CN112079833A - 一种有机电致发光化合物及其制备方法和应用 - Google Patents

一种有机电致发光化合物及其制备方法和应用 Download PDF

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CN112079833A
CN112079833A CN202010987121.5A CN202010987121A CN112079833A CN 112079833 A CN112079833 A CN 112079833A CN 202010987121 A CN202010987121 A CN 202010987121A CN 112079833 A CN112079833 A CN 112079833A
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马晓宇
王士凯
顾鑫
孙艳春
李东
田庚
汪康
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

本发明公开了一种有机电致发光化合物，其结构通式如通式1所示：
Figure DDA0002689631080000011
X为化学键，或O、S、SO2、C(R4)(R5)、N(R6)、Si(R7)(R8)、Sn(R9)(R10)或Ge(R11)(R12)；所述R1‑R3为C1‑C30烷基、C6‑C30芳基C3‑C30杂芳基；或与相邻取代基连接形成单环或多环；所述R4～R12为C1‑C30烷基C6‑C30芳基、C3‑C30杂芳基；或与相邻取代基连接形成单环或多环；L为取代或非取代的C6‑C30芳基。本发明有机电致发光化合物合成路线较短，工艺简单，原料易得，成本低，适合工业化生产；本发明制备的有机电致发光化合物具有高量子效率、高寿命等优点。

Description

一种有机电致发光化合物及其制备方法和应用
技术领域
本发明涉及发光材料技术领域，具体涉及一种有机电致发光化合物及其制备方法和应用。
背景技术
电致发光装置(EL装置)为自动发光装置，其优点在于其提供较宽的视角、较大的对比率和较快的响应时间。
有机EL元件是利用了如下原理的自发光元件：通过施加电场，利用由阳极注入的空穴与由阴极注入的电子的复合能使荧光性物质发光。它具有如下结构:阳极、阴极以及介于两者之间的有机层。为了提高有机EL元件的效率和稳定性，有机材料层包括具有不同材料的多层，例如空穴注入层(HIL)、空穴传输层(HTL)、发光层、电子传输层(ETL)和电子注入层(EIL)。
在这种有机EL装置中，当在阳极和阴极之间施加电压时，来自阳极的空穴和来自阴极的电子注入有机材料层。产生的激子在迁移至基态时产生具有特定波长的光。
决定有机EL装置中的发光效率的最重要因素是发光材料。到目前为止，荧光材料已经广泛用作发光材料。然而，鉴于电致发光机制，由于磷光材料在理论上与荧光材料相比使发光效率增强四倍，因此磷光发光材料的开发得到广泛研究。铱(III)络合物已广泛地被称为磷光掺杂材料。目前，4，4′-N，N′-二咔唑-联苯(CBP)、9，10-二(2-萘基)蒽(ADN)等作为已知的磷光主体材料得到广泛的应用。尽管这些材料提供良好发光特征，但其具有以下缺点：(1)由于其较低玻璃态转变温度和不良热稳定性，导致装置的寿命降低。(2)包含磷光主体材料的有机EL装置需要较高的驱动电压。同时，为了提高有机EL装置的效率和稳定性，需要其具有包含空穴注入层、空穴传输层、发光层、电子传输层和电子注入层的多层结构。空穴传输层可改变空穴到发光层的空穴传输效率、发光效率、寿命等。因此，使用铜酞菁(CuPc)、4，4′-双[N-(1-萘基)-N-苯基氨基]联苯(NPB)、N，N′-二苯基-N，N′-双(3-甲基苯基)-(1，1′-联苯)-4，4′-二胺(TPD)等作为空穴传输材料。然而，使用这些材料的有机EL装置在量子效率和使用寿命方面存在问题，量子效率和寿命需要进一步提高。
因此，提供一种高量子效率、高寿命的有机电致发光化合物是本领域技术人员亟需解决的技术问题。
发明内容
有鉴于此，本发明有效解决现有有机EL装置的量子效率和寿命不理想的技术问题，提供了一种有机电致发光化合物，本发明提供的化合物制备的器件具有极佳电流效率和功率效率以及长寿命。
为了实现上述目的，本发明采用如下技术方案：
一种有机电致发光化合物，所述有机电致发光化合物的结构通式如通式1所示：
Figure BDA0002689631070000021
其中，X为化学键，或X选自-O-、-S-、-SO2-、-C(R4)(R5)-、-N(R6)-、-Si(R7)(R8)-、-Sn(R9)(R10)-或-Ge(R11)(R12)；
X优选为化学键；
所述R1-R3各自独立地选自：取代或非取代的C1-C30烷基、取代或非取代C6-C30芳基、取代或非取代的C3-C30杂芳基；或R1-R3各自独立地与相邻取代基连接形成单环或多环；
所述R4～R12各自独立地选自：取代或非取代的C1-C30烷基、取代或非取代C6-C30芳基、取代或非取代的C3-C30杂芳基；或R4～R12各自独立与相邻取代基连接形成单环或多环；
所述Ar1、Ar2、Ar3各自独立地选自：取代或非取代的C1-C30烷基、取代或非取代的C2-C30烯基、取代或非取代的C2-C30炔基、取代或非取代的C6-C30芳基、取代或非取代的3到30元杂芳基、取代或非取代的C6～C60芳烷基胺基、取代或非取代的C6～C60杂芳基胺基、取代或非取代的C6～C60芳基胺基；或Ar1、Ar2、Ar3各自独立与相邻取代基连接形成单环或多环，具体为C3-C30脂环族环或芳香族环；
所述L为取代或非取代的C6-C30芳基，优选为苯或氘代苯。
进一步，上述单环或多环均为C3-C30脂环族环或芳香族环。
在上述技术方案中，术语“取代或非取代的”意指被选自以下的一个、两个或更多个取代基取代：氘；卤素基团；腈基；羟基；羰基；酯基；甲硅烷基；硼基；取代或非取代的烷基；经取代或非取代的环烷基；经取代或非取代的烷氧基；经取代或非取代的烯基；经取代或非取代的烷基胺基；经取代或非取代的杂环基胺基；经取代或非取代的芳基胺基；经取代或非取代的芳基；和经取代或非取代的杂环基，或者被以上所示的取代基中的两个或更多个取代基相连接的取代基取代，或者不具有取代基。例如，“两个或更多个取代基相连接的取代基”可以包括联苯基。换言之，联苯基可以为芳基，或者可以解释为两个苯基相连接的取代基。
在上述技术方案中，优选的有机电致发光化合物选自下述结构中的任意一个：
Figure BDA0002689631070000041
Figure BDA0002689631070000051
本发明还提供了上述有机电致发光化合物的制备方法，
合成路线为：
Figure BDA0002689631070000052
制备方法为：
(1)将原料2溶于THF中，然后用N2置换气体3次，并降温至-78℃，向溶液中缓慢加入n-BuLi,反应2h后在N2保护下加入原料1并缓慢升温至25℃，搅拌反应10h，然后向反应溶液中滴加蒸馏水淬灭反应，并用DCM萃取反应溶液；使用硫酸镁干燥萃取的有机层，并旋转蒸发去除溶剂，然后用DCM和PE混合溶液析出固体制备得到中间体1；
(2)将原料3和原料4加入到甲苯溶液中，然后用N2置换气体3次，在N2保护下加入钯催化剂、三叔丁基膦及叔丁醇钠，搅拌均匀并升温至110℃反应5h，反应完毕后向反应溶液中加入蒸馏水和DCM萃取反应溶液；然后使用硫酸镁干燥萃取的有机层，并旋转蒸发去除溶剂后用DCM和EtOH混合溶液(1：4)析出固体获得中间体2；
(3)将中间体1和中间体2加入到甲苯和THF混合溶液中，缓慢加入MSA，反应12h，然后向反应溶液中加入蒸馏水和DCM萃取反应溶液，浓缩有机相，用柱色谱法提纯产品，获得化学式1所示有机电致发光化合物。
进一步，步骤(1)中所述原料1与原料2的摩尔比为1:1.15-1.25；
步骤(2)中所述原料3与原料4的摩尔比为1:1.15-1.25；
步骤(3)中所述中间体1和中间体2的摩尔比为1:1.20-1.25。
进一步，步骤(1)中所述DCM和PE混合溶液的比例为1：6；
步骤(2)中所述DCM和EtOH混合溶液的体积比为1：4；
步骤(3)中所述甲苯和THF混合溶液的体积比为1:1。
进一步，步骤(2)中所述钯催化剂、三叔丁基膦和叔丁醇钠的摩尔比为1:5:200。
进一步，步骤(3)中所述柱色谱法采用DCM和PE混合液作为洗脱剂；
所述DCM和PE的比例为1：12。
本发明的有益效果在于：本发明有机电致发光化合物合成路线较短，工艺简单，原料易得，成本低，适合工业化生产；本发明制备的有机电致发光化合物具有高量子效率、高寿命等优点。
本发明还提供了上述有机电致发光化合物在制备有机电致发光器件中的应用。
一种有机电致发光器件，依次包括第一电极、若干个有机物层和第二电极；至少一个所述有机物层上述苯并蒽衍生物的有机电致发光化合物。
进一步，上述有机物层包括空穴注入层、空穴传输层、发光辅助层、空穴注入-空穴传输功能层、发光层、电子传输层、电子注入层的一层或几层，且至少一层包上述有机电致发光化合物；优选所述有机物层中至少一层包含空穴注入物质、空穴传输物质、发光辅助物质或既空穴注入-空穴传输功能层。
所述有机物层为单层结构时，有机物层为发光层，所述有机物层为多层结构时，所述有机物层包括发光层；
更进一步，所述发光层中为磷光主体、荧光主体、磷光掺杂材料和荧光掺杂材料中的一种或多种。当所述有机物层包括空穴传输层或发光辅助层时，所述空穴传输层包括化学式1所示的有机发光化合物。
与现有技术相比本发明的有益效果在于：本发明提供的有机电致发光器件具有发光效率高、低驱动电压且寿命较长。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通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，都属于本发明保护的范围。
实施例1：制备化合物1
Figure BDA0002689631070000081
(1)在反应容器中加入原料2(7g，44.6mmol)和100mlTHF，换气3次降温至-78℃，在氮气氛围下加入n-BuLi(44.4mmol)搅拌2h，加入原料1(10g，37.1mmol)升温至25℃，搅拌10h，反应完毕。接着将蒸馏水添加到反应溶液中以淬灭反应，并且用DCM萃取反应溶液。接着使用硫酸镁干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂，用DCM和PE(1：6)析出固体获得中间体1(8.5g，产率为65.9％，MW:347.42)。
(2)将原料3(10g，59mmol)、原料4(11.1g，70.9mmol)溶于150mL甲苯中换气3次，在氮气氛围下加入钯催化剂(0.59mmol)，三叔丁基膦(2.95mmol)和叔丁醇钠(118mmol)升温至120℃，搅拌5h，反应完毕。接着用二氯甲烷和水萃取混合物；接着使用硫酸钠干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂；DCM和无水乙醇按体积比1：4混合析出获得中间体2(13g，产率为89.8％，MW:245.33)。
(3)将中间体1(8.5g，24.4mmol)和中间体2(7.2g，29.28mmol)溶于40ml甲苯和40mlTHF的混合溶液中，加入MSA(11.7g，122mmol)室温反应12h；接着用二氯甲烷和水萃取混合物；接着使用硫酸钠干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂；用柱色谱法纯化剩余物质，洗脱液采用DCM：PE＝1：12，获得化合物1(8.1g，产率为57.8％，MW:574.73)。
实施例2：制备化合物10
Figure BDA0002689631070000091
(1)在反应容器中加入原料2(7g，44.6mmol)和100mlTHF，换气3次降温至-78℃，在氮气氛围下加入n-BuLi(44.4mmol)搅拌2h，加入原料1(10g，37.1mmol)升温至25℃，搅拌10h，反应完毕。接着将蒸馏水添加到反应溶液中以淬灭反应，并且用DCM萃取反应溶液。接着使用硫酸镁干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂，用DCM和PE(1：6)析出固体获得中间体1(8.9g，产率为69.0％，MW:347.28)。
(2)将原料3(18.2g，59mmol)、原料4(11.1g，70.9mmol)溶于150mL甲苯中换气3次，在氮气氛围下加入钯催化剂(0.59mmol)，三叔丁基膦(2.95mmol)和叔丁醇钠(118mmol)升温至120℃，搅拌5h，反应完毕。接着用二氯甲烷和水萃取混合物；接着使用硫酸钠干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂；DCM和无水乙醇(体积比1：4)析出获得中间体2(15.5g，产率为68.3％，MW:385.21)。
(3)将中间体1(8.5g，24.4mmol)和中间体2(11.5g，30.0mmol)溶于40ml甲苯和40mlTHF的混合溶液中，加入MSA(11.7g，122mmol)室温反应12h；接着用二氯甲烷和水萃取混合物；接着使用硫酸钠干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂；用柱色谱法纯化剩余物质，洗脱液采用DCM：PE＝1：12，获得化合物10(15.2g，产率为87.4％，MW:714.30)。
实施例3：制备化合物18
Figure BDA0002689631070000101
(1)在反应容器中加入原料2(10.3g，44.6mmol)和100mlTHF，换气3次降温至-78℃，在氮气氛围下加入n-BuLi(44.4mmol)搅拌2h，加入原料1(10g，37.1mmol)升温至25℃，搅拌10h，反应完毕。接着将蒸馏水添加到反应溶液中以淬灭反应，并且用DCM萃取反应溶液。接着使用硫酸镁干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂，用DCM和PE(1：6)析出固体获得中间体1(8.8g，产率为68.2％，MW:347.15)。
(2)将原料3(21.9g，59mmol)、原料4(11.1g，70.9mmol)溶于150mL甲苯中换气3次，在氮气氛围下加入钯催化剂(0.59mmol)，三叔丁基膦(2.95mmol)和叔丁醇钠(118mmol)升温至120℃，搅拌5h，反应完毕。接着用二氯甲烷和水萃取混合物；接着使用硫酸钠干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂；DCM和无水乙醇(体积比1：4)析出获得中间体2(15.9g，产率为60.2％，MW:447.25)。
(3)将中间体1(8.5g，24.4mmol)和中间体2(13.4g，30.0mmol)溶于40ml甲苯和40mlTHF的混合溶液中，加入MSA(11.7g，122mmol)室温反应12h；接着用二氯甲烷和水萃取混合物；接着使用硫酸钠干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂；用柱色谱法纯化剩余物质，洗脱液采用DCM：PE＝1：12，获得化合物18(15.5g，产率为74.5％，MW:852.33)。
实施例4：制备化合物35
Figure BDA0002689631070000111
(1)在反应容器中加入原料2(9.2g，44.6mmol)和100mlTHF，换气3次降温至-78℃，在氮气氛围下加入n-BuLi(44.4mmol)搅拌2h，加入原料1(10g，37.1mmol)升温至25℃，搅拌10h，反应完毕。接着将蒸馏水添加到反应溶液中以淬灭反应，并且用DCM萃取反应溶液。接着使用硫酸镁干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂，用DCM和PE(1：6)析出固体获得中间体1(9.1g，产率为70.5％，MW:347.18)。
(2)将原料3(24.1g，59mmol)、原料4(11.1g，70.9mmol)溶于150mL甲苯中换气3次，在氮气氛围下加入钯催化剂(0.59mmol)，三叔丁基膦(2.95mmol)和叔丁醇钠(118mmol)升温至120℃，搅拌5h，反应完毕。接着用二氯甲烷和水萃取混合物；接着使用硫酸钠干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂；DCM和无水乙醇(体积比1：4)析出获得中间体2(20.3g，产率为71.0％，MW:485.25)。
(3)将中间体1(8.5g，24.4mmol)和中间体2(14.6g，30.0mmol)溶于40ml甲苯和40mlTHF的混合溶液中，加入MSA(11.7g，122mmol)室温反应12h；接着用二氯甲烷和水萃取混合物；接着使用硫酸钠干燥萃取的有机层，并且使用旋转式蒸发器去除溶剂；用柱色谱法纯化剩余物质，洗脱液采用DCM：PE＝1：12，获得化合物18(18.3g，产率为86.75％，MW:852.33)。
其他化合物的合成方法与上述实施例相同，在此不一一赘述，其他合成实施例质谱和分子式如下表所示：
化合物 分子式 质谱计算值 质谱测试值
化合物31 C<sub>55</sub>H<sub>39</sub>N<sub>3</sub> 741.31 741.35
化合物33 C67H46N2 878.37 878.35
化合物39 C<sub>50</sub>H<sub>36</sub>N<sub>2</sub>O 680.28 680.25
化合物40 C<sub>60</sub>H<sub>40</sub>N<sub>2</sub>O<sub>2</sub> 820.31 820.36
[器件实施例1]有机电致发光器件(空穴传输层)
将本发明实施例合成的化合物作为空穴传输材料，采用通常方法制备有机电致发光器件。首先ITO(阳极)上面蒸镀N1-(萘-2-yl)-N4,N4-二(4-(萘-2-yl(苯基)氨基)苯基)-N1-苯基苯-1,4-二胺("2-TNATA")60nm厚度，紧接着蒸镀本发明合成的化合物1厚度45nm为空穴传输层、主体物质4,4'-N,N'-二咔唑-联苯("CBP")和掺杂物质三(2-苯基吡啶)合铱("Ir(ppy)3")按照98:2重量比混合蒸镀25nm厚度为发光层、蒸镀空穴阻挡层("BAlq")10nm厚度、蒸镀"Alq3"35nm厚度为电子传输层、蒸镀电子注入层LiF 0.2nm厚度、蒸镀阴极Al120nm厚度，形成有机电致发光器件。
器件实施例2-4，按照器件实施例1的方法，蒸镀器件实施例2-4，不同之处将化合物1替换成化合物10、化合物18、化合物35、化合物31、化合物33、化合物39、化合物40。
[比较例1]-[比较例3]
采用与实施例1的同样方法制备有机电致发光器件，其中[比较例1]中用比较化合物1替代化合物1、[比较例2]中用比较化合物2替代化合物1、[比较例3]中用比较化合物3替代化合物1。
Figure BDA0002689631070000121
Figure BDA0002689631070000131
本发明的实施例1-实施例4，比较例1-比较例3制备的有机电致发光器件加偏压以后用Photoresearch公司的PR-650测试电致发光特性(EL)，在5000cd/m2基准亮度下，用Mcscience制备的寿命装备测试T95。测定结果如表2表示。
表2
Figure BDA0002689631070000132
由上述表2的结果能确认使用本发明提供的化合物作为空穴材料的有机电致发光器件表现出高的发光效率低电压以及长寿命。
以上的说明是本发明的简单的说明而已，本发明的应用不限于上述举例，对本领域普通技术人员来说，可以根据上述说明范围内加以改进或变换，所有这些改进和变换应属于本发明权利要求的保护范围。假如本发明实施例是为了说明本发明而已，发明内容范围不是限定在这个范围。本发明的保护范围是必须下面权利要求范围内解析，跟本发明同等范围的一切技术是包含在本发明的权利范围内。

Claims (10)

1.一种有机电致发光化合物，其特征在于，所述有机电致发光化合物的结构通式如通式1所示：
Figure FDA0002689631060000011
其中，X为化学键，或X选自-O-、-S-、-SO2-、-C(R4)(R5)-、-N(R6)-、-Si(R7)(R8)-、-Sn(R9)(R10)-或-Ge(R11)(R12)-；
所述R1-R3各自独立地选自：取代或非取代的C1-C30烷基、取代或非取代C6-C30芳基、取代或非取代的C3-C30杂芳基；或R1-R3各自独立地与相邻取代基连接形成单环或多环；
所述R4～R12各自独立地选自：取代或非取代的C1-C30烷基、取代或非取代C6-C30芳基、取代或非取代的C3-C30杂芳基；或R4～R12各自独立与相邻取代基连接形成单环或多环；
所述Ar1、Ar2、Ar3各自独立地选自：取代或非取代的C1-C30烷基、取代或非取代的C2-C30烯基、取代或非取代的C2-C30炔基、取代或非取代的C6-C30芳基、取代或非取代的3到30元杂芳基、取代或非取代的C6～C60芳烷基胺基、取代或非取代的C6～C60杂芳基胺基、取代或非取代的C6～C60芳基胺基；或Ar1、Ar2、Ar3各自独立与相邻取代基连接形成单环或多环，具体为C3-C30脂环族环或芳香族环；
所述L为取代或非取代的C6-C30芳基。
2.根据权利要求1所述一种有机电致发光化合物，其特征在于，所述单环或多环均为C3-C30脂环族环或芳香族环。
3.一种有机电致发光化合物的制备方法，其特征在于，
合成路线为：
Figure FDA0002689631060000021
制备方法为：
(1)将原料2溶于THF中，然后用N2置换气体3次，并降温至-78℃，向溶液中缓慢加入n-BuLi,反应2h后在N2保护下加入原料1并缓慢升温至25℃，搅拌反应10h，然后向反应溶液中滴加蒸馏水淬灭反应，并用DCM萃取反应溶液；使用硫酸镁干燥萃取的有机层，并旋转蒸发去除溶剂，然后用DCM和PE混合溶液析出固体制备得到中间体1；
(2)将原料3和原料4加入到甲苯溶液中，然后用N2置换气体3次，在N2保护下加入钯催化剂、三叔丁基膦及叔丁醇钠，搅拌均匀并升温至110℃反应5h，反应完毕后向反应溶液中加入蒸馏水和DCM萃取反应溶液；然后使用硫酸镁干燥萃取的有机层，并旋转蒸发去除溶剂后用DCM和EtOH混合溶液(1：4)析出固体获得中间体2；
(3)将中间体1和中间体2加入到甲苯和THF混合溶液中，缓慢加入MSA，反应12h，然后向反应溶液中加入蒸馏水和DCM萃取反应溶液，浓缩有机相，用柱色谱法提纯产品，获得化学式1所示有机电致发光化合物。
4.根据权利要求3所述一种有机电致发光化合物的制备方法，其特征在于，步骤(1)中所述原料1与原料2的摩尔比为1:1.15-1.25；
步骤(2)中所述原料3与原料4的摩尔比为1:1.15-1.25；
步骤(3)中所述中间体1和中间体2的摩尔比为1:1.20-1.25。
5.根据权利要求3所述一种有机电致发光化合物的制备方法，其特征在于，步骤(1)中所述DCM和PE混合溶液的体积比1：6；
步骤(2)中所述DCM和EtOH混合溶液的体积比为1：4；
步骤(3)中所述甲苯和THF混合溶液的体积比为1:1。
6.根据权利要求3所述一种有机电致发光化合物的制备方法，其特征在于，步骤(2)中所述钯催化剂、三叔丁基膦和叔丁醇钠的摩尔比为1:5:200。
7.根据权利要求3所述一种有机电致发光化合物的制备方法，其特征在于，步骤(3)中所述柱色谱法采用DCM和PE混合液作为洗脱剂；
所述DCM和PE的体积比为1：12。
8.一种根据权利要求1或2所述有机电致发光化合物在制备有机电致发光器件中的应用。
9.根据权利要求8所述一种有机电致发光器件，其特征在于，依次包括第一电极、若干层有机物层和第二电极；至少一个所述有机物层包括权利要求1或2所述有机电致发光化合物。
10.根据权利要求9所述一种有机电致发光器件，其特征在于，所述有机物层包括空穴注入层、空穴传输层、发光辅助层、空穴注入-空穴传输功能层、发光层、电子传输层、电子注入层的一层或几层，且至少一层包括权利要求1或2所述有机电致发光化合物。
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