CN113861143B - 一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件 - Google Patents

一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件 Download PDF

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CN113861143B
CN113861143B CN202111187348.2A CN202111187348A CN113861143B CN 113861143 B CN113861143 B CN 113861143B CN 202111187348 A CN202111187348 A CN 202111187348A CN 113861143 B CN113861143 B CN 113861143B
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solvent
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CN113861143A (zh
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孟鸿
张鑫康
王胧佩
邹东文
贺耀武
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Peking University Shenzhen Graduate School
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Abstract

本发明公开一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件，所述热激活延迟荧光深蓝光材料具有如下结构：D—A或D—A—D，D为基于五元杂环的电子给体单元，基于五元杂环的电子给体单元的结构式为：或其中，X、Y各自独立地选自氧、硫、硒、碲或氮烷基，R1‑R4各自独立地选自氢、氘、氰基或烷基链；A为电子受体单元；“”表示连接位点。基于五元杂环的电子给体单元具有刚性结构，使得热激活延迟荧光材料具有较高的荧光效率。该系列五元杂环在基本不影响分子最低未占据轨道的情况下有效地降低分子最高占据轨道，从而增大带隙，使分子发光光谱蓝移至深蓝光区，从而可得到热激活延迟荧光深蓝光材料且具有寿命长和发光率高的优点。

Description

一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发 光器件
技术领域
本发明涉及有机电致发光材料领域，尤其涉及一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件。
背景技术
有机发光二极管因具有柔性显示、色域广、视角宽等诸多优点，在手机、平板电脑、电视和穿戴设备等领域有着广泛的应用，深蓝光材料是当前有机发光二极管产业界的核心材料。当前商业化产品中以传统荧光材料为主，但其发光效率低，而使用贵金属的蓝光磷光材料配位键较弱，发光稳定性差。
热激活延迟荧光蓝光材料效率较高，是目前最有希望替代传统荧光材料的选择。然而，当前普遍采用的热激活延迟荧光蓝光材料多以咔唑、苯胺等含氮富电子基团作为电子给体，但是在高亮度下其连接键易解离，咔唑、苯胺等基团的引入不利于器件寿命的提升。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件，旨在解决现有热激活延迟荧光蓝光材料制备的有机电致发光器件寿命较低的问题。
本发明的技术方案如下：
本发明的第一方面，提供一种热激活延迟荧光深蓝光材料，其中，所述热激活延迟荧光深蓝光材料具有如下结构：
D—A或D—A—D，
D为基于五元杂环的电子给体单元，所述基于五元杂环的电子给体单元的结构式为：
其中，X、Y各自独立地选自氧、硫、硒、碲或氮烷基，R1-R4各自独立地选自氢、氘、氰基或烷基链；A为电子受体单元；/>表示连接位点。
可选地，所述电子受体单元具有以下结构中的一种：
其中/>表示连接位点。
可选地，所述热激活延迟荧光深蓝光材料具有以下结构中的一种：
本发明的第二方面，提供一种如上所述的热激活延迟荧光深蓝光材料的制备方法，其中，当D选自R1-R4选自氢时，包括步骤：
将与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到/>
将与/>溶解在第二溶剂中，反应后得到/>
可选地，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到/>
在无水无氧条件下，将与/>四三苯基膦钯、碳酸钾溶解在第二溶剂中，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到/>
本发明的第三方面，提供又一种如上所述的热激活延迟荧光深蓝光材料的制备方法，其中，当D选自R1-R4选自氢时，包括步骤：
将与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到/>
将与/>溶解在第三溶剂中，反应后得到/>
将与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，反应后得到
将与N-溴代琥珀酰亚胺溶解在第四溶剂中，反应后得到
将与/>溶解在第二溶剂中，反应后得到/>
可选地，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到/>
在无水无氧条件下，将与/>溶解在第三溶剂中，60-80℃下反应16-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱分离得到
在无氧条件下，将与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，搅拌回流12-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
在无水无氧条件下，将与N-溴代琥珀酰亚胺溶解在第四溶剂中，在80-100℃下反应12-24小时后冷却至室温，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到/>
在无水无氧条件下，将与/>四三苯基膦钯、碳酸钾溶解在第二溶剂，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到/>
可选地，所述第一溶剂为二氯甲烷；和/或，
所述第二溶剂为分子筛脱水的甲苯；和/或，
所述第三溶剂为N,N-二甲基甲酰胺；和/或，
所述第四溶剂为聚碳酸酯。
本发明的第四方面，提供一种有机电致发光器件，包括发光层，其中，所述发光层的材料包括如上所述的热激活延迟荧光深蓝光材料。
有益效果：本发明提供了一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件。所述基于五元杂环的电子给体单元具有刚性结构，可将其作为热激活延迟荧光材料的电子给体，由于前线分子轨道在电子给体和电子受体上的充分分离，能够使得热激活延迟荧光材料利用暗激子，从而具有较高荧光效率。同时该系列五元杂环在基本不影响分子最低未占据轨道的情况下有效地降低分子最高占据轨道，从而增大带隙，使分子发光光谱蓝移至深蓝光区，从而可得到热激活延迟荧光深蓝光材料。将所述热激活延迟荧光深蓝光材料用于制备有机电致发光器件时，由于材料本身发光效率高，而且基团之间均为稳定的C-C键连接，可以使得有机电致发光器件具有较长的寿命和较高的发光效率。
附图说明
图1为本发明实施例4中有机电致发光器件的结构示意图。
图2为本发明实施例3中化合物99的光致发光荧光光谱图。
具体实施方式
本发明提供一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供一种热激活延迟荧光深蓝光材料，其中，所述热激活延迟荧光深蓝光材料具有如下结构：
D—A或D—A—D，
D为基于五元杂环的电子给体单元，所述基于五元杂环的电子给体单元的结构式为：
其中，X、Y各自独立地选自氧、硫、硒、碲或氮烷基，R1-R4各自独立地选自氢、氘、氰基或烷基链；A为电子受体单元；/>表示连接位点。
本实施例中，X、Y可以相同，也可以不同，他们各自独立地选自氧、硫、硒、碲或氮烷基。R1-R4可以相同，也可以不同，他们各自独立地选自氢、氘、氰基或烷基链。D1中的连接位点可在X的邻位，也可在X的间位；D2中的连接位点可以在R1或R2的邻位，也可以在R1或R2的间位，可以在R3或R4的邻位，也可以在R3或R4的间位。
上述基于五元杂环的电子给体单元具有刚性结构，可将其作为热激活延迟荧光材料的电子给体，由于前线分子轨道在电子给体和电子受体上的充分分离，将上述基于五元杂环的电子给体单元作为热激活延迟荧光材料的电子给体时，能够使得热激活延迟荧光材料利用暗激子，从而具有较高的荧光效率。同时该系列五元杂环在基本不影响分子最低未占据轨道的情况下有效地降低分子最高占据轨道，从而增大带隙，使分子发光光谱蓝移至深蓝光区，从而可得到热激活延迟荧光深蓝光材料。
将所述热激活延迟荧光深蓝光材料用于制备有机电致发光器件时，由于材料本身发光效率高，而且基团之间均为稳定的C-C键连接，可以使得有机电致发光器件具有较长的寿命和较高的发光效率。
在一种实施方式中，所述电子受体单元具有以下结构中的一种：
其中/>表示连接位点。
上述结构的电子受体单元可以使得热激活延迟荧光深蓝光材料具有更深的最高电子占据轨道，从而实现深蓝光发射。
在一种实施方式中，所述热激活延迟荧光深蓝光材料具有以下结构中的一种：
/>
/>
本发明实施例还提供一种如上所述的热激活延迟荧光深蓝光材料的制备方法，以所述热激活延迟荧光深蓝光材料具有D-A结构为例，其中，当D选自R1-R4选自氢时，包括步骤：
将与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到/>
将与/>溶解在第二溶剂中，反应后得到/>
本发明实施例提供的制备方法，以为反应物，依次通过亲电取代反应、Suzuki反应，引入电子受体单元，制备得到/>该制备方法操作相对简单，制备得到的产率高。
在一种实施方式中，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到/>
在无水无氧条件下，将与/>四三苯基膦钯、碳酸钾溶解在第二溶剂中，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到/>
具体地，的合成路线为：
本发明实施例提供了另一种如上所述的热激活延迟荧光深蓝光材料的制备方法，以所述热激活延迟荧光深蓝光材料具有D-A结构为例，其中，当D选自R1-R4选自氢时，包括步骤：
将与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到/>
将与/>溶解在第三溶剂中，反应后得到/>
将与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，反应后得到
将与N-溴代琥珀酰亚胺溶解在第四溶剂中，反应后得到
将与/>溶解在第二溶剂中，反应后得到/>本发明实施例提供的制备方法，以/>为反应物，依次通过亲电取代反应、芳环亲电取代反应、环化反应、卤代反应、Suzuki反应，引入电子受体单元，制备得到/>该制备方法操作相对简单，制备得到的/>产率高。
在一种实施方式中，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到/>
在无水无氧条件下，将与/>溶解在第三溶剂中，60-80℃下反应16-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱分离得到
在无氧条件下，将与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，搅拌回流12-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
在无水无氧条件下，将与N-溴代琥珀酰亚胺溶解在第四溶剂中，在80-100℃下反应12-24小时后冷却至室温，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到/>
在无水无氧条件下，将与/>四三苯基膦钯、碳酸钾溶解在第二溶剂，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到/>
具体地，的合成路线为：/>
在一种实施方式中，所述第一溶剂为二氯甲烷，但不限于此。
在一种实施方式中，所述第二溶剂为分子筛脱水的甲苯，但不限于此。
在一种实施方式中，所述第三溶剂为N,N-二甲基甲酰胺，但不限于此。
在一种实施方式中，所述第四溶剂为聚碳酸酯，但不限于此。
本发明实施例还提供一种有机电致发光器件，包括发光层，其中，所述发光层的材料包括本发明实施例如上所述的热激活延迟荧光深蓝光材料。
本实施例中，有机电致发光器件寿命长、发光效率高。
下面通过具体的实施例对本发明作进一步地说明。
需要说明的是，以下实施例中所用试剂或仪器未注明生产厂商的，均为可通过市购购买获得的常规产品。实施例中未提及其合成方法的化合物均为可通过商业途径获得的原料产品。实施例中所用溶剂和试剂均可从国内化工市场购买，例如购买自国药集团试剂公司，安耐吉公司，阿拉丁公司，上海毕得医药公司等，另外，本领域技术人员也可以通过公知方法进行合成。实施例中未注明具体实验步骤或反应条件的，按照本领域内熟知的常规实验步骤或反应条件即可进行。
实施例1
本实施例提供一种热激活延迟荧光深蓝光材料，记作化合物4，化合物4的合成路线如下所示：
化合物4的合成方法具体包括以下步骤：
中间体1的合成：在无水无氧条件下，将原料1(13.4g，100mmol)、N-溴代琥珀酰亚胺(21.4g，120mmol)和二氯甲烷(200mL)放入圆底烧瓶中，常温下反应12小时，加入饱和硫代硫酸钠溶液(50mL)淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤。使用无水硫酸钠干燥后，粗产物以硅胶柱层析(石油醚/乙酸乙酯为3/1(体积比))纯化，得到中间体1(20.2g，产率95％)。
化合物4的合成：取双颈圆底烧瓶(500mL)，上接球形冷凝管，干燥后充入氮气，分别加入中间体1(10.7g，50mmol)，原料2(16.9g，55mmol)，四三苯基膦钯(458mg，0.5mmol)，碳酸钾水溶液(2mol/L，75mL)，甲苯(200mL)。加热回流24小时，冷却至室温，将溶液倒入水中，使用二氯甲烷萃取，水相用乙酸乙酯萃取三次，合并有机相，使用无水硫酸钠干燥后，粗产物以硅胶柱层析(石油醚/乙酸乙酯为4/1(体积比))纯化，得到化合物4(10.9g，产率70％)。高分辨质谱：314.0612(理论值314.0765)。
实施例2
本实施例提供一种热激活延迟荧光深蓝光材料，记作化合物70，化合物70的合成路线如下所示：
化合物70的合成方法具体包括以下步骤：
中间体2的合成：同实施例1中中间体1的合成，区别仅在于：使用原料3(11.8g，100mmol)，得到中间体2(17.3g，产率88％)。
化合物70的合成：同实施例1中化合物4的合成，区别仅在于：使用中间体2(9.8g，50mmol)，原料4(21.0g，55mmol)，得到化合物70(5.9g，产率65％)。高分辨质谱：362.0920(理论值362.1055)。
实施例3
本实施例提供一种热激活延迟荧光深蓝光材料，记作化合物99，化合物99的合成路线如下所示：
化合物99的合成方法具体包括以下步骤：
中间体1的合成：同实施例1中中间体1的合成。
中间体3的合成：在无水无氧条件下，将中间体1(4.26g，20mmol)、苯硫酚(42.42g，22mmol)、碳酸钾(5.52g)和干燥的N,N-二甲基甲酰胺(100mL)放入圆底烧瓶中，60-80℃下反应20小时，将溶液倒入水中，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤。使用无水硫酸钠干燥后，粗产物以硅胶柱层析(石油醚/乙酸乙酯为5/1(体积比))纯化，得到中间体3(3.98g，产率82％)。
中间体4的合成：在无氧条件下，将中间体3(2.42g，10mmol)与催化量Pd(OPiv)2和Ag(OPiv)溶于甲苯(50mL)中，搅拌回流16小时，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱(石油醚/乙酸乙酯为3/1(体积比)分离，得到中间体4(2.04g，产率85％)。
中间体5的合成：在无水无氧条件下，将中间体4(1.20g，5mmol)与N-溴代琥珀酰亚胺(1.07g，6mmol)溶于聚碳酸酯(50mL)中，在80℃下反应20小时后冷却至室温，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱(石油醚/乙酸乙酯为5/1(体积比)分离，得到中间体5(1.49g，产率93％)。
化合物99的合成：同实施例1中化合物4的合成，区别仅在于：使用中间体5(0.32g，1.0mmol)，原料6(0.98g，2.2mmol)，得到化合物99(0.47g，产率71％)。高分辨质谱：667.9557(理论值667.9638)。
实施例4
本实施例提供了一种有机电致发光器件，如图1所示，包括从上至下依次层叠设置的金属阴极1、电子注入层2、电子传输层3、发光层4、空穴传输层5、空穴注入层6、阳极7以及玻璃基板8。
其中，金属阴极1选用铝；电子注入层2选用氟化锂；电子传输层3选用化合物LET003，其结构式为发光层4由主体材料和客体材料共掺杂形成，其中主体材料选用化合物mCBP，其结构式为/>客体材料选用实施例3中制备得到的化合物99，主体材料与客体材料掺杂的质量比为85：15；空穴传输层5选用化合物NPB，其结构式为/>空穴注入层6选用化合物HATCN，其结构式为阳极7选用氧化铟锡。
实施例5
本实施例提供了一种有机电致发光器件，与实施例4中提供的有机电致发光器件的区别仅在于：发光层4的客体材料选用实施例1中制备得到的化合物4。
实施例6
本实施例提供了一种有机电致发光器件，与实施例4中提供的有机电致发光器件的区别仅在于：发光层4的客体材料选用实施例2中制备的化合物70。
对比例1
本对比例提供了一种有机电致发光器件，与实施例4中提供的有机电致发光器件的区别仅在于：发光层4的客体材料选用商业化材料5TCzBN(2,3,4,5,6-五(3,6-二叔丁基-9H-咔唑-9-基)苯甲腈)。
测试
(1)对实施例3制备得到的化合物99进行光致发光测试，其光致发光荧光光谱如图2所示，由此结果可知，化合物99可发深蓝光。
(2)对实施例4和对比例1中的有机电致发光器件进行发光效率测试，结果如表1所示，可以看出，对比采用传统咔唑5TCzBN作为电子给体的发光材料，采用新型五元杂环作为电子给体的化合物99显示出更高的电致发光亮度和更高的量子效率，同时器件寿命是对比器件的两倍以上，因此该新型五元杂环作为电子给体的发光材料更具商业化潜力。
表1发光效率测试结果
综上所述，本发明提供一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件。所述基于五元杂环的电子给体单元具有刚性结构，可将其作为热激活延迟荧光材料的电子给体，由于前线分子轨道在电子给体和受体上的充分分离，能够使得热激活延迟荧光材料利用暗激子，从而具有较高荧光效率率。同时该系列五元杂环在基本不影响分子最低未占据轨道的情况下有效地降低分子最高占据轨道，从而增大带隙，使分子发光光谱蓝移至深蓝光区，从而可得到热激活延迟荧光深蓝光材料。将所述热激活延迟荧光深蓝光材料用于制备有机电致发光器件时，由于材料本身发光效率高，而且基团之间均为稳定的C-C键连接，可以使得有机电致发光器件具有较长的寿命和较高的发光效率。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (4)

1.一种有机电致发光器件，包括发光层，其特征在于，所述发光层的材料包括热激活延迟荧光深蓝光材料，所述热激活延迟荧光深蓝光材料具有如下结构中的一种：
2.根据权利要求1所述的有机电致发光器件，其特征在于，热激活延迟荧光深蓝光材料的制备方法包括步骤：
将与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到/>
将与/>溶解在第三溶剂中，反应后得到/>
将与Pd(OPiv)2，Ag(OPiv)溶解在第二溶剂中，反应后得到/>
将与N-溴代琥珀酰亚胺溶解在第四溶剂中，反应后得到将/>与/>溶解在第二溶剂中，反应后得到所述热激活延迟荧光深蓝光材料。
3.根据权利要求2所述的有机电致发光器件，其特征在于，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到/>
在无水无氧条件下，将与/>溶解在第三溶剂中，60-80℃下反应16-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱分离得到/>
在无氧条件下，将与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，搅拌回流12-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
在无水无氧条件下，将与N-溴代琥珀酰亚胺溶解在第四溶剂中，在80-100℃下反应12-24小时后冷却至室温，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到/>
在无水无氧条件下，将与/>四三苯基膦钯、碳酸钾溶解在第二溶剂中，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到所述热激活延迟荧光深蓝光材料。
4.根据权利要求2-3任一项所述的有机电致发光器件，其特征在于，
所述第一溶剂为二氯甲烷；和/或，
所述第二溶剂为分子筛脱水的甲苯；和/或，
所述第三溶剂为N,N-二甲基甲酰胺；和/或，
所述第四溶剂为聚碳酸酯。
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