CN113045542B - 一种基于七元环二酰亚胺受体的热活化延迟荧光oled材料的制备及其应用 - Google Patents

一种基于七元环二酰亚胺受体的热活化延迟荧光oled材料的制备及其应用 Download PDF

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CN113045542B
CN113045542B CN201911362391.0A CN201911362391A CN113045542B CN 113045542 B CN113045542 B CN 113045542B CN 201911362391 A CN201911362391 A CN 201911362391A CN 113045542 B CN113045542 B CN 113045542B
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delayed fluorescence
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游劲松
黄珍梅
宾正杨
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Sichuan University
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Abstract

本发明公开了一种基于七元环二酰亚胺受体的热活化延迟荧光OLED材料及其应用，属于有机光电材料技术领域。其具有式Ⅰ与式Ⅱ所示的结构：

Description

一种基于七元环二酰亚胺受体的热活化延迟荧光OLED材料的 制备及其应用
技术领域
本发明涉及一种以七元环二酰亚胺为核心的热活化延迟荧光OLED材料及其应用，属于有机光电材料技术领域。
背景技术
目前，基于OLED显示技术的商品，已经实现产业化。与液晶类显示技术相比，OLED显示技术具有自发光、无辐射、质量轻、厚度薄、广视角、宽色域、颜色稳定、响应速度快、环境适应强、可实现柔性显示等诸多优点，因此，OLED显示技术正在获得人们越来越多的关注和相应的技术投入。
OLED显示的基础结构单元为OLED器件，OLED器件根据发光机制的不同，可分为荧光器件和磷光器件两种。基于单线态发光的荧光0LED作为第一代发光材料其理论上的内量子效率只有25％，无法进一步提高其效率；磷光0LED被称为第二代，其内量子效率能达到100％。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间穿越速率，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达100％。但磷光材料存在价格昂贵、材料稳定性较差、使用寿命短、器件效率滚降严重等问题限制了其在OLED的应用。
2009年，日本九州大学的Adachi教授，设计并合成了一类咔唑苯腈类衍生物，继而发现了基于三线态-单线态跃迁的热活化延迟荧光(TADF)新材料，其内量子效率接近100％，这类材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(△EST)，三线态激子可以通过反系间穿越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子，器件的内量子效率可以达到100％。同时，材料结构可控，性质稳定，价格便宜无需贵重金属，在OLED领域的应用前景广阔。但是材料结构与其光物理性质及器件效率的相关性目前还不清楚，限制了高效延迟荧光材料的开发，导致现有TADF材料种类单一，器件的效率较低，无法满足高效有机发光二极管的要求。
现已报道的具有TADF性能的有机化合物，结构上均是供电子基团与吸电子基团直接或间接连接而成的具有明显推拉结构的有机小分子化合物。新型TADF材料无疑具有广阔发展前景。
发明内容
本发明的目的之一，是提供一种基于七元环二酰亚胺受体的热活化延迟荧光OLED材料。本发明的化合物以七元环二酰亚胺为核心，作为发光材料应用于有机发光二极管，本发明制作的器件具有良好的光电性能，能够满足面板制造企业的要求。
本发明解决上述技术问题的技术方案如下：一种以七元环二酰亚胺为核心的热活化延迟荧光OLED材料，具有式Ⅰ或式Ⅱ所示的结构：
Figure GDA0003512230340000021
其中，Ar1、Ar2分别独立表示为苯环；R1表示为亚苯基；R2为：
Figure GDA0003512230340000031
中的任一种；R3表示为叔丁基、氰基单取代的苯基，进一步，所述OLED材料的代表性结构式为：
Figure GDA0003512230340000041
中的任一种。
本发明的目的之二，是提供一种有机电致发光器件。使用本发明所述材料制作的有机电致发光器件，具有简易的器件结构、高的外量子效率和低的效率滚降。
本发明解决上述技术问题的技术方案如下：一种有机电致发光器件，至少一层功能层含有上述以七元环二酰亚胺为核心的热活化延迟荧光OLED材料。
进一步，所述功能层为发光层。
本发明的有益效果是：
1、本发明提供了一类有机电致发光材料，该材料以七元环二酰亚胺为显著特征，可以作为具有TADF性质的发光材料，应用在有机电致发光领域中。
2、以本发明提供的材料作为发光层，制作的有机电致发光器件，具有较好的性能。
其特点在于：
(1)本发明通过氧化脱氢偶联、Buchwald–Hartwig偶联等反应，合成了一种以七元环二酰亚胺为核心的热活化延迟荧光OLED材料，并通过芳香基团连接各类供电基团构成目标化合物分子群，这类分子具有小的单线态—三线态能级差(即△EST)、较高的分解温度Td和玻璃化转变温度Tg，适合作为OLED器件中的发光材料。
(2)本发明中由于七元环二酰亚胺核心受体兼具刚性和旋转性，R1、R2、R3的引入。使得分子构型更加扭曲，从而在大概率上同时具有AIE和TADF两种特性，适用于作为非掺杂OLED中的发光材料，从而构筑高效非掺杂有机发光OLED器件。
(3)以该类材料作为非掺杂OLED中的发光材料，所制备的有机电致发光器件具有较好的性能，最大外量子效率可达24.7％。
3、本发明所述化合物材料在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
附图说明
图1为化合物C1的核磁图谱H谱。
图2为化合物C1的核磁图谱C谱。
图3为化合物C1的单晶结构。
图4为化合物C1的紫外可见光吸收光谱、室温荧光发射光谱和低温磷光发射光谱。
图5为化合物C1分别在溶液和薄膜状态下的瞬态荧光光谱。
具体实施方式
在Agilent 400-MR DD2仪器上于CDCl3或DMSO-d6溶液中以400MHz记录1H图谱，以100MHz记录13C NMR图谱，化学位移参照残留的氘代(protiated)溶剂。在Shimadzu LCMS-IT-TOF(ESI)上记录质谱。
以下结合具体附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1：
中间体B1的制备
Figure GDA0003512230340000061
在250mL三口瓶中放入磁力搅拌子，加入对溴苯甲酸(10g,50mmol)，三氯化钌(II)(518.6mg,2.5mmol)，1,8-二氮杂二环[5.4.0]十一碳-7-烯(7.2mL,50mmol)，置换氧气三次以上，加入乙二醇二甲醚60mL，升温至110℃并反应30小时。反应结束并冷却至室温后，加入碳酸钾(20.7g,150mmol)，碘甲烷(9.5mL,150mmol)，室温下搅拌4小时后，减压过滤，真空蒸发溶剂及低沸物，粗产品经柱层析纯化，洗脱剂为石油醚:乙酸乙酯＝10:1。得到目标中间体B1，白色固体5.56g，收率为52％。
高分辨质谱，ESI源，正离子模式，分子式[C16H12Br2O4+Na]+，理论值450.8974(100.0％),448.8995(51.4％),452.8954(48.6％)，实测值450.8972,448.8995,452.8950.
中间体B2的制备
Figure GDA0003512230340000071
在25mL高压管中放入磁力搅拌子，加入中间体B1(214mg,0.5mmol)，9,10-二氢-9,9-二甲基吖啶(230mg,1.1mmol)，醋酸钯(11.2mg,0.05mmol)，三苯基磷(39mg,0.15mmol)，碳酸铯(650mg,2.0mmol)，置换氮气三次以上，加入脱气甲苯5.0mL，回流反应24小时。反应结束冷却至室温，减压过滤，真空蒸发溶剂及低沸物，粗产品经柱层析纯化，洗脱剂为石油醚:乙酸乙酯＝10:1。得到目标中间体B2，白色固体331mg，收率为97％。
高分辨质谱，ESI源，正离子模式，分子式[C46H40N2O4+Na]+，理论值707.2880，实测值707.2888.
中间体B3的制备
Figure GDA0003512230340000072
在500mL圆底烧瓶中放入磁力搅拌子，加入中间体B2(1.37g,2.0mmol)，四氢呋喃90mL，甲醇30mL，待其全部溶解后，加入2M氢氧化钠溶液90mL，回流反应12小时。反应结束冷却至室温，真空蒸发低沸溶剂，剩余固体溶于水中，并用2M稀盐酸调节pH值至2～3，减压过滤，得到的固体于60℃真空干燥箱中干燥过夜，得到目标中间体B3，白色固体1.28g，收率为98％
中间体B4的制备
Figure GDA0003512230340000081
在100mL圆底烧瓶中放入磁力搅拌子，加入中间体B3(1.28g，1.96mmol)，醋酸酐12mL，回流反应6小时，反应结束冷却至室温，真空蒸发溶剂，剩余固体即粗产品B4，不经进一步纯化，投入下一步反应。
化合物C1的制备
Figure GDA0003512230340000082
在100mL圆底烧瓶中放入磁力搅拌子，加入未经纯化的化合物B4(1.25g,1.96mmol)，对叔丁基苯胺(374μL,2.35mmol)，三乙胺(817μL,5.88mmol)，4-二甲氨基吡啶(47.9mg,0.39mmol)，二氯甲烷30mL，室温下搅拌12小时，反应结束后，加入2M稀盐酸调节体系至弱酸性，加入乙酸乙酯萃取分液，收集有机相，无水硫酸钠干燥，真空蒸发溶剂，向剩余固体中加入醋酸酐12mL，回流反应6小时，反应结束冷却至室温，真空蒸发溶剂，粗产品经柱层析纯化，洗脱剂为石油醚:二氯甲烷＝2:1。得到目标化合物C1，淡绿色固体1.42g，收率为94％。
高分辨质谱，ESI源，正离子模式，分子式[C54H47N3O2+Na]+，理论值792.3560，实测值792.3566.
实施例2：
中间体D1的制备
Figure GDA0003512230340000091
在250mL三口瓶中放入磁力搅拌子，加入对溴苯甲酸(10g,50mmol)，苯甲酸(1.525g,12.5mmol)，二氯(p-甲基异丙苯)钌(II)二聚体(736mg,1.25mmol)，氧化铜(1.5g,18.75mmol)，1,8-二氮杂二环[5.4.0]十一碳-7-烯(9.0mL,62.5mmol)，置换氧气三次以上，加入无水1,4-二氧六环60mL，升温至110℃并反应30小时。反应结束并冷却至室温后，加入碳酸钾(8.625g,62.5mmol)，碘甲烷(3.96mL,62.5mmol)，室温下搅拌4小时后，减压过滤，真空蒸发溶剂及低沸物，粗产品经柱层析纯化，洗脱剂为石油醚:乙酸乙酯＝10:1。得到目标中间体D1，白色固体1.74g，收率为40％。
高分辨质谱，ESI源，正离子模式，分子式[C16 H13 BrO4+Na]+，理论值370.9889(100％),372.9869(97.3％)，实测值370.9888,372.9864.
中间体D2的制备
Figure GDA0003512230340000092
在25mL高压管中放入磁力搅拌子，加入中间体D1(174mg,0.5mmol)，9,10-二氢-9,9-二甲基吖啶(115mg,0.55mmol)，醋酸钯(11.2mg,0.05mmol)，三苯基磷(39mg,0.15mmol)，碳酸铯(650mg,2.0mmol)，置换氮气三次以上，加入脱气甲苯5.0mL，回流反应24小时。反应结束冷却至室温，减压过滤，真空蒸发溶剂及低沸物，粗产品经柱层析纯化，洗脱剂为石油醚:乙酸乙酯＝10:1。得到目标中间体D2，白色固体227mg，收率为95％。
高分辨质谱，ESI源，正离子模式，分子式[C31H27NO4+Na]+，理论值500.1832，实测值500.1826.
中间体D3的制备
Figure GDA0003512230340000101
在500mL圆底烧瓶中放入磁力搅拌子，加入中间体D2(955mg,2.0mmol)，四氢呋喃90mL，甲醇30mL，待其全部溶解后，加入2M氢氧化钠溶液90mL，回流反应12小时。反应结束冷却至室温，真空蒸发低沸溶剂，剩余固体溶于水中，并用2M稀盐酸调节pH值至2～3，减压过滤，得到的固体于60℃真空干燥箱中干燥过夜，得到目标中间体D3，白色固体0.88g，收率为98％。
中间体D4的制备
Figure GDA0003512230340000102
在100mL圆底烧瓶中放入磁力搅拌子，加入中间体D3(0.88g，1.96mmol)，醋酸酐12mL，回流反应6小时，反应结束冷却至室温，真空蒸发溶剂，剩余固体即粗产品D4，不经进一步纯化，投入下一步反应。
化合物C2的制备
Figure GDA0003512230340000111
在100mL圆底烧瓶中放入磁力搅拌子，加入未经纯化的化合物D4(845mg,1.96mmol)，对叔丁基苯胺(374μL,2.35mmol)，三乙胺(817μL,5.88mmol)，4-二甲氨基吡啶(47.9mg,0.39mmol)，二氯甲烷30mL，室温下搅拌12小时，反应结束后，加入2M稀盐酸调节体系至弱酸性，加入乙酸乙酯萃取分液，收集有机相，无水硫酸钠干燥，真空蒸发溶剂，向剩余固体中加入醋酸酐12mL，回流反应6小时，反应结束冷却至室温，真空蒸发溶剂，粗产品经柱层析纯化，洗脱剂为石油醚:二氯甲烷＝2:1。得到目标化合物C2，淡绿色固体1.014g，收率为92％。
高分辨质谱，ESI源，正离子模式，分子式[C39H34N2O2+Na]+，理论值585.2512，实测值585.2510.
实施例3：
化合物C4的制备与化合物C1的制备类似，不同之处在于使用4-(9,9-二甲基-9,10二氢吖啶)苯硼酸替换9,10-二氢-9,9-二甲基吖啶，制备得到中间体E2，进而制备得到化合物C4，淡黄色固体，总收率为37％。
高分辨质谱，ESI源，正离子模式，分子式[C66H55N3O2+Na]+，理论值944.4186，实测值944.4182.
中间体E2的制备
Figure GDA0003512230340000121
在25mL高压管中放入磁力搅拌子，加入中间体B1(214mg,0.5mmol)，4-(9,9-二甲基-9,10二氢吖啶)苯硼酸(362mg,1.1mmol)，四(三苯基膦)钯(57.8mg,0.05mmol)，碳酸钾(276mg,2.0mmol)，置换氮气三次以上，加入脱气四氢呋喃5.0mL，回流反应24小时。反应结束冷却至室温，减压过滤，真空蒸发溶剂及低沸物，粗产品经柱层析纯化，洗脱剂为石油醚:乙酸乙酯＝10:1。得到目标中间体E2，白色固体318mg，收率为76％。
高分辨质谱，ESI源，正离子模式，分子式[C58H48N2O4+Na]+，理论值859.3506，实测值859.3501.
实施例4：
化合物C5的制备与化合物C2的制备类似，不同之处在于使用4-(9,9-二甲基-9,10二氢吖啶)苯硼酸替换9,10-二氢-9,9-二甲基吖啶，制备得到中间体F2，进而制备得到化合物C5，淡黄色固体，总收率为41％。
高分辨质谱，ESI源，正离子模式，分子式[C45H38N2O2+Na]+，理论值661.2825，实测值661.2820.
中间体F2的制备
Figure GDA0003512230340000131
在25mL高压管中放入磁力搅拌子，加入中间体D1(174mg,0.5mmol)，4-(9,9-二甲基-9,10二氢吖啶)苯硼酸(181mg,0.55mmol)，四(三苯基膦)钯(57.8mg,0.05mmol)，碳酸钾(276mg,2.0mmol)，置换氮气三次以上，加入脱气四氢呋喃5.0mL，回流反应24小时。反应结束冷却至室温，减压过滤，真空蒸发溶剂及低沸物，粗产品经柱层析纯化，洗脱剂为石油醚:乙酸乙酯＝10:1。得到目标中间体F2，白色固体241mg，收率为87％。
高分辨质谱，ESI源，正离子模式，分子式[C37H31NO4+Na]+，理论值576.2145，实测值576.2149.
实施例5：
化合物C8的制备与化合物C1的制备类似，不同之处在于使用对氰基苯胺替换对叔丁基苯胺，制备得到化合物C8，浅黄色固体，总收率为36％。
Figure GDA0003512230340000132
高分辨质谱，ESI源，正离子模式，分子式[C51H38N4O2+Na]+，理论值761.2887，实测值761.2890.
实施例6：
化合物C9的制备与化合物C2的制备类似，不同之处在于使用对氰基苯胺替换对叔丁基苯胺，制备得到化合物C9，浅黄色固体，总收率为40％。
Figure GDA0003512230340000141
高分辨质谱，ESI源，正离子模式，分子式[C36H25N3O2+Na]+，理论值554.1839，实测值554.1832.
实施例7：
化合物C6的制备与化合物C4的制备类似，不同之处在于使用对氰基苯胺替换对叔丁基苯胺，制备得到化合物C6，浅黄色固体，总收率为35％。
Figure GDA0003512230340000142
高分辨质谱，ESI源，正离子模式，分子式[C63H46N4O2+Na]+，理论值913.3513，实测值913.3508.
实施例8：
化合物C7的制备与化合物C5的制备类似，不同之处在于使用对氰基苯胺替换对叔丁基苯胺，制备得到化合物C7，浅黄色固体，总收率为34％。
Figure GDA0003512230340000151
高分辨质谱，ESI源，正离子模式，分子式[C42H29N3O2+Na]+，理论值630.2152，实测值630.2158.
实施例9：
化合物C3的制备与化合物C1的制备类似，不同之处在于使用邻溴苯甲酸替换对溴苯甲酸，制备得到中间体G1，进而制备得到化合物C3，浅绿色固体，总收率为39％。
高分辨质谱，ESI源，正离子模式，分子式[C54H47N3O2+Na]+，理论值792.3560，实测值792.3566.
中间体G1的制备
Figure GDA0003512230340000152
在250mL三口瓶中放入磁力搅拌子，加入邻溴苯甲酸(10g,50mmol)，三氯化钌(II)(518.6mg,2.5mmol)，1,8-二氮杂二环[5.4.0]十一碳-7-烯(7.2mL,50mmol)，置换氧气三次以上，加入乙二醇二甲醚60mL，升温至110℃并反应30小时。反应结束并冷却至室温后，加入碳酸钾(20.7g,150mmol)，碘甲烷(9.5mL,150mmol)，室温下搅拌4小时后，减压过滤，真空蒸发溶剂及低沸物，粗产品经柱层析纯化，洗脱剂为石油醚:乙酸乙酯＝10:1。得到目标中间体G1，白色固体5.88g，收率为55％。
高分辨质谱，ESI源，正离子模式，分子式[C16H12Br2O4+Na]+，理论值450.8974(100.0％),448.8995(51.4％),452.8954(48.6％)，实测值450.8975,448.8988,452.8959.
以下通过实施例10-13详细说明本发明合成的化合物作为非掺杂OLED中的发光材料的应用效果。本发明所述实施例10-13与实施例10相比所述器件的制作工艺完全相同，并且所采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是器件中电子阻挡层的厚度。
实施例10：
透明基板层1/ITO阳极层2/空穴传输层3(TAPC，25nm)/发光层4(化合物C1，35nm)/电子传输层5(Tmpypb，55nm)/电子注入层6(LiF，0.8nm)/阴极电极层7(Al，100nm)。各化合物的分子结构式如下：
Figure GDA0003512230340000161
具体制备过程如下：
透明基板层1采用透明玻璃；对ITO阳极层2进行洗涤，即依次进行碱洗涤、纯净水洗涤、干燥后再进行紫外线-臭氧洗涤以清除透明ITO表面的有机残留物。
在进行了上述洗涤之后的ITO阳极层2上，利用真空蒸镀装置，蒸镀膜厚为25nm的TAPC作为空穴传输层3。
上述空穴传输材料蒸镀结束后，紧接着蒸镀膜厚为35nm的化合物C1作为OLED器件的发光层4。
在上述发光层4之后，继续真空蒸镀电子传输层Tmpypb，膜厚为55nm，此层为电子传输层5。
在电子传输层5上，蒸镀膜厚为0.8nm的氟化锂(LiF)层，此层为电子注入层6。
在电子注入层6上，蒸镀膜厚为100nm的铝(Al)层，此层为阴极反射电极层7使用。
如上所述地完成OLED发光器件的制作后，用Keithley B1500A半导体测试仪对器件的电流-亮度-电压特性进行测试，分别用DLM-100Z型光度计和OPT2000型分光光度计收集亮度和电致发光光谱。
实施例11：
透明基板层1/ITO阳极层2/空穴传输层3(TAPC，25nm)/电子阻挡层4(TCTA，10nm)/发光层5(化合物C1，35nm)/电子传输层6(Tmpypb，55nm)/电子注入层7(LiF，0.8nm)/阴极电极层8(Al，100nm)。
实施例12：
透明基板层1/ITO阳极层2/空穴传输层3(TAPC，25nm)/电子阻挡层4(TCTA，5nm)/发光层5(化合物C1，35nm)/电子传输层6(Tmpypb，55nm)/电子注入层7(LiF，0.8nm)/阴极电极层8(Al，100nm)。
实施例13：
透明基板层1/ITO阳极层2/空穴传输层3(TAPC，25nm)/电子阻挡层4(TCTA，8nm)/发光层5(化合物C1，35nm)/电子传输层6(Tmpypb，55nm)/电子注入层7(LiF，0.8nm)/阴极电极层8(Al，100nm)。
所制作的OLED发光器件的测试结果见下表：
Figure GDA0003512230340000181
本发明涉及的一种热活化延迟荧光材料，其同时具有AIE和TADF两种特性，适用于作为非掺杂OLED中的发光材料，从而构筑高效非掺杂有机发光OLED器件。将本发明涉及的这种AIDF热活化延迟荧光材料应用于非掺杂OLED器件的发光层中，通过所述器件的测试数据可知，其取得的器件效果可与最好的掺杂OLED相媲美。
本发明的技术范围不仅仅局限于上述说明中的内容，本领域技术人员可以在不脱离本发明技术思想的前提下，对上述实施例进行多种变形和修改，而这些变形和修改均应当属于本发明的范围内。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (4)

1.一种基于七元环二酰亚胺受体的热活化延迟荧光OLED材料，其特征在于，其具有式Ⅰ或式Ⅱ所示的结构：
Figure FDA0003512230330000011
其中，Ar1、Ar2分别独立表示为苯环；R1表示为亚苯基；R2为：
Figure FDA0003512230330000012
中的任一种；R3表示为叔丁基、氰基单取代的苯基。
2.一种以七元环二酰亚胺为核心的热活化延迟荧光OLED材料，其代表性结构式为：
Figure FDA0003512230330000021
中的任一种。
3.一种有机电致发光器件，其特征在于，至少有一个功能层含有权利要求1-2任一项所述的以七元环二酰亚胺为核心受体的热活化延迟荧光OLED材料。
4.根据权利要求3所述的一种有机电致发光器件，其特征在于，所述功能层为发光层。
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