CN115490733A - 含oncn四齿配体的杂环修饰的铂配合物 - Google Patents
含oncn四齿配体的杂环修饰的铂配合物 Download PDFInfo
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- CN115490733A CN115490733A CN202110673530.2A CN202110673530A CN115490733A CN 115490733 A CN115490733 A CN 115490733A CN 202110673530 A CN202110673530 A CN 202110673530A CN 115490733 A CN115490733 A CN 115490733A
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Abstract
Description
技术领域
本发明涉及发光材料领域,具体涉及含杂环铂配合物及其在有机发光二极管中的应用。
背景技术
磷光有机发光二极管(OLED)由于其OLEDs器件具有具备超轻超薄、低功耗、自主发光、工作温度范围大、宽色域、宽视角、响应速度快、更易实现柔性显示等诸多优点,在过去的几十年中已经引起了学术界与产业界极大的关注。对于磷光OLED分子来说,过渡金属中心与有机框架的协调提供了巨大的合成多样性。源于金属中心性质的变化,金属络合的键合模式以及配体设计,和构成了具有代表性的积木类。合理设计具有多功能的金属配合物,不仅可以调节电子吸收、发光和激发态氧化还原性质,而且可以实现多样化的光功能特性。是一种有巨大应用前景的新一代显示器和固态照明技术。
自1998年磷光OLED被发现以来,由于磷光OLED对比与传统荧光能够高效地利用单线态和三线态激子发光,理论上可以实现100%的内量子效率,在很大程度上促进了OLEDs的商业化进程。绝大多数金属配合物的发展来自于以Ir(III)为金属核心的六齿配合物。近十年金属配合物的最新发展使方形平面Pt(II)和Pd(II)配合物在许多方面甚至超过了Ir配合物的性能。特别是,N-杂环卡宾基发射体和四齿环金属化Pt和Pd配合物的发展,显着改善了光发射效率并降低了激子辐射寿命,使它们与Ir配合物更具有竞争力。此外,他们独特而多样的分子设计,可以获得更窄的发射光谱,能与不同的取代基微调各项如PL,HOMO,LUMO,CIE和T3能级等各项光物理属性。同时尽管铱配合物是目前OLED中最常见发光材料,但是铱金属是地壳中相对含量最低的元素,相对而言,同为重金属的铂和钯在地壳中的储量都高出很多。
含有氮原子或碳给体的双齿和三齿配体,比如C^N,C^N^N和N^C^N体系,经常用于开发磷光铂配合物。应用这些配体合成d8电子构型的配合物时,通常的选择是一个“三齿配体加一个单齿配体”或者“两个双齿配体”。而基于ONCN的Pt(II)四齿配合物由于多齿配体的螯合效应,金属离子被稳定在配合物的中心,一般配合物的去金属化能够被抑制,所以该类配合物将会有很高的热稳定性和相对高的化学稳定性;金属离子的dx2-y2轨道能级由于强场配体的存在而提高,从而减弱了激发态的分子形变,有望提高发光量子效率;共价性质的金属-碳键增加了金属d轨道和配体轨道的混合,从而也提高化合物的稳定性。金属d轨道和配体轨道的混合能够增强金属中心对配体本身的激发态的影响,增强自旋-轨道耦合效应,从而提高三重态的量子产率并促进高效的磷光辐射。
虽然基于ONCN的Pt(II)四齿配合物拥有诸多优点,Pt金属配合物发光材料已经在产业上无限靠近于应用。但其性能方面,如OLED器件对的发光效率、使用寿命仍须进一步提升,以满足商业化放大量产的需要。
发明内容
基于上述领域中的需求,本发明提供一种含ONCN四齿配体的杂环修饰的铂配合物,其所具有的含氮杂环结构的修饰能够显著提高其在特定光学元器件中的发光强度,出光效率。
一种含ONCN四齿配体的杂环修饰的铂配合物,其结构如式(I)所示,
其中:
R1至R15各自独立地选自:氢、氘、卤素、胺基、羰基、羧基、硫烷基、氰基、磺酰基、膦基、取代或未取代的具有1-20个碳原子的烷基、取代或未取代的具有3-20个环碳原子的环烷基、取代或未取代的具有2-20个碳原子的烯基、取代或未取代的具有1-20个碳原子的烷氧基;
Ar选自含有取代或未取代的具有6-30个碳原子的芳基、取代或未取代的具有3-30个碳原子的杂芳基;
所述杂芳基中的杂原子为N、S、O中的一个或多个;
所述取代为被卤素、胺基、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
优选地,R1至R15各自独立地选自:氢、氘、卤素、胺基、硫烷基、氰基、取代或未取代的具有1-6个碳原子的烷基、取代或未取代的具有3-6个环碳原子的环烷基、取代或未取代的具有2-6个碳原子的烯基、取代或未取代的具有1-6个碳原子的烷氧基;
Ar选自含有取代或未取代的具有6-30个碳原子的芳基、取代或未取代的具有3-30个碳原子的杂芳基;
所述取代为被卤素、胺基、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
优选地,R1至R15各自独立地选自:氢、氘、卤素、氰基、C1-C4烷基、取代或未取代的具有3-6个环碳原子的环烷基;
Ar选自含有取代或未取代的具有6-30个碳原子的芳基、取代或未取代的具有3-30个碳原子的杂芳基;
所述取代为被卤素、胺基、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
优选地,R1至R15各自独立地选自:氢、氘、氰基、甲基、异丙基、异丁基、叔丁基、取代或未取代的环戊基、取代或未取代的环己基;
Ar选自含有取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的吡嗪基、取代或未取代的嘧啶基、取代或未取代的咪唑基、取代或未取代的咔唑基;
所述取代为被卤素、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
优选地,通式(I)中,R1至R15各自独立地选自:氢、氘、甲基、叔丁基、氰基;
Ar选自含有取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的咪唑基、取代或未取代的咔唑基;
所述取代为被卤素、胺基、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
进一步优选,通式(I)中,R1至R15中的R13为叔丁基,其余为氢;
Ar选自含有取代或未取代苯基、取代或未取代吡啶基或者取代或未取代咔唑基。
以下列出按照本发明的铂金属配合物例子,但不限于所列举的结构:
上述金属配合物的前体,即配体,结构式如下:
上述铂配合物在有机发光二极管,有机薄膜晶体管,有机光伏器件,发光电化学池或化学传感器中的应用。
有机发光二极管,包括阴极、阳极和有机层,所述有机层为空穴注入层、空穴传输层、发光层、空穴阻挡层、电子注入层、电子传输层中的一层或多层,所述有机层中含有上述的铂配合物。
优选上述的铂配合物所在层为发光层。
本发明基于ONCN的铂配体骨架,通过修饰结构的加入,提高了材料的电致发光性能。
该类化合物合成步骤简单,很容易具备成熟工艺。
该化合物相比较与传统有机电致发光化合物化合物相比有较高的电致磷光电子产率和较低的激子辐射衰减寿命。
该化合物所具有的含氮杂环结构的修饰能够显著提高其在特定光学元器件中的发光强度,出光效率。
该类结构具有较多的可修饰位点,所含的咔唑基团增加的位阻,能有效降低分子间的聚集作用。
该类化合物可通过功能基团在不同位点的连接,改善分子空间构型,改善分子的工艺制备性能。
器件结果表明,本发明的铂配合物材料应用于有机发光二极管,具有更低的驱动电压和更高的发光效率。此外,基于本发明配合物的有机发光二极管的器件寿命显著优于对比例中的配合物材料,可以满足显示产业对于发光材料的要求,具有良好的产业化前景。
附图说明
图1为本发明的有机发光二极管器件结构图,
其中10代表为玻璃基板,20代表为阳极,30代表为空穴注入层,40代表为空穴传输层,50代表发光层,60电子传输层,70代表电子注入层,80代表阴极。
具体实施方式
本发明对材料的合成方法不作要求,为了更详细叙述本发明,特举以下例子,但不限于此。下述合成中所用到的原料如无特别说明均为市售产品。
实施例1:配合物1的合成
化合物1b的合成:
取500ml单口瓶,将化合物1a(30.0g,0.15mol)和I2(39.0g,0.15mol)溶于吡啶(200mL)中,氮气保护下,升温至120℃,搅拌过夜。将上述反应液冷却至室温,抽滤,得棕色固体,固体用甲醇热打浆1小时,过滤得化合物1b浅黄色固体44.0g,收率为72%。
H NMR(400MHz,DMSO)δ8.97(d,J=5.6Hz,2H),8.74(t,J=7.8Hz,1H),8.33–8.25(m,2H),8.19(s,1H),8.04(d,J=7.8Hz,1H),7.99(d,J=8.0Hz,1H),7.62(t,J=7.9Hz,1H),6.48(s,2H).
化合物1d的合成:
取500ml单口瓶,将化合物1c(20g,142.28mmol)、化合物1c-1(19.08g,156.51mmol)、Pd132(1.5g,2.11mmol)和碳酸钾(58.99g,426.84mmol)加入二氧六环(200ml)和水(50ml)中。氮气保护下,80℃搅拌反应2小时。冷至室温后,加水和二氯甲烷萃取两次,合并有机相,旋除溶剂后,剩余物经乙酸乙酯和正己烷比例为1比100的混合溶剂柱层析分离得到白色固体14.4g,收率为55.54%。
1H NMR(400MHz,Chloroform-d)δ9.99(s,1H),8.06–8.02(m,1H),7.61(td,J=7.5,1.4Hz,1H),7.52–7.30(m,7H).
化合物1e的合成:
取500ml三口瓶,将化合物1d(20g,109.76mmol)、化合物1d-1(19.98g,99.78mmol)加入甲醇(150ml)中,氮气保护下升温至47℃反应。用氢氧化钾(27.99g,498.90mmol)和水(38ml)所制备的碱溶液,滴加入三口瓶中,0.5小时滴加完毕。搅拌反应2小时。冷至室温后,加水和二氯甲烷萃取两次,合并有机相,旋除溶剂后,剩余物经乙酸乙酯和正己烷比例为1比20的混合溶剂柱层析分离得到黄色液体27.78g,收率为81.7%。
1H NMR(400MHz,Chloroform-d)δ7.84–7.79(m,1H),7.68(d,J=15.9Hz,1H),7.56(dd,J=7.6,1.6Hz,1H),7.50–7.27(m,10H),7.02–6.92(m,2H),3.86(s,3H).
化合物1f的合成:
取500ml单口瓶,将化合物1e(27.3g,86.83mmol)、化合物1b(35.06g,86.83mmol)、乙酸铵(58.66g,0.78mol)加入乙酸(196ml)中。氮气保护下,120℃搅拌反应2小时。冷至室温后,浓缩大部分乙酸,加水和二氯甲烷萃取两次,合并有机相,旋除溶剂后,硅胶漏斗过滤。用四氢呋喃和甲醇1比4重结晶,得到白色固体32.47g,收率为76.1%。
1H NMR(400MHz,Chloroform-d)δ7.94(dd,J=7.5,1.7Hz,2H),7.82(d,J=1.3Hz,1H),7.73(d,J=7.8Hz,1H),7.57–7.46(m,5H),7.41–7.36(m,1H),7.34–7.25(m,7H),7.11(t,J=7.5Hz,1H),7.00(d,J=8.2Hz,1H),3.81(s,3H).
化合物1g的合成:
取500ml单口瓶,将化合物1f(23.5g,47.72mmol)、联硼酸频那醇酯(13.3g,52.5mmol)、醋酸钾(14.48g,143.17mmol)、双(二苯基膦)二茂铁二氯化钯(1.75g,2.39mmol)加入二氧六环中(240ml)。氮气保护下,90℃搅拌反应6小时。加水和二氯甲烷萃取两次,合并有机相,旋除溶剂后,剩余物经乙酸乙酯和正己烷比例为1比10的混合溶剂柱层析分离得到3.4g白色固体20.33g,产率为79.1%。
1H NMR(400MHz,Chloroform-d)δ8.18(s,1H),8.12(d,J=7.9Hz,1H),7.93(dd,J=7.6,1.7Hz,1H),7.83(d,J=7.3Hz,1H),7.69(d,J=1.3Hz,1H),7.57–7.43(m,6H),7.40–7.26(m,6H),7.09(t,J=7.1Hz,1H),6.97(d,J=8.1Hz,1H),3.76(s,3H),1.39(s,12H).
化合物1h的合成:
取500ml单口瓶,将化合物1g(10g,18.53mmol),化合物1g-1(3.7g,22.24ml),碳酸钾(7.67g,55.59mmol),四三苯基膦钯(0.21g,0.185mmol)溶于1,4-二氧六环(50ml)和水(10ml)的混合溶剂。氮气保护下,100℃搅拌反应12小时。反应液用100ml乙酸乙酯萃取两次,旋干有机相,剩余物经乙酸乙酯和正己烷比例为1比10的混合溶剂柱层析分离得到白色固体6.5g,产率为64.3%。
1H NMR(400MHz,Chloroform-d)δ8.56(d,J=3.6Hz,1H),8.20(t,J=2.0Hz,1H),8.04(d,J=2.0Hz,1H),7.95(d,J=2.2Hz,1H),7.92(dd,J=8.6,1.3Hz,1H),7.92–7.86(m,2H),7.69–7.62(m,2H),7.61–7.43(m,8H),7.42–7.35(m,2H),7.31(dd,J=3.7,2.2Hz,1H),7.15(ddd,J=8.6,7.5,1.1Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.37(s,9H).
化合物1i的合成:
取250ml单口瓶,投入化合物1h(5.8g,10.63mmol),吡啶盐酸盐(58g,0.5mol)和邻二氯苯(10ml)加入烧瓶中。氮气保护下,100℃搅拌反应10小时。反应液用100ml乙酸乙酯萃取两次,旋干有机相,剩余物经乙酸乙酯和正己烷比例为1比5的混合溶剂柱层析分离得到产品黄色粉末5.5g,产率为97.5%。
1H NMR(400MHz,Chloroform-d)δ8.56(d,J=3.6Hz,1H),8.20(t,J=2.0Hz,1H),8.04(d,J=2.2Hz,1H),8.00(dd,J=8.7,1.2Hz,1H),7.92–7.85(m,3H),7.69–7.62(m,2H),7.61–7.43(m,8H),7.41–7.34(m,1H),7.31(dd,J=3.7,2.2Hz,1H),7.25(td,J=8.0,1.3Hz,1H),7.02–6.94(m,2H),1.37(s,9H).
配合物1的合成:
取1L单口瓶,将化合物1i(5g,9.4mmol)和K2PtCl4(5.64g,14.1mmol)和四丁基溴化铵(TBAB,438.6mg,1.41mmol)溶于乙酸中(400mL)。氮气保护下,135℃搅拌反应72小时。反应液加水析出固体,过滤得粗产物。剩余物经二氯甲烷过硅胶漏斗,旋干拌硅胶,经乙酸乙酯和正己烷比例为5比1的混合溶剂柱层析分离得到产品橙黄色粉末5.12g,产率为72.7%。
1H NMR(500MHz,Chloroform-d)δ8.91(d,J=8.9Hz,1H),7.94(dd,J=8.2,1.2Hz,1H),7.80(d,J=2.2Hz,1H),7.74–7.69(m,2H),7.61–7.43(m,13H),7.41–7.34(m,1H),7.30(td,J=7.4,1.2Hz,1H),7.17(dd,J=7.5,1.2Hz,1H),7.09(ddd,J=8.4,7.5,1.3Hz,1H),7.00(s,1H),1.37(s,7H).ESI-MS(m/z):723.2(M+1)。
实施例2:配合物8的合成
化合物8b的合成
取2L三口瓶,投入化合物8a(20g,117.15mmol)、化合物8a-1(29.08g,234.3mmol)、K2CO3(48.5g,351.45mmol)和DMF(1L),氮气保护,150℃搅拌反应72h。结束后浓缩大部分DMF,加水和二氯甲烷萃取两次,合并有机相,旋除溶剂后得到棕黑油状液体,经乙酸乙酯和正己烷比例为1比15的混合溶剂柱层析分离,得到无色油状物化合物8b,共18.01g,反应收率69.5%。
1H NMR(400MHz,Chloroform-d)δ9.48(d,J=0.7Hz,1H),7.89(dd,J=7.0,1.2Hz,1H),7.79(dt,J=6.8,1.4Hz,1H),7.67–7.60(m,2H),7.59–7.53(m,2H),7.37(td,J=7.0,1.3Hz,1H),7.30(td,J=6.6,1.2Hz,1H),7.21–7.14(m,1H),6.86(dd,J=5.1,1.2Hz,1H).
化合物8c的合成
取500ml单口瓶,投入化合物8b(17g,76.8mmol)、化合物1d-1(11.5g,76.8mmol)、MeOH(250ml),室温搅拌下滴加KOH水溶液(3.36g溶于30ml水),完毕后室温搅拌过夜(12h)。反应结束后有大量固体析出,直接抽滤并用少量甲醇洗涤多次,干燥得化合物8c,白色固体22.28g,反应收率为82.1%。
1H NMR(400MHz,Chloroform-d)δ8.07–8.00(m,1H),7.92(dd,J=7.4,1.8Hz,1H),7.79(dt,J=6.6,1.4Hz,1H),7.67–7.59(m,2H),7.54(dd,J=5.0,1.5Hz,2H),7.55–7.47(m,2H),7.47(ddd,J=8.4,7.4,1.7Hz,1H),7.33–7.25(m,2H),7.16(dtd,J=17.2,7.1,1.4Hz,2H),7.07(dd,J=8.4,1.3Hz,1H),6.88–6.83(m,1H),3.88(s,3H).
化合物8d的合成
取500ml单口瓶,投入化合物8c(15g,42.4mmol)、化合物1b(17.14g,42.4mmol)、醋酸铵(70.0g)和醋酸(200ml),130℃反应8h。反应结束后,冷却将反应液缓慢加到冰水浴中,大量灰绿色固样析出,抽滤干燥得灰绿色粗品,经乙酸乙酯和正己烷比例为1比15的混合溶剂柱层析分离,得12.1g黄色泡沫状固样,反应收率为53.7%。
1H NMR(400MHz,Chloroform-d)δ8.22(t,J=1.9Hz,1H),8.03–7.97(m,2H),7.96–7.90(m,2H),7.80(dt,J=7.0,1.2Hz,1H),7.67(dd,J=6.9,1.2Hz,1H),7.63(ddd,J=12.5,6.3,1.4Hz,2H),7.58–7.51(m,2H),7.46–7.38(m,2H),7.38(dd,J=7.6,1.2Hz,1H),7.29(dtd,J=8.4,6.8,1.2Hz,2H),7.21–7.11(m,2H),6.90(dd,J=7.7,1.2Hz,1H),6.88–6.83(m,1H),3.90(s,3H).
化合物8e的合成
取500ml单口瓶,投入化合物8d(7.6g,14.3mmol)、联硼酸频那醇酯(5.44g,21.4mmol)、醋酸钯(160.5mg,0.72mmol)、X-phos(667.4mg,1.4mmol)、醋酸钾(4.2g,42.9mmol)和二氧六环(250ml),氮气保护,90℃搅拌反应9h。反应结束后直接抽滤,取母液直接旋干,经乙酸乙酯和正己烷比例为1比15的混合溶剂柱层析分离。收集得到化合物8e共6.4g白色固体,反应收率77.36%。
1H NMR(400MHz,Chloroform-d)δ8.06(t,J=1.9Hz,1H),7.99(d,J=2.2Hz,1H),7.95–7.90(m,2H),7.82–7.76(m,2H),7.74(ddd,J=7.1,1.9,1.2Hz,1H),7.67(dd,J=6.9,1.2Hz,1H),7.63(ddd,J=12.5,6.3,1.4Hz,2H),7.55–7.47(m,2H),7.45–7.35(m,2H),7.32–7.25(m,2H),7.21–7.12(m,2H),6.90(dd,J=7.7,1.2Hz,1H),6.87–6.83(m,1H),3.90(s,3H),1.24(s,12H).
化合物8f的合成
取500ml单口瓶,投入化合物8e(6g,10.37mmol)、化合物1g-1(2.1g,12.4mmol)、Pd132(367mg,0.52mmol)、K2 CO3(4.29g,31.1mmol)、二氧六环(160ml)和水(40ml),氮气保护,90℃搅拌反应16h。反应结束后,旋除二氧六环,反应液用100ml乙酸乙酯萃取两次,旋干有机相,经乙酸乙酯和正己烷比例为1比6的混合溶剂柱层析分离。得到化合物8f共4.1g淡黄色固体,反应收率67.2%。
1H NMR(400MHz,Chloroform-d)δ8.56(d,J=3.6Hz,1H),8.20(t,J=2.0Hz,1H),8.02(d,J=2.0Hz,1H),7.96–7.86(m,4H),7.80(dt,J=6.9,1.2Hz,1H),7.70–7.63(m,3H),7.63(ddd,J=12.4,5.6,1.6Hz,2H),7.53(d,J=5.1Hz,1H),7.46–7.35(m,2H),7.34–7.28(m,2H),7.30–7.25(m,1H),7.21–7.11(m,2H),6.90(dd,J=7.7,1.2Hz,1H),6.88–6.83(m,1H),3.90(s,3H),1.37(s,9H).
化合物8g的合成
取250ml单口瓶,投入8f(4g,6.82mmol)、吡啶盐酸盐(40g)和2.4mL邻二氯苯,氮气保护,180℃反应12h。反应结束后,用二氯甲烷和水体系萃取洗涤两次,取有机相旋干。经乙酸乙酯和正己烷比例为1比6的混合溶剂柱层析分离,得化合物8g淡黄色固体3.1g,反应收率为79.5%。
1H NMR(400MHz,Chloroform-d)δ8.56(d,J=3.6Hz,1H),8.20(t,J=2.0Hz,1H),8.05–7.98(m,2H),7.92–7.86(m,3H),7.80(dt,J=7.1,1.3Hz,1H),7.70–7.59(m,5H),7.53(d,J=5.1Hz,1H),7.46–7.39(m,1H),7.34–7.28(m,2H),7.30–7.25(m,1H),7.25(td,J=8.0,1.3Hz,1H),7.17(td,J=6.8,1.6Hz,1H),7.02–6.94(m,2H),6.88–6.83(m,1H),1.37(s,9H).
配合物8的合成
取500ml单口瓶,将化合物8g(2.5g,4.37mmol)和K2PtCl4(2.47g,6.56mmol)和四丁基溴化铵(TBAB,211.3mg,0.65mmol)溶于乙酸中(250mL)。氮气保护下,135℃搅拌反应72小时。反应液加水析出固体,过滤得粗产物。剩余物经二氯甲烷过硅胶漏斗,旋干拌硅胶,经乙酸乙酯和正己烷比例为1比5的混合溶剂柱层析分离得到产品。橙黄色粉末状配合物8,共2.34g,产率为70.1%。
1H NMR(400MHz,Chloroform-d)δ8.91(d,J=8.9Hz,1H),8.08–8.03(m,2H),7.94(dd,J=8.2,1.2Hz,1H),7.80(td,J=3.7,3.1,1.5Hz,2H),7.67–7.47(m,7H),7.43(ddd,J=7.3,6.3,1.2Hz,1H),7.29(tdd,J=7.0,6.2,1.2Hz,3H),7.18(ddd,J=7.5,4.8,1.4Hz,2H),7.09(ddd,J=8.4,7.5,1.3Hz,1H),7.00(s,1H),6.88–6.83(m,1H),1.37(s,9H).ESI-MS(m/z):764.2(M+1)。
实施例3:配合物16的合成
化合物16b的合成
取1L三口瓶投入化合物8a(6.68g,40.0mmol)、8b(10.0g,80.0mmol)、K2CO3(8.28g,60.0mmol)和DMF(400ml),氮气保护,150℃搅拌反应72h。反应结束后,用二氯甲烷和水萃取洗涤两次;取有机相旋干得到棕黑油状液体,样品用乙酸乙酯和正己烷比例为1比15的混合溶剂柱层析分离;得化合物16b,淡黄色油状物17.0g,反应收率78.4%。
1H NMR(400MHz,CDCl3)δ9.60(d,J=0.7Hz,1H),8.22(dd,J=7.8,1.4Hz,1H),8.18(d,J=7.5Hz,2H),7.85(td,J=7.7,1.6Hz,1H),7.67(t,J=7.6Hz,1H),7.55(dd,J=7.9,0.7Hz,1H),7.46–7.38(m,2H),7.37–7.29(m,2H),7.17(d,J=8.1Hz,2H).
化合物16c的合成
取250ml单口瓶,投入化合物16b(5.42g,20.0mmol)、化合物1d-1(3.0g,20.0mmol)、MeOH(80ml),室温搅拌下滴加KOH水溶液(1.12g溶于10ml水),完毕后室温搅拌过夜(16h)。反应结束后有大量固体析出,直接抽滤并用少量甲醇洗涤多次,干燥得白色固体化合物16c共6.8g,反应收率为84.4%。
1H NMR(400MHz,CDCl3)δ8.12(d,J=7.7Hz,2H),8.00–7.94(m,1H),7.59(p,J=7.5Hz,2H),7.47–7.41(m,1H),7.35(t,J=7.6Hz,2H),7.28(d,J=7.1Hz,2H),7.23(s,1H),7.13(d,J=16.1Hz,1H),7.07–6.97(m,4H),6.69(dd,J=15.9,8.0Hz,2H),3.57(s,3H).
化合物16d的合成
取250ml单口瓶,投入化合物16c(12.9g,32.0mmol)、1b(12.9g,32.0mmol)、醋酸铵(62.0g)和醋酸(130ml),130℃反应8h。反应结束后,冷却将反应液缓慢加到冰水浴中,大量灰绿色固样析出,抽滤干燥得灰绿色粗品,乙酸乙酯和正己烷比例为1比15的混合溶剂柱层析分离;得10.5g黄色泡沫状固态化合物16d,反应收率为56.5%。
1H NMR(400MHz,CDCl3)δ8.08(d,J=7.7Hz,2H),7.77(t,J=3.8Hz,2H),7.75–7.71(m,1H),7.68(dt,J=7.2,3.6Hz,2H),7.66–7.61(m,1H),7.53(d,J=1.6Hz,1H),7.40–7.35(m,2H),7.35–7.31(m,2H),7.24(s,1H),7.18–7.11(m,3H),7.09(s,1H),7.06(dd,J=8.0,1.4Hz,2H),6.99–6.91(m,2H),3.74(s,3H).
化合物16e的合成
取250ml单口瓶,投入化合物16d(3.5g,6.0mmol)、联硼酸频那醇酯(2.29g,9.0mmol)、醋酸钯(67mg,0.3mmol)、X-phos(283mg,0.6mmol)、醋酸钾(1.77g,18.0mmol)和二氧六环(100ml),氮气保护,90℃搅拌反应12h。反应结束后直接抽滤,取母液直接旋干,乙酸乙酯和正己烷比例为1比15的混合溶剂柱层析分离;得3.5g白色产品化合物16e,反应收率92.5%。
1H NMR(400MHz,CDCl3)δ8.18(s,1H),8.03(d,J=7.7Hz,2H),7.76(dd,J=12.5,5.8Hz,2H),7.65(dt,J=11.3,7.6Hz,3H),7.60–7.52(m,2H),7.46(d,J=7.9Hz,1H),7.34–7.26(m,5H),7.17(dd,J=18.0,7.8Hz,4H),6.98(t,J=7.4Hz,1H),6.86(d,J=8.2Hz,1H),3.56(s,3H),1.36(s,12H).
化合物16f的合成
取500ml单口瓶,投入化合物16e(5.9g,11.8mmol,1.0eq)、化合物1g-1(2.4g,14.1mmol)、三[二亚苄基丙酮]二钯(538mg,0.59mmol,0.05eq)、X-phos(563mg,1.18mmol)、K2 CO3(4.88g,35.3mmol)、二氧六环(160ml)和水(40ml),氮气保护,90℃搅拌反应16h。反应结束后,旋除二氧六环,用EA/水的体系萃取洗涤,取有机相旋干,用乙酸乙酯和正己烷比例为1比6的混合溶剂柱层析分离,得3.6g淡黄色固体化合物16f,反应收率60.3%。
1H NMR(400MHz,CDCl3)δ8.61(d,J=5.2Hz,1H),8.38(s,1H),8.01(d,J=7.7Hz,2H),7.88(d,J=7.3Hz,1H),7.81–7.76(m,1H),7.68(dd,J=6.3,4.4Hz,3H),7.65(d,J=6.9Hz,1H),7.64–7.56(m,2H),7.40–7.26(m,5H),7.25–7.19(m,2H),7.16(t,J=7.0Hz,4H),6.98(t,J=7.5Hz,1H),6.89(d,J=8.3Hz,1H),3.60(s,3H),1.37(s,9H).
化合物16g的合成
取50ml单口瓶,投入化合物16f(2.4g,3.77mmol)、吡啶盐酸盐(24g)和2.4mL邻二氯苯,氮气保护,175℃反应12h。反应结束后,用二氯甲烷/水体系萃取洗涤两次,取有机相旋干;用乙酸乙酯和正己烷比例为1比6的混合溶剂柱层析分离,得到淡黄色固体化合物16g,共重2.0g,反应收率为85.21%。
1H NMR(400MHz,CDCl3)δ8.64(d,J=5.2Hz,1H),8.33(s,1H),8.04(d,J=7.7Hz,2H),7.97(d,J=7.6Hz,1H),7.86–7.81(m,1H),7.77–7.70(m,3H),7.69–7.64(m,1H),7.49–7.43(m,2H),7.42–7.31(m,4H),7.29(dd,J=5.2,1.7Hz,1H),7.24–7.16(m,3H),7.13(d,J=8.1H z,2H),6.89(d,J=8.3Hz,1H),6.64(d,J=6.1Hz,2H),1.40(s,9H).
配合物16的合成
取250ml单口瓶,投入化合物16g(1.5g,2.41mmol)、K2PtCl4(1.2g,2.90mmol)、四丁基溴化铵(TBAB,117mg,0.36mmol)和乙酸(150mL),氮气保护,130度反应48h。反应结束后,加入过量的去离子水,固体析出,抽滤,固体用二氯甲烷溶解,有机相旋干后用二氯甲烷作为洗脱剂柱层析分离,所得粗样再用混合溶剂(正己烷:二氯甲烷:乙酸乙酯=10:10∶1)柱层析分离纯化一遍,得配合物16橙色固体共重1.5g。最后用二氯甲烷与正己烷1比2重结晶,得到橙色固体1.27g,反应收率为64.6%。
1H NMR(400MHz,CDCl3)δ8.69(d,J=6.0Hz,1H),8.06(d,J=7.8Hz,2H),7.88–7.83(m,1H),7.78–7.73(m,2H),7.68(dd,J=8.7,4.4Hz,2H),7.59(s,1H),7.37(t,J=7.3Hz,2H),7.28(s,2H),7.21(dd,J=16.6,6.1Hz,6H),7.16(s,1H),6.83(t,J=7.6Hz,1H),6.78–6.69(m,2H),6.35(t,J=7.4Hz,1H),1.39(s,9H).
本领域技术人员应该知晓,上述制备方法只是一个示例性的例子,本领域技术人员能够通过对其改进从而获得本发明的其他化合物结构。
实施例4:
氮气氛围下,分别称量约5.0mg经过充分干燥的铂配合物1,9,16的样品,设置加热扫描速度为10℃/min,扫描范围25-800℃,测得热分解温度分别为416,403,427℃(热失重0.5%对应的温度),表明这类配合物具有非常优良的热稳定性。
实施例5:
使用本发明的配合物发光材料制备有机发光二极管,器件结构见图1。
首先,将透明导电ITO玻璃基板10(上面带有阳极20)依次经:洗涤剂溶液和去离子水,乙醇,丙酮,去离子水洗净,再用氧等离子处理30秒。
然后,在ITO上蒸镀10nm厚的HATCN作为空穴注入层30。
然后,蒸镀化合物HT,形成40nm厚的空穴传输层40。
然后,在空穴传输层上蒸镀20nm厚的发光层50,发光层由铂配合物1(20%)与CBP(80%)混合掺杂组成。
然后,在发光层上蒸镀40nm厚的AlQ3作为电子传输层60。
最后,蒸镀1nm LiF为电子注入层70和100nm Al作为器件阴极80。
实施例6:使用配合物8替换配合物1,采用实施例5中所描述的方法制备有机发光二极管。
实施例7:使用配合物16替换配合物1,采用实施例5中所描述的方法制备有机发光二极管。
比较例1:
使用配合物Ref-1(CN110872325A)替换配合物9,采用实施例7中所描述的方法制备有机发光二极管。
比较例2:
使用配合物Ref-2(Chem.Sci.,2014,5,4819)替换配合物9,采用实施例7中所描述的方法制备有机发光二极管。
器件中HATCN、HT、AlQ3、Ref-1、Ref-2及CBP结构式如下:
实施例5、实施例6、实施例7、比较例1、比较例2、中的有机电致发光器件在20mA/cm2电流密度下的器件性能列于表1:
表1
由表1数据可以看出,相同条件下,本发明的铂配合物材料应用于有机发光二极管,具有更低的驱动电压和更高的发光效率。此外,基于本发明配合物的有机发光二极管的器件寿命显著优于对比例中的配合物材料,可以满足显示产业对于发光材料的要求,具有良好的产业化前景。
上述多种实施方案仅作为示例,不用于限制本发明范围。在不偏离本发明精神的前提下,本发明中的多种材料和结构可以用其它材料和结构替代。应当理解,本领域的技术人员无需创造性的劳动就可以根据本发明的思路做出许多修改和变化。因此,技术人员在现有技术基础上通过分析、推理或者部分研究可以得到的技术方案,均应在权利要求书所限制的保护范围内。
Claims (11)
2.根据权利要求1所述的铂配合物,其中R1至R15各自独立地选自:氢、氘、卤素、胺基、硫烷基、氰基、取代或未取代的具有1-6个碳原子的烷基、取代或未取代的具有3-6个环碳原子的环烷基、取代或未取代的具有2-6个碳原子的烯基、取代或未取代的具有1-6个碳原子的烷氧基;
Ar选自含有取代或未取代的具有6-30个碳原子的芳基、取代或未取代的具有3-30个碳原子的杂芳基;
所述取代为被卤素、胺基、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
3.根据权利要求1所述的铂配合物,其中R1至R15各自独立地选自:氢、氘、卤素、氰基、C1-C4烷基、取代或未取代的具有3-6个环碳原子的环烷基;
Ar选自含有取代或未取代的具有6-30个碳原子的芳基、取代或未取代的具有3-30个碳原子的杂芳基;
所述取代为被卤素、胺基、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
4.根据权利要求1所述的铂配合物,其中R1至R15各自独立地选自:氢、氘、氰基、甲基、异丙基、异丁基、叔丁基、取代或未取代的环戊基、取代或未取代的环己基;
Ar选自含有取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的吡嗪基、取代或未取代的嘧啶基、取代或未取代的咪唑基、取代或未取代的咔唑基;
所述取代为被卤素、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
5.根据权利要求1所述的铂配合物,其中通式(I)中,R1至R15各自独立地选自:氢、氘、甲基、叔丁基、氰基;
Ar选自含有取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的咪唑基、取代或未取代的咔唑基;
所述取代为被卤素、胺基、氰基、C1-C4烷基或氟代的C1-C4烷基所取代。
6.根据权利要求1所述的铂配合物,其中通式(I)中,R1至R15中的R13为叔丁基,其余为氢;
Ar选自含有取代或未取代苯基、取代或未取代吡啶基或者取代或未取代咔唑基。
9.权利要求1-7任一所述的铂配合物在有机发光二极管,有机薄膜晶体管,有机光伏器件,发光电化学池或化学传感器中的应用。
10.有机发光二极管,包括阴极、阳极和有机层,所述有机层为空穴注入层、空穴传输层、发光层、空穴阻挡层、电子注入层、电子传输层中的一层或多层,所述有机层中含有权利要求1-7任一所述的铂配合物。
11.根据权利要求10所述的有机发光二极管,权利要求1-7任一所述的铂配合物位于发光层。
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CN103097395A (zh) * | 2010-07-21 | 2013-05-08 | 港大科桥有限公司 | 应用于有机发光二极管的铂(ii)四齿oncn络合物 |
US20180062088A1 (en) * | 2016-08-25 | 2018-03-01 | Samsung Electronics Co., Ltd. | Organometallic compound, organic light-emitting device including the organometallic compound, and diagnostic composition including the organometallic compound |
CN109802047A (zh) * | 2018-12-29 | 2019-05-24 | 香港大学深圳研究院 | 一种基于红外波段的有机发光器件及其制备方法 |
CN110872325A (zh) * | 2018-09-03 | 2020-03-10 | 广东阿格蕾雅光电材料有限公司 | 基于铂四齿oncn络合物的有机发光材料、制备方法及其在有机发光二极管中的应用 |
CN110945669A (zh) * | 2017-07-19 | 2020-03-31 | 香港大学 | 基于单发射体的颜色-可调谐有机发光二极管装置及其方法 |
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CN103097395A (zh) * | 2010-07-21 | 2013-05-08 | 港大科桥有限公司 | 应用于有机发光二极管的铂(ii)四齿oncn络合物 |
US20180062088A1 (en) * | 2016-08-25 | 2018-03-01 | Samsung Electronics Co., Ltd. | Organometallic compound, organic light-emitting device including the organometallic compound, and diagnostic composition including the organometallic compound |
CN110945669A (zh) * | 2017-07-19 | 2020-03-31 | 香港大学 | 基于单发射体的颜色-可调谐有机发光二极管装置及其方法 |
CN110872325A (zh) * | 2018-09-03 | 2020-03-10 | 广东阿格蕾雅光电材料有限公司 | 基于铂四齿oncn络合物的有机发光材料、制备方法及其在有机发光二极管中的应用 |
CN109802047A (zh) * | 2018-12-29 | 2019-05-24 | 香港大学深圳研究院 | 一种基于红外波段的有机发光器件及其制备方法 |
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