CN114685501B - 一种苯基咔唑螺环衍生物及其应用、有机电子器件、显示装置或照明装置 - Google Patents
一种苯基咔唑螺环衍生物及其应用、有机电子器件、显示装置或照明装置 Download PDFInfo
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Abstract
本发明提供一种苯基咔唑螺环衍生物及有机电子器件、显示装置或照明装置，该苯基咔唑螺环衍生物通过其母核整体结构及支链搭配形成的分子构型和分子轨道特性，使其具有优异的成膜性、热稳定性及光电特性，可用于制备有机电致发光器件、有机场效应晶体管和有机太阳能电池。另外，本发明的苯基咔唑螺环衍生物可以作为电子器件的空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层的构成材料，能够降低驱动电压，提高效率、亮度和寿命等。更为重要的是，本发明的苯基咔唑螺环化合物能有效地隔离给体和受体基团，是构建热激活延迟荧光材料的理想骨架。本发明的苯基咔唑螺环衍生物的制备方法简单，原料易得，能够满足工业化的发展需求。
Description
技术领域
本发明涉及一种苯基咔唑螺环衍生物及其应用、有机电子器件及显示器件或照片器件，属于有机光电材料技术领域。
背景技术
有机发光二极管(OLED)是一种自发光器件，通过施加电压，从阴极注入的电子和阳极注入的空穴在发光中心复合形成分子激子，并且该分子激子在回到基态时释放能量来发光。有机电致发光器件具有开启电压低、亮度高、色域广、色纯度高、视角宽、响应快、温度适应性好等特性，可以广泛应用于手机、电脑、MP3、电视等电子产品显示器。
目前商业化的有机电致发光材料分为传统荧光材料和磷光材料，其中荧光材料只能利用25％的单线态激子，剩余的75％三线态激子通过热或者其他无辐射方式损失，而磷光材料由于重原子效应可以利用100％的激子，虽然使其发光效率远高于传统荧光材料，但是大部分磷光器件大都具有较为严重的效率滚降，即在较低亮度或较低电流密度下具有最大效率，随着亮度或电流密度的增大，器件的外量子效率普遍出现严重的降低并且受到贵重金属价格的制约。这无疑增加了器件的成本，影响了有机电致磷光器件在照明和全彩显示上的应用。如何开发或设计出高效的且能够适用场景更广的材料、匹配客体更有效的材料体现是产业中重要的研究客体，特别是面向新型的热激活延迟荧光客体材料的性能匹配和改善方面。
发明内容
本发明的目的在于提供一种苯基咔唑螺环衍生物及其在热激活延迟荧光材料骨架中的应用、有机电子器件、显示装置或照明装置，能有效提高三线态能级，减小单线态与三线态能隙差和提高荧光量子产率以及热稳定性，从而改善有机电致发光器件的发光效率、效率滚降和工作电压等性能。
为达到上述目的，本发明提供如下技术方案：一种苯基咔唑螺环衍生物，其特征在于，其由下述通式(1)表示：
其中，R选自具有6至30个碳原子的芳香族烃基，或选自具有5至30个碳原子的芳香族杂环基中的一个或多个。
进一步可选地，所述R中的至少一个选自氰基或卤素。
进一步可选地，所述R中的至少一个选自三苯基硅烷基或四苯基硅烷基。
进一步可选地，所述R氢原子或者选自以下通式Ar-1至Ar-5中的任一种：
其中，波浪线表示与苯基咔唑螺环母核键合的键，
进一步地，所述苯基咔唑螺环化合物选自以下通式1-1至1-6中的任一种：
作为本发明另一个方面，本发明还提供上述苯基咔唑螺环衍生物作为热激活延迟荧光材料或在构建热激活延迟荧光材料骨架中的应用。
作为本发明另一个方面，本发明还提供根据所述的苯基咔唑螺环化合物在用于制备电子器件中的应用，所述电子器件选自有机电致发光器件、有机场效应晶体管或有机太阳能电池，尤其是在用于制备有机电致发光器件中的发光客体材料、发光主体材料、激子阻挡材料或电子传输材料的应用。
具体地，本发明还提供一种有机电子器件，其具有所述的苯基咔唑螺环化合物。
进一步地，所述有机电子器件包括第一电极、与所述第一电极对置的第二电极、以及夹设在所述第一电极与所述第二电极之间的至少一个有机层。
进一步地，所述有机层包括发光材料、敏化材料或主体材料中的一种或多种。
进一步地，所述有机层包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层或电子注入层中的一层或多层。
作为本发明再一个方面，本发明还提供一种显示装置件或一种照明装置，包括所述有机电子器件。
与现有技术相比，本发明的有益效果在于：本发明的苯基咔唑螺环衍生物通过引入苯基咔唑螺环刚性结构，其的成膜性和热稳定性优异，可用于制备有机电致发光器件、有机场效应晶体管和有机太阳能电池。另外，本发明的苯基咔唑螺环化合物可以作为空穴注入层、空穴传输层、发光层、电子阻挡层、空穴阻挡层或电子传输层的构成材料，能够降低驱动电压，提高效率、亮度和寿命等。
本发明的苯基咔唑螺环衍生物，通过在苯基咔唑螺环的咔唑部分两端引入的基团，如氰基或三苯基硅烷基或Ar-1，能有效地隔离给体和受体基团，从而是构建热激活延迟荧光材料的理想骨架，同时，通过在母核的螺环位置上引入了氧原子，使得衍生物获得较小的电荷转移单线态和三线态能级差(ΔEST)，在设计新型热激活延迟荧光客体材料时是构建热激活延迟荧光材料的理想骨架，从而改善有机电致发光器件的器件，提高有机电子器件的器件性能或效率，并明显改善器件的效率滚降问题。本发明的苯基咔唑螺环化合物的制备方法简单，原料易得，能够满足工业化的发展需求。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1为本发明实施例1和2(化合物1-1和1-2)的在甲苯溶液里的室温荧光光谱(PL)光谱；
图2为本发明实施例4和5中OLED器件的外量子效率滚降谱图；
图3为本发明实施例中有机电子器件的结构示意图。
附图标记说明
1-基板、2-阳极、3-空穴注入层、4-空穴传输层、5-电子阻挡层、6-发光层、7-空穴阻挡层、8-电子传输层。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1：化合物1-1的合成
化合物1-1的结构式和合成路线如下图所示：
式M1化合物的制备方法为：在250mL两口烧瓶中依次加入2.8g(16.8mmol)咔唑、11.6g(67.2mmol)1-溴-2-氟苯、10.9g(33.5mmol)碳酸铯和120mLN，N-二甲基甲酰胺，搅拌加热至150℃反应24小时。反应完全后，将体系冷却至室温，倒入水中，减压抽滤，并用大量水洗滤渣，将滤渣用二氯甲烷∶石油醚＝1∶4(体积比)的洗脱剂在硅胶柱上进行分离提纯，得到4.9g M1，收率90.8％。MS(ET)：m/z 321.05[M+]。元素分析计算值C18H12BrN(％)：C，67.10；H，3.75；N，4.35；实测值：C，67.05；H，3.70；N，4.25。
化合物1-1的制备方法为：在氮气保护下，在100mL两口烧瓶中将1.0g(5.0mmol)M1溶解在30mL无水四氢呋喃中，搅拌，冷却到-78℃。将2.3mL(5.5mmol)2.4M正丁基锂通过恒压滴液漏斗滴加到溶液中，加毕，在-78℃下继续搅拌1小时。然后将1.6g(5.0mmol)蒽醌在氮气保护下分散到30mL的无水四氢呋喃中并在滴加到反应液中。加毕，逐渐升至室温，反应12小时。反应完全后，加入5mL水猝灭反应，并旋干除去四氢呋喃。将粗产物溶于150mL二氯甲烷并用60mL水洗3次。有机相用无水硫酸钠干燥后旋干除去溶剂得粗产物。粗产物用二氯甲烷∶石油醚＝3∶1(体积比)的洗脱剂在硅胶柱上进行分离提纯，得到中间产物2.0g。在50mL两口瓶中将所得中间产物溶解在25mL醋酸中并加入2.5mL盐酸，搅拌加热至回流，反应6小时。反应完全后，将反应体系冷却至室温，倒入300mL冰水中，减压抽滤，水洗滤渣三次。将滤渣用二氯甲烷∶石油醚＝1∶4(体积比)的洗脱剂在硅胶柱上进行分离提纯，得到1.5g1-1，产率为70％。MS(EI)：m/z 433.10[M+]。元素分析计算值C32H19NO(％)：C，88.66；H，4.42；N，3.23；实测值：C，88.60；H，4.35；N，3.20。
实施例2：化合物1-2的合成
化合物1-2的结构式和合成路线如下图所示：
式M2化合物的制备方法为：在250mL两口烧瓶中依次加入2.3g(5.5mmol)3，6-二碘咔唑、3.8g(22.0mmol)1-溴-2-氟苯、3.6g(11.0mmol)碳酸铯和120mLN，N-二甲基甲酰胺，搅拌加热至150℃反应24小时。反应完全后，将体系冷却至室温，倒入水中，减压抽滤，并用大量水洗滤渣，将滤渣用二氯甲烷∶石油醚＝1∶4(体积比)的洗脱剂在硅胶柱上进行分离提纯，得到2.9g M2，收率92.0％。MS(EI)：m/z 572.75[M+]。元素分析计算值C18H10BrI2N(％)：C，37.67；H，1.76；N，2.44；实测值：C，37.60；H，1.75；N，2.40。
式M3化合物的制备方法为：在250mL两口烧瓶中依次加入2.2g(3.8mmol)M2、1.3g(7.7mmol)咔唑、1.1g(11.5mmol)叔丁醇钠、22.2mg(76.7μmol)四氟硼酸三叔丁基膦、60.0mg(76.7μmol)三(二亚苄基丙酮)二钯，将反应体系除气后在氮气保护下，加入120mL甲苯，搅拌加热至回流反应12小时。反应完全后，将体系冷却至室温，减压抽滤，并用大量二氯甲烷洗涤滤渣，将滤液浓缩得到粗产物，粗产物用二氯甲烷∶石油醚＝2∶3(体积比)的洗脱剂在硅胶柱上进行分离提纯，得到2.2g，M3。产率为88％。MS(EI)：m/z651.10[M+]。元素分析计算值C42H26BrN3(％)：C，77.30；H，4.02；N，6.44；实测值：C，77.25；H，4.00；N，6.35。
化合物1-2的制备方法为：在氮气保护下，在100mL两口烧瓶中将3.2g(4.9mmol)M3溶解在40mL无水四氢呋喃中，搅拌，冷却到-78℃。将2.3mL(5.5mmol)2.4M正丁基锂通过恒压滴液漏斗滴加到溶液中，加毕，在-78℃下继续搅拌1小时。然后将1.0g(4.9mmol)蒽醌在氮气保护下分散到40mL的无水四氢呋喃中并在滴加到反应液中。加毕，逐渐升至室温，反应12小时。反应完全后，加入5mL水猝灭反应，并旋干除去四氢呋喃。将粗产物溶于150mL二氯甲烷并用60mL水洗3次。有机相用无水硫酸钠干燥后旋干除去溶剂得粗产物。粗产物用二氯甲烷∶石油醚＝3∶1(体积比)的洗脱剂在硅胶柱上进行分离提纯，得到中间产物3.5g。在50mL两口瓶中将所得中间产物溶解在25mL醋酸中并加入2.5mL盐酸，搅拌加热至回流，反应6小时。反应完全后，将反应体系冷却至室温，倒入300mL冰水中，减压抽滤，水洗滤渣三次。将滤渣用二氯甲烷∶石油醚＝1∶4(体积比)的洗脱剂在硅胶柱上进行分离提纯，得到2.6g1-2，产率为70％。MS(ET)：m/z 763.30[M+]。元素分析计算值C56H33N3O(％)：C，88.05；H，4.35；N，5.50；实测值：C，88.00；H，4.25；N，5.45。
实施例3：化合物1-3的合成
化合物1-3的结构式和合成路线如下图所示：
Claims (6)
1.一种苯基咔唑螺环衍生物，其特征在于，所述苯基咔唑螺环衍生物选自以下化学式1-1至1-3中的任一种：
2.权利要求1所述的苯基咔唑螺环衍生物，作为热激活延迟荧光材料或在构建热激活延迟荧光材料骨架中的应用。
3.一种有机电子器件，其特征在于，其包括：第一电极、与所述第一电极对置的第二电极、以及夹设在所述第一电极与所述第二电极之间的至少一个有机层，所述至少一个有机层包含权利要求1所述的化合物。
4.如权利要求3所述的有机电子器件，其特征在于，所述有机层包括发光材料、敏化材料或主体材料中的一种或多种。
5.如权利要求3所述的有机电子器件，其特征在于，所述有机层包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层或电子注入层中的一层或多层。
6.一种显示装置件或一种照明装置，其特征在于，包括如权利要求3至5中任一项所述的有机电子器件。
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