CN114044781A - 一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料及其在有机电致发光器件中的应用 - Google Patents

一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料及其在有机电致发光器件中的应用 Download PDF

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CN114044781A
CN114044781A CN202111405396.4A CN202111405396A CN114044781A CN 114044781 A CN114044781 A CN 114044781A CN 202111405396 A CN202111405396 A CN 202111405396A CN 114044781 A CN114044781 A CN 114044781A
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phenanthroline
pyrazine
red light
parent nucleus
thermal activation
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李成龙
王悦
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Jilin University
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Abstract

一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料及其在有机电致发光器件中的应用，属于有机电致发光技术领域。本发明将氰基取代香豆素与邻菲罗啉吡嗪整合在一起，作为强吸电子能力片段，结合给电子基团，设计TADF材料的基础上，通过分子内氢键的作用更进一步增强了分子刚性，确保高荧光量子效率。本发明所述的以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料作为客体材料掺杂到主体材料中作为发光层使用，客体材料的掺杂比例为2～5wt％，从而获得了EQE高的红光、深红光有机电致发光器件。

Description

一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料及 其在有机电致发光器件中的应用
技术领域
本发明属于有机电致发光技术领域，具体涉及一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料及其在有机电致发光器件中的应用。
背景技术
近年来，热活化延迟荧光(Thermally activated delayed fluorescence，TADF)材料及其有机发光二极管(Organic light-emitting diodes，OLED)取得了突飞猛进的发展。大多数的TADF发光分子为纯有机给(D)-受体(A)结构。利用D-A间强的分子内电荷转移作用减小单-三重态劈裂能，实现高效的反向系间窜越(RISC)，从而利用三重态激子发光。因此，与荧光和磷光技术相比，TADF技术在100％激子利用率、低成本、环保和可持续性等方面具有突出的优势。然而，相较于外量子效率(EQE:External Quantum Efficiency)已经超过30％的蓝光和绿光TADF材料，由于窄带隙导致非辐射跃迁速率高、分子内电荷转移(ICT:intramolecular charge transfer)效应强引起光致发光效率(PLQY:PhotoluminescenceQuantum Yield)差的红光、深红光TADF材料的外量子效率(EQE)普遍较低。因此，设计EQE更高、发光峰波长位于红光特别是深红至近红外区域的TADF材料是有机电致发光材料领域一项函待解决的技术难题。
发明内容
鉴于现有技术的不足，本发明的目的在于提供了一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料及其在有机电致发光器件中的应用。
本发明所述的一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料，其结构如通式(Ⅰ)所示：
Figure BDA0003372615780000011
其中，D代表给体基团，选自取代或未取代的C12-C40的咔唑基及其衍生物基团、取代或未取代的C12-C40的二苯胺基及其衍生物基团、取代或未取代的C13-C40的吖啶基及其衍生物基团、取代或未取代的C12-C40的吩噻嗪及其衍生物基团、取代或未取代的C12-C40的吩噁嗪及其衍生物基团、取代或未取代的C12-C40的二苯并氮杂硅烷及其衍生物基团；
虚线表示氢键；
优选的，D选自如下结构之一：
Figure BDA0003372615780000021
波浪线表示与苯环键连。
本发明所述具体实施方案中，以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料作为发光层客体的结构式如下之一所示，但不限于此：
Figure BDA0003372615780000022
Figure BDA0003372615780000031
Figure BDA0003372615780000041
Figure BDA0003372615780000051
本发明所述具体实施方案中，以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料的制备步骤和条件可参考本领域类似反应的步骤和条件。
本发明提供了如通式Ⅰ所示，以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料的制备方法：
Figure BDA0003372615780000052
上述反应步骤中涉及的中间反应物结构为：
Figure BDA0003372615780000061
本发明所述的以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料可以在有机电致发光器件中得到应用，具体的以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料作为客体材料掺杂到主体材料中作为发光层使用，客体材料的掺杂比例为 2～5wt％。
本发明提供的一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料在将氰基取代香豆素与邻菲罗啉吡嗪整合在一起，作为强吸电子能力片段，结合给电子基团，设计TADF材料的基础上，通过分子内氢键的作用更进一步增强了分子刚性，确保高荧光量子效率，获得了EQE高的红光、深红光有机电致发光器件。
具体实施方式
下面结合具体的实施例，对本发明作进一步地详细说明，但本发明的实施方式不限于此。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。基于本发明中的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。
合成实施例1
表1.合成实施例产物数据汇总：
Figure BDA0003372615780000071
以化合物21、49为例说明合成实施例实验具体细节：
Figure BDA0003372615780000081
将6.21g 2,3-二氨基苯酚(50mmol)和18.40g 2,9-二溴-1,10-菲罗啉-5,6-二酮(50mmol)按照1:1的摩尔比加入到醋酸(1mol，60mL)和82g醋酸钠(1mol) 中，回流6个小时，冷却至室温后，将反应液倒入水中，过滤，分别用水和甲醇洗涤滤饼，所得滤饼真空干燥，得到3,6-二溴二吡啶并[3,2-a:2’,3’-c]-吩嗪-10-醇。
将9.12g 3,6-二溴二吡啶并[3,2-a:2’,3’-c]-吩嗪-10-醇(20mmol)与2.33g苯甲醛 (22mmol)、1.32丙二腈(22mmol)按照摩尔比1：1.1加入300mL乙醇中，加 10滴三乙胺(每毫摩尔原料添加0.5滴)，在氮气氛围下，加热回流8小时。待反应完成后，停止加热，反应体系自行冷却至室温析出固体，过滤并用乙醇洗滤饼，烘箱干燥后得到2-氨-10,13-二溴-4-苯-2H-吡喃酮[2,3-h]二吡啶并[3,2-a:2’,3’-c]吩嗪 -3-腈。
将6.10g 2-氨-10,13-二溴-4-苯-2H-吡喃酮[2,3-h]二吡啶并[3,2-a:2’,3’-c]吩嗪-3- 腈(10mmol)与2.54g碘(10mmol)等摩尔比加入150mL乙醇溶液中，加热回流反应12小时。待反应完成后，停止加热，反应体系自行冷却至室温析出固体，过滤并用乙醇洗滤饼，烘箱干燥后得到10,13-二溴-2-氧代-4-苯-2H-吡喃酮[2,3-h]二吡啶并[3,2-a:2’,3’-c]吩嗪-3-腈。
将3.05g 10,13-二溴-2-氧代-4-苯-2H-吡喃酮[2,3-h]二吡啶并[3,2-a:2’,3’-c]吩嗪 -3-腈(5mmol)和中间反应物4.02g(2-([1,1’-二苯基]-4-(苯基)胺)苯基)硼酸(11mmol) 按照1:2.2摩尔比溶于四氢呋喃(THF)中，再加入2.07g K2CO3(原料与其摩尔比1：3)于上述溶液中，搅拌10min。在N2氛围下，加入催化剂0.067g Pd(PPh3)4(原料与其摩尔比1：0.013)，于90℃下回流反应24h。将产物倒入H2O中，用CH2Cl2萃取，有机相旋干得到固体。用CH2Cl2作洗脱剂，通过硅胶过滤催化剂和杂质，蒸馏除去滤液中的溶剂后，再用少量CH2Cl2溶解，加入正己烷作为不良溶剂，对粗品进行重结晶，得到目标产物，然后通过真空升华得到红色纯品4.09g(产率 75％)。
Figure BDA0003372615780000091
按照前述三步反应得到10,13-二溴-2-氧代-4-苯-2H-吡喃酮[2,3-h]二吡啶并[3,2-a:2’,3’-c]吩嗪-3-腈。
将3.05g 10,13-二溴-2-氧代-4-苯-2H-吡喃酮[2,3-h]二吡啶并[3,2-a:2’,3’-c]吩嗪 -3-腈(5mmol)和中间反应物4.96g(3-(10H-螺[吖啶-9,9,-芴]-10-基)苯基)硼酸(11mmol)按照1:2.2摩尔比溶于四氢呋喃(THF)中，再加入2.07g K2CO3(原料与其摩尔比1：3)于上述溶液中，搅拌10min。在N2氛围下，加入催化剂0.067g Pd(PPh3)4(原料与其摩尔比1：0.013)，于90℃下回流反应24h。将产物倒入H2O 中，用CH2Cl2萃取，有机相旋干得到固体。用CH2Cl2作洗脱剂，通过硅胶过滤催化剂和杂质，蒸馏除去滤液中的溶剂后，再用少量CH2Cl2溶解，加入正己烷作为不良溶剂，对粗品进行重结晶，得到目标产物，然后通过真空升华得到红色纯品 4.74g(产率75％)。
获得的目标化合物有关数据见表1。
效果实施例
以下利用本发明所述的以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料制备有机电致发光器件实施例，该有机电致发光器件由阳极、阴极和布置在阳极和阴极之间的至少一层有机功能层组成；且有机功能层中应当包括发光层，本发明所述的以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料作为客体材料掺杂到主体材料中作为发光层使用。
具体的器件制备工艺及器件性能测试实验操作如下：透明ITO玻璃作为制备器件的基底材料，后先以5％ITO洗液超声处理30min，之后依次以蒸馏水(2次)、丙酮(2次)、异丙醇(2次)超声洗涤，最后将ITO玻璃保存在异丙醇中。每次使用前，先用丙酮棉球和异丙醇棉球小心擦拭ITO玻璃表面，待异丙醇冲洗后烘干，之后用等离子体处理5min。器件的制备利用真空镀膜设备采用真空蒸镀工艺完成，当真空蒸镀系统的真空度达到5*10-4Pa以下时开始蒸镀，沉积速率由赛恩斯膜厚仪监控，利用真空蒸镀工艺在ITO玻璃上依次沉积各种有机层(空穴注入层、空穴传输层、发光层和电子传输层)及LiF电子注入层和金属Al电极(具体器件结构见如下效果实施例)。器件的电流、电压、亮度、发光光谱等特性采用 PR655光谱扫描亮度计和Keithley K 2400数字源表系统同步测试。器件的性能测试在空气中进行。
实施例1～20
实施例1有机电致发光器件结构为：
[ITO/TAPC(45nm)/TCTA(10nm)/EML(DCzDPy:Dopant(5wt％),20nm)/B3PymPm(50nm)/LiF(1nm)/Al(100nm)](其中，空穴注入层TAPC、空穴传输层TCTA、发光层EML和电子传输层B3PymPm)。应用实施例中发光层主体为DczDPy，发光层客体(Dopant)分别为化合物1、5、9、10、14、17、21、22、26、30、31、35、 39、40、44、48、49、53、57、58，客体掺杂比均为5wt％。效果实施例结果见表 2。
Figure BDA0003372615780000101
表2.效果实施例所提供的电致发光器件数据参数：
器件代号 发光层客体 启亮电压(V) 发光峰峰位(nm) 最大EQE(％)
应用实施例1 化合物1 2.5 638 15.2
应用实施例2 化合物5 2.4 642 15.6
应用实施例3 化合物9 2.6 644 14.8
应用实施例4 化合物10 2.5 645 15.3
应用实施例5 化合物14 2.4 640 14.2
应用实施例6 化合物17 2.6 643 15.6
应用实施例7 化合物21 2.5 646 16.5
应用实施例8 化合物22 2.3 648 16.2
应用实施例9 化合物26 2.6 612 25.8
应用实施例10 化合物30 2.5 609 25.5
应用实施例11 化合物31 2.3 615 26.2
应用实施例12 化合物35 2.4 612 24.9
应用实施例13 化合物39 2.4 614 24.6
应用实施例14 化合物40 2.6 615 25.2
应用实施例15 化合物44 2.5 628 18.1
应用实施例16 化合物48 2.4 630 18.3
应用实施例17 化合物49 2.3 620 17.2
应用实施例18 化合物53 2.5 662 12.6
应用实施例19 化合物57 2.4 665 12.5
应用实施例20 化合物58 2.6 624 16.8
依据效果实施例的结果证明，本发明所提供的以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料作为TADF红光客体材料应用于有机电致发光器件，器件最大 EQE均达到了较高水平，尤其给体基团为吩噻嗪和吩噁嗪的深红光器件最大EQE 均超过12％，优于文献中普遍报道的最大EQE约10％的深红光器件。
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 (5)

1.一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料，其结构如通式(Ⅰ)所示：
Figure FDA0003372615770000011
其中，D代表给体基团，选自取代或未取代的C12-C40的咔唑基及其衍生物基团、取代或未取代的C12-C40的二苯胺基及其衍生物基团、取代或未取代的C13-C40的吖啶基及其衍生物基团、取代或未取代的C12-C40的吩噻嗪及其衍生物基团、取代或未取代的C12-C40的吩噁嗪及其衍生物基团、取代或未取代的C12-C40的二苯并氮杂硅烷及其衍生物基团；
虚线表示氢键。
2.如权利要求1所述的一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料，其特征在于：给体基团D选自如下结构之一：
Figure FDA0003372615770000012
波浪线表示与苯环键连。
3.如权利要求2所述的一种以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料，其特征在于：其结构如下之一所示，
Figure FDA0003372615770000021
Figure FDA0003372615770000031
Figure FDA0003372615770000041
Figure FDA0003372615770000051
4.权利要求1～3任何一项所述的以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料在有机电致发光器件中的应用。
5.如权利要求4所述的以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料在有机电致发光器件中的应用，其特征在于：以香豆素并菲啰啉吡嗪为母核的热活化延迟红光材料作为客体材料掺杂到主体材料中作为发光层使用，客体材料的掺杂比例为2～5wt％。
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