中,空穴传输速度远远大于电子传输速度,两者的差值往往达到一个数量级,为了保证器件中电子和空穴的平衡,人们往往需要引入专门的空穴阻挡层,或者要求电子传输层本身,具有一定的空穴阻挡能力,因此,开发具有优良性能的电子传输材料,具有较强的现实意义。
发明内容
发明目的:针对上述技术问题,本发明提供了
为了达到上述发明目的,本发明所采用的技术方案如下:
一种电子传输材料,其结构式如下所示:
其中,L为单键或亚苯基;
X、Y、Z各自独立的选自C或N,且X、Y、Z中至少两个为N;
R1、R2各自独立的选自取代或未取代的C6-C18的芳香基、取代或未取代的C6-C30的杂芳香基;
m为0或1。
进一步地,R1、R2各自独立的选自未取代的C6-C18的芳香基、C1-C4烷基取代的C6-C18的芳香基、三氘甲基取代的C6-C18的芳香基、苯基取代的C6-C18的芳香基、未取代的C6-C30的杂芳香基、苯基取代的C6-C30的杂芳香基。
进一步地,R1、R2各自独立的选自以下结构式的基团:
进一步地,所述电子传输材料为以下结构式化合物中的一种:
上述电子传输材料的制备方法,包括以下步骤:
(1)
惰性气体保护下,将结构通式为的化合物a加入到无水四氢呋喃中溶解后降温至-78℃以下,再将正丁基锂的己烷溶液缓慢滴入,滴加完毕后搅拌20-50min,再将结构式为的化合物b加入到无水四氢呋喃中溶解后滴入反应体系中,滴加完毕后搅拌20-50min,缓慢恢复室温反应8-15h,反应结束后将反应淬灭,再加入乙酸乙酯,搅拌20-50后分液,有机相干燥后减压浓缩,柱层析提纯得到化合物c;
(2)
惰性气体保护下,将镁、碘加入到无水四氢呋喃中,室温搅拌10-30min后,加热至50-60℃继续搅拌10-30min得到溶液A,结构通式为R1-Br的化合物e加入到无水四氢呋喃中,搅拌溶解后滴入溶液A中,滴毕后搅拌1-3h,加热至回流反应搅拌2-4h,冷却至室温后冰浴得到溶液B,将结构式为的化合物d加入到无水四氢呋喃中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌反应5-10h,反应结束后滴加盐酸,再搅拌10-30min后,加入甲苯,继续搅拌10-30min,分液,有机相干燥后减压浓缩,柱层析提纯得到化合物f;
(3)
惰性气体保护下,将镁、碘加入到无水四氢呋喃中,室温搅拌10-30min后,加热至50-60℃继续搅拌10-30min得到溶液A,结构通式为R2-Br的化合物g加入到无水四氢呋喃中,搅拌溶解后滴入溶液A中,滴毕后搅拌1-3h,加热至回流反应搅拌2-4h,冷却至室温后冰浴得到溶液B,将结构式为的化合物f加入到无水四氢呋喃中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌反应5-10h,反应结束后滴加盐酸,再搅拌10-30min后,加入甲苯,继续搅拌10-30min,分液,有机相干燥后减压浓缩,柱层析提纯得到化合物h;
(4)
将结构通式为的化合物h、结构通式为的化合物c、四硼酸钠加入到无水四氢呋喃和水中,搅拌溶解后,再将双(三苯基膦)二氯化钯(II)和水合肼加入,惰性气体保护下升温至回流,搅拌反应45-60h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取分液,有机相干燥后减压浓缩,柱层析提纯即可得到所述电子传输材料。
上述电子传输材料在制备有机电致发光器件中的应用。
一种有机电致发光器件,包括顺次设置的阴极、电子注入层、电子传输层、发光层、空穴传输层、空穴注入层、阳极,所述电子传输层中含有至少一种上述电子传输材料。
进一步地,所述电子传输层中含有一种或两种上述电子传输材料。
一种电子显示设备,包括上述有机电致发光器件。
一种照明设备,包括上述有机电致发光器件。
本发明所述的室温为25±5℃。
本发明的有益效果:
本发明提供的电子传输材料,该类电子传输材料具备以下两个结构特征:
1、结构II,该结构由于六个甲基及其与萘环构成的五元环的结构特征,使其具备丰富的电子云密度及良好的热稳定性,丰富的电子云密度提高了材料分子的载流子迁移速率,并且大幅降低了材料分子的LOMO能级,该两种特性决定了该类材料可以做为性能优良的电子传输材料使用。
2、结构III,当该结构中的X、Y、Z,其中一个或多个为氮时,由于氮原子上多余的一对孤对电子,导致该结构的电子云密度大幅度提高,使得以该结构为基团的材料分子具备良好的载流子传输性能,该基团的引入,同时增大了材料分子的分子量,能够有效提高材料分子的Tg,并降低了材料分子的结晶性,该结构与结构II组合使用,能够起到良好的倍增效应。
经器件验证,本发明提供的电子传输材料具有非常高的电子迁移率及电子亲和势,并且具备良好的热稳定性能,器件实验表明,使用本发明电子传输材料的有机电致发光器件,其发光效率和发光寿命均有显著的提高,而且驱动电压也有大幅度的降低。
附图说明
图1为本发明应用例1、对照例1、对照例2亮度随电压变化的关系图;
图2为本发明应用例1发光寿命图。
具体实施方式
实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1:
电子传输材料(1)的具体合成方法如下:
(1)
氮气保护下,将化合物1(10g,330g/mol,30.3mmol)加入到无水四氢呋喃中(100g,化合物1质量的10倍)搅拌溶解后液氮降温至-78℃,将正丁基锂(33.33mmol)的己烷溶液(1.6M)缓慢滴入,滴加完毕后搅拌30min,再将化合物2(1.1eq,6.2g,186.14g/mol,33.33mmol)加入到无水四氢呋喃中(62g,化合物2质量的10倍)搅拌溶解后滴入反应体系,滴加完毕后搅拌30min,缓慢恢复室温反应10h,反应结束后用饱和氯化铵溶液(500g,化合物1质量的50倍)将反应淬灭,再加入乙酸乙酯(500g,化合物1质量的50倍),搅拌20min后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物3(10.6g,收率92.6%,MS(EI):378(M+))。
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物5(2.1eq,205.97g/mol,23.65g,114.8mmol)加入到无水四氢呋喃中(236.5g,化合物5的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物4(10g,182.92g/mol,54.67mmol)加入到无水四氢呋喃(100g,化合物4的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物6(10.07g,收率50.2%,MS(EI):367(M+))。
(3)
将化合物3(10g,378g/mol,26.46mmol)、化合物6(1eq,9.71g,367g/mol,26.46mmol)、四硼酸钠(1.5eq,15.14g,381.37g/mol,39.69mmol)加入到THF(100g,化合物3的10倍质量)和水(30g,化合物3的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.37g,701.9g/mol,0.53mmol)和水合肼(3%eq,0.039g,50.06g/mol,0.79mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(1)(11.18g,收率72.5%,MS(EI):583(M+))。
实施例2:
电子传输材料(2)的具体合成方法如下:
步骤(1)与实施例1基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物5(2.1eq,205.97g/mol,23.65g,114.8mmol)加入到无水四氢呋喃中(236.5g,化合物5的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物7(10g,181.92g/mol,57.97mmol)加入到无水四氢呋喃(100g,化合物7的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物8(10.88g,收率51.3%,MS(EI):366(M+))。
(3)
将化合物3(10g,378g/mol,26.46mmol)、化合物8(1eq,9.68g,366g/mol,26.46mmol)、四硼酸钠(1.5eq,15.14g,381.37g/mol,39.69mmol)加入到THF(100g,化合物3的10倍质量)和水(30g,化合物3的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.37g,701.9g/mol,0.53mmol)和水合肼(3%eq,0.039g,50.06g/mol,0.79mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(2)(11.07g,收率71.9%,MS(EI):582(M+))。
实施例3:
电子传输材料(3)的具体合成方法如下:
步骤(1)与实施例1基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物9(2.1eq,231.99g/mol,26.63g,114.8mmol)加入到无水四氢呋喃中(266.3g,化合物9的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物4(10g,182.92g/mol,54.67mmol)加入到无水四氢呋喃(100g,化合物4的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物10(11.57g,收率50.5%,MS(EI):419(M+))。
(3)
将化合物3(10g,378g/mol,26.46mmol)、化合物10(1eq,11.09g,419.12g/mol,26.46mmol)、四硼酸钠(1.5eq,15.14g,381.37g/mol,39.69mmol)加入到THF(100g,化合物3的10倍质量)和水(30g,化合物3的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.37g,701.9g/mol,0.53mmol)和水合肼(3%eq,0.039g,50.06g/mol,0.79mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(3)(11.07g,收率71.9%,MS(EI):582(M+))。
实施例4:
电子传输材料(4)的具体合成方法如下:
步骤(1)与实施例1基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物9(2.1eq,231.99g/mol,26.63g,114.8mmol)加入到无水四氢呋喃中(266.3g,化合物9的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物7(10g,181.92g/mol,54.96mmol)加入到无水四氢呋喃(100g,化合物7的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物11(11.62g,收率50.6%,MS(EI):418(M+))。
(3)
将化合物3(10g,378g/mol,26.46mmol)、化合物11(1eq,11.06g,418g/mol,26.46mmol)、四硼酸钠(1.5eq,15.14g,381.37g/mol,39.69mmol)加入到THF(100g,化合物3的10倍质量)和水(30g,化合物3的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.37g,701.9g/mol,0.53mmol)和水合肼(3%eq,0.039g,50.06g/mol,0.79mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(4)(11.84g,收率70.6%,MS(EI):634(M+))。
实施例5:
电子传输材料(5)的具体合成方法如下:
(1)
氮气保护下,将化合物12(10g,406g/mol,24.6mmol)加入到无水四氢呋喃中(100g,化合物12质量的10倍)搅拌溶解后液氮降温至-78℃,将正丁基锂(33.33mmol)的己烷溶液(1.6M)缓慢滴入,滴加完毕后搅拌30min,再将化合物2(1.1eq,5.2g,186.14g/mol,28.0mmol)加入到无水四氢呋喃中(52g,化合物2质量的10倍)搅拌溶解后滴入反应体系,滴加完毕后搅拌30min,缓慢恢复室温反应10h,反应结束后用饱和氯化铵溶液(500g,化合物12质量的50倍)将反应淬灭,再加入乙酸乙酯(500g,化合物12质量的50倍),搅拌20min后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物13(10.3g,收率92.3%,MS(EI):454(M+))。
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物5(2.1eq,205.97g/mol,23.65g,114.8mmol)加入到无水四氢呋喃中(236.5g,合物5的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物4(10g,182.92g/mol,54.67mmol)加入到无水四氢呋喃(100g,化合物4的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物6(10.29g,收率51.3%,MS(EI):367(M+))。
(3)
将化合物13(10g,454g/mol,22.03mmol)、化合物6(1eq,8.09g,367.09g/mol,22.03mmol)、四硼酸钠(1.5eq,12.6g,381.37g/mol,33.05mmol)加入到THF(100g,化合物13的10倍质量)和水(30g,化合物13的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.31g,701.9g/mol,0.44mmol)和水合肼(3%eq,0.033g,50.06g/mol,0.66mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(5)(10.34g,收率71.2%,MS(EI):659(M+))。
实施例6:
电子传输材料(6)的具体合成方法如下:
步骤(1)与实施例5基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物5(2.1eq,205.97g/mol,23.65g,114.8mmol)加入到无水四氢呋喃中(236.5g,化合物5的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物7(10g,181.92g/mol,57.97mmol)加入到无水四氢呋喃(100g,化合物7的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物8(10.78g,收率50.8%,MS(EI):366(M+))。
(3)
将化合物13(10g,454g/mol,22.03mmol)、化合物8(1eq,8.06g,366.09g/mol,22.03mmol)、四硼酸钠(1.5eq,12.6g,381.37g/mol,33.05mmol)加入到THF(100g,化合物13的10倍质量)和水(30g,化合物13的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.31g,701.9g/mol,0.44mmol)和水合肼(3%eq,0.033g,50.06g/mol,0.66mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(6)(10.24g,收率70.5%,MS(EI):658(M+))。
实施例7:
电子传输材料(7)的具体合成方法如下:
步骤(1)与实施例5基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物9(2.1eq,231.99g/mol,26.63g,114.8mmol)加入到无水四氢呋喃中(266.3g,化合物9的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物4(10g,182.92g/mol,54.67mmol)加入到无水四氢呋喃(100g,化合物4的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物10(11.77g,收率51.4%,MS(EI):419(M+))。
(3)
将化合物13(10g,454g/mol,22.03mmol)、化合物10(1eq,9.23g,419.12g/mol,22.03mmol)、四硼酸钠(1.5eq,12.6g,381.37g/mol,33.05mmol)加入到THF(100g,化合物13的10倍质量)和水(30g,化合物13的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.31g,701.9g/mol,0.44mmol)和水合肼(3%eq,0.033g,50.06g/mol,0.66mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(7)(11.15g,收率71.2%,MS(EI):711(M+))。
实施例8:
电子传输材料(8)的具体合成方法如下:
步骤(1)与实施例5基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物9(2.1eq,231.99g/mol,26.63g,114.8mmol)加入到无水四氢呋喃中(266.3g,化合物9的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物7(10g,181.92g/mol,54.96mmol)加入到无水四氢呋喃(100g,化合物7的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物11(11.53g,收率50.2%,MS(EI):418(M+))。
(3)
将化合物13(10g,454g/mol,22.03mmol)、化合物11(1eq,9.21g,418.12g/mol,22.03mmol)、四硼酸钠(1.5eq,12.6g,381.37g/mol,33.05mmol)加入到THF(100g,化合物13的10倍质量)和水(30g,化合物13的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.31g,701.9g/mol,0.44mmol)和水合肼(3%eq,0.033g,50.06g/mol,0.66mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(7)(11.18g,收率71.5%,MS(EI):710(M+))。
实施例9:
电子传输材料(9)的具体合成方法如下:
步骤(1)与实施例5基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物14(2.1eq,245.97g/mol,28.24g,114.8mmol)加入到无水四氢呋喃中(282.4g,化合物14的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物4(10g,182.92g/mol,54.67mmol)加入到无水四氢呋喃(100g,化合物4的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物15(12.56g,收率51.4%,MS(EI):447(M+))。
(3)
将化合物13(10g,454g/mol,22.03mmol)、化合物15(1eq,9.85g,447g/mol,22.03mmol)、四硼酸钠(1.5eq,12.6g,381.37g/mol,33.05mmol)加入到THF(100g,化合物13的10倍质量)和水(30g,化合物13的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.31g,701.9g/mol,0.44mmol)和水合肼(3%eq,0.033g,50.06g/mol,0.66mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(9)(11.85g,收率72.8%,MS(EI):739(M+))。
实施例10:
电子传输材料(10)的具体合成方法如下:
步骤(1)与实施例5基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物16(2.1eq,261.95g/mol,30.23g,115.4mmol)加入到无水四氢呋喃中(302.3g,化合物16的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物7(10g,181.92g/mol,54.96mmol)加入到无水四氢呋喃(100g,化合物7的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物17(12.9g,收率49.2%,MS(EI):478(M+))。
(3)
将化合物13(10g,454g/mol,22.03mmol)、化合物17(1eq,10.49g,478g/mol,22.03mmol)、四硼酸钠(1.5eq,12.6g,381.37g/mol,33.05mmol)加入到THF(100g,化合物13的10倍质量)和水(30g,化合物13的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.31g,701.9g/mol,0.44mmol)和水合肼(3%eq,0.033g,50.06g/mol,0.66mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(10)(12.77g,收率75.4%,MS(EI):770(M+))。
实施例11:
电子传输材料(11)的具体合成方法如下:
步骤(1)与实施例1基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物16(2.1eq,261.95g/mol,30.07g,114.8mmol)加入到无水四氢呋喃中(300g,化合物16的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物4(10g,182.92g/mol,54.67mmol)加入到无水四氢呋喃(100g,化合物4的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物18(12.9g,收率49.6%,MS(EI):479(M+))。
(3)
将化合物3(10g,378g/mol,26.46mmol)、化合物18(1eq,12.67g,479g/mol,26.46mmol)、四硼酸钠(1.5eq,15.14g,381.37g/mol,39.69mmol)加入到THF(100g,化合物3的10倍质量)和水(30g,化合物3的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.37g,701.9g/mol,0.53mmol)和水合肼(3%eq,0.039g,50.06g/mol,0.79mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(1)(14.12g,收率76.8%,MS(EI):695(M+))。
实施例12:
电子传输材料(12)的具体合成方法如下:
步骤(1)与实施例1基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物19(2.1eq,245.97g/mol,28.24g,114.8mmol)加入到无水四氢呋喃中(282.4g,化合物19的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物7(10g,181.92g/mol,54.96mmol)加入到无水四氢呋喃(100g,化合物7的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物20(12.9g,收率52.9%,MS(EI):446(M+))。
(3)
将化合物3(10g,378g/mol,26.46mmol)、化合物20(1eq,11.83g,446g/mol,26.46mmol)、四硼酸钠(1.5eq,15.14g,381.37g/mol,39.69mmol)加入到THF(100g,化合物3的10倍质量)和水(30g,化合物3的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.37g,701.9g/mol,0.53mmol)和水合肼(3%eq,0.039g,50.06g/mol,0.79mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(12)(12.99g,收率74.2%,MS(EI):662(M+))。
实施例13:
电子传输材料(26)的具体合成方法如下:
步骤(1)与实施例1基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物21(1eq,302g/mol,16.5g,54.67mmol)加入到无水四氢呋喃中(165g,化合物21的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物4(10g,182.92g/mol,54.67mmol)加入到无水四氢呋喃(100g,化合物4的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物22(8.55g,收率46.4%,MS(EI):371(M+))。
(3)
氮气保护下,将镁(3.0eq,1.57g,24.3g/mol,64.68mmol)、碘(催化量)加入到无水四氢呋喃中(78.5g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物23(1eq,155.96g/mol,3.36g,21.56mmol)加入到无水四氢呋喃中(33.6g,化合物23的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物22(8g,371g/mol,21.56mmol)加入到无水四氢呋喃(80g,化合物22的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物24(5.93g,收率60.5%,MS(EI):413(M+))。
(4)
将化合物3(5g,378g/mol,13.23mmol)、化合物24(1eq,5.46g,413g/mol,13.23mmol)、四硼酸钠(1.5eq,7.57g,381.37g/mol,19.85mmol)加入到THF(50g,化合物3的10倍质量)和水(15g,化合物3的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.16g,701.9g/mol,0.27mmol)和水合肼(3%eq,0.0195g,50.06g/mol,0.395mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(26)(6.38g,收率76.7%,MS(EI):629(M+))。
实施例14:
电子传输材料(28)的具体合成方法如下:
步骤(1)、(2)与实施例13基本相同,其余步骤如下:
(3)
氮气保护下,将镁(3.0eq,1.57g,24.3g/mol,64.68mmol)、碘(催化量)加入到无水四氢呋喃中(78.5g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物25(1eq,173g/mol,3.73g,21.56mmol)加入到无水四氢呋喃中(37.3g,化合物25的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物22(8g,371g/mol,21.56mmol)加入到无水四氢呋喃(80g,化合物22的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物26(6.4g,收率62.8%,MS(EI):430(M+))。
(4)
将化合物3(5g,378g/mol,13.23mmol)、化合物26(1eq,5.69g,430g/mol,13.23mmol)、四硼酸钠(1.5eq,7.57g,381.37g/mol,19.85mmol)加入到THF(50g,化合物3的10倍质量)和水(15g,化合物3的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.16g,701.9g/mol,0.27mmol)和水合肼(3%eq,0.0195g,50.06g/mol,0.395mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(28)(6.73g,收率78.8%,MS(EI):646(M+))。
实施例15:
电子传输材料(97)的具体合成方法如下:
步骤(1)与实施例5基本相同,其余步骤如下:
(2)
氮气保护下,将镁(3.0eq,3.98g,24.3g/mol,164mmol)、碘(催化量)加入到无水四氢呋喃中(199g,镁的50倍质量),室温搅拌20min后,加热至55℃搅拌10min得到溶液A,将化合物23(2.1eq,155.96g/mol,17.9g,114.8mmol)加入到无水四氢呋喃中(179g,化合物23的10倍质量),搅拌溶解后滴入溶液A中,滴毕后搅拌1h,加热至回流反应搅拌2h,冷却至室温后冰浴得到溶液B,将化合物7(10g,181.92g/mol,54.96mmol)加入到无水四氢呋喃(100g,化合物7的10倍质量)中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌5h,滴加浓度为10%的盐酸,搅拌30min后,再加入甲苯,继续搅拌10min,分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到化合物20(8.5g,收率58.5%,MS(EI):266(M+))。
(3)
将化合物13(10g,454g/mol,22.03mmol)、化合物27(1eq,5.86g,266g/mol,22.03mmol)、四硼酸钠(1.5eq,12.6g,381.37g/mol,33.05mmol)加入到THF(100g,化合物13的10倍质量)和水(30g,化合物13的3倍质量)中,搅拌混匀溶解后,再将双(三苯基膦)二氯化钯(II)(2%eq,0.31g,701.9g/mol,0.44mmol)和水合肼(3%eq,0.033g,50.06g/mol,0.66mmol)加入,氮气保护下升温至回流,搅拌反应48h,冷却至室温后过滤,减压浓缩除去一定量THF后加乙酸乙酯,萃取后分液,有机相用无水硫酸钠干燥后减压浓缩,硅胶拌样后柱层析提纯得到电子传输材料(97)(9.12g,收率74.2%,MS(EI):558(M+))。
以下将通过实施例和对照例对本发明进行详细的说明。下属实施例于对照例只是为了举例说明本发明,本发明的范围并不限于下述实施例和对照例。
应用例1:
其采用ITO作为反射层阳极基板材料,并以N2等离子或UV-Ozone对其进行表面处理,在阳极基板上方,向空穴注入层(HIL)沉积HAT-CN 10纳米厚度的HAT-CN,在其上方选使用NPD以120纳米厚度形成空穴传输层(HTL),在上述空穴传输层(HTL)上方,真空蒸镀形成blue EML的9,10-Bis(2-naphthyl)anthraces(ADN)作为发光层,形成以2,5,8,11-Tetra-Butyl-Perilene(t-Bu-Perylene)为dopant材料,掺杂约5%的25纳米厚度形成发光层,在上述发光层上,选择本发明的有机电致发光材料1,并按照化合物1:LiQ=1:1的比例进行掺杂,蒸镀35纳米厚度形成电子传输层(ETL),之后在电子传输层上以2纳米厚度的LiQ进行蒸镀,形成电子注入层(EIL)上,此后在阴极将镁(Mg)和银(Ag)以9:1的比例混合且以厚度为15纳米进行蒸镀,在上述阴极封口层上沉积65纳米厚度的N4,N4′-BIS[4-BIS(3-methylphenyl)Amino phenyl)]-N4,N4′-Diphenyl-[1,1′-Biphenyl]-4,4′Diamin(DNTPD)。
此外,在阴极表面以UV硬化胶合剂和含有除湿剂的封装薄膜(seal cap)进行密封,以保护有机电致发光器件不被大气中的氧气或水分所影响至此制备获得有机电致发光器件。
应用例2-15
分别以本发明实施例2-15中的电子传输材料(2)、(3)、(4)、(5)、(6)、(7)、(8)、(9)、(10)、(11)、(12)、(26)、(28)、(97)作为电子输送层(ETL),其他部分与应用例1一致,据此制作出应用例2-15的有机电致发光器件。
对照例1、2
与应用例1的区别在于,分别用PBD和p-EtAZ作为电子输送层(ETL),其余与应用例1相同,据此制作出对照例1、2的有机电致发光器件。
上述应用例制造的有机电致发光器件及对照例制造的有机电致发光器件的特性是在电流密度为10mA/cm2的条件下测定的,结果如表1所示。
表1不同实验组器件性能测试结果:
由如上表1的实验对比数据可知,采用本发明电子传输材料作为电子输送层制备的有机电致发光器件的应用例1~15,与对照例1、2相比,电压有一定程度降低,发光效率提升90%以上,且OLED器件的蓝光色彩饱和度有一定程度提高,由此可见,本发明的化合物能使器件的驱动电压大大降低,减少了电能的消耗、显著提高了发光效率,另外通过低驱动电压,高的色彩饱和度,有机电致发光器件的寿命有效提高,色彩更加鲜艳。
Claims (9)
4.一种如权利要求1-3中任一项所述的电子传输材料的制备方法,其特征在于,包括以下步骤:
(1)
惰性气体保护下,将结构通式为的化合物a加入到无水四氢呋喃中溶解后降温至-78℃以下,再将正丁基锂的己烷溶液缓慢滴入,滴加完毕后搅拌20-50min,再将结构式为的化合物b加入到无水四氢呋喃中溶解后滴入反应体系中,滴加完毕后搅拌20-50min,缓慢恢复室温反应8-15h,反应结束后将反应淬灭,再加入乙酸乙酯,搅拌20-50后分液,有机相干燥后减压浓缩,柱层析提纯得到化合物c;
(2)
惰性气体保护下,将镁、碘加入到无水四氢呋喃中,室温搅拌10-30min后,加热至50-60℃继续搅拌10-30min得到溶液A,结构通式为R1-Br的化合物e加入到无水四氢呋喃中,搅拌溶解后滴入溶液A中,滴毕后搅拌1-3h,加热至回流反应搅拌2-4h,冷却至室温后冰浴得到溶液B,将结构式为的化合物d加入到无水四氢呋喃中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌反应5-10h,反应结束后滴加盐酸,再搅拌10-30min后,加入甲苯,继续搅拌10-30min,分液,有机相干燥后减压浓缩,柱层析提纯得到化合物f;
(3)
惰性气体保护下,将镁、碘加入到无水四氢呋喃中,室温搅拌10-30min后,加热至50-60℃继续搅拌10-30min得到溶液A,结构通式为R2-Br的化合物g加入到无水四氢呋喃中,搅拌溶解后滴入溶液A中,滴毕后搅拌1-3h,加热至回流反应搅拌2-4h,冷却至室温后冰浴得到溶液B,将结构式为的化合物f加入到无水四氢呋喃中,搅拌溶解后滴入溶液B中,滴毕后室温下搅拌反应5-10h,反应结束后滴加盐酸,再搅拌10-30min后,加入甲苯,继续搅拌10-30min,分液,有机相干燥后减压浓缩,柱层析提纯得到化合物h;
(4)
5.如权利要求1-3中任一项所述的电子传输材料在制备有机电致发光器件中的应用。
6.一种有机电致发光器件,其特征在于,包括顺次设置的阴极、电子注入层、电子传输层、发光层、空穴传输层、空穴注入层、阳极,所述电子传输层中含有至少一种如权利要求1-3中任一项所述的电子传输材料。
7.如权利要求6有机电致发光器件,其特征在于,所述电子传输层中含有一种或两种如权利要求1-3中任一项所述的电子传输材料。
8.一种电子显示设备,其特征在于,包括如权利要求6所述的有机电致发光器件。
9.一种照明设备,其特征在于,包括如权利要求6所述的有机电致发光器件。
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