CN112079834B - 一种有机电致发光化合物及其应用 - Google Patents

一种有机电致发光化合物及其应用 Download PDF

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CN112079834B
CN112079834B CN202010984128.1A CN202010984128A CN112079834B CN 112079834 B CN112079834 B CN 112079834B CN 202010984128 A CN202010984128 A CN 202010984128A CN 112079834 B CN112079834 B CN 112079834B
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马晓宇
王士凯
刘锟
李金磊
刘静
高尚明
段小亮
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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，结构通式如式I所示：
Figure DDA0002688626500000011
其中，其中，Ar1、Ar2各自独立的选自取代或未经取代的C1‑C30烷基、C2‑C30烯基、C2‑C30炔基、取代或未经取代的C3‑C30环烷基、取代或未经取代的C3‑C30杂环烷基、取代或未经取代的C6‑C30芳基、取代或未经取代的3元到30元杂芳基；取代或未经取代的3元到30元杂芳基胺基、取代或未经取代的C6‑C60芳基胺基、C1‑C30烷氧基、C6‑C60芳氧基；或，Ar1、Ar2各自独立的与相邻取代基连接形成单环或多环。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。

Description

一种有机电致发光化合物及其应用
技术领域
本发明涉及有机发光材料技术领域，更具体的说是涉及一种有机电致发光化合物及其应用。
背景技术
有机电致发光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材料层，为了提高有机电致发光元件的效率和稳定性，有机材料层通常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)；在这种有机发光元件中，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，其中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。
目前使用铜酞菁(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，使用这些材料的有机电致发光元件虽然在空穴传输效率、发光效率、寿命等方面有所提高，但是在量子效率和使用寿命方面仍然不是很理想。
为此，能够提供一种性能优良的高效有机发光化合物是本领域技术人员亟需解决的问题。
发明内容
有鉴于此，本发明提供了一种有机电致发光化合物及其应用，该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。
为了达到上述目的，本发明采用如下技术方案：
一种有机电致发光化合物，所述化合物的结构通式如式I所示：
Figure BDA0002688626490000021
其中，Ar1、Ar2各自独立的选自取代或未经取代的C1-C30烷基、C2-C30烯基、C2-C30炔基、取代或未经取代的C3-C30环烷基、取代或未经取代的C3-C30杂环烷基、取代或未经取代的C6-C30芳基、取代或未经取代的3元到30元杂芳基；取代或未经取代的3元到30元杂芳基胺基、取代或未经取代的C6-C60芳基胺基、C1-C30烷氧基、C6-C60芳氧基；或，Ar1、Ar2各自独立的与相邻取代基连接形成单环或多环；
R1、R2、R3、R4各自独立的选自取代或未经取代的C1-C30烷基、取代或未经取代C6-C30芳基、取代或未经取代的C3-C30杂芳基；或，R1、R2、R3、R4各自独立的与相邻取代基连接形成单环或多环；
所述R1、R2、R4表示取代基个数为单、二、三、四或无取代基；所述R3表示取代基个数为单、二、三或无取代基；
X选自O、S、SO2、C(R5)(R6)、N(R7)、Si(R8)(R9)、Sn(R10)(R11)、Ge(R12)(R13)和连接键中的任意一种；
L为取代或未经取代的C6-C30芳基或者连接键。
优选地，所述Ar1、Ar2各自独立的选自取代或未经取代C6-C20芳基、取代或未经取代的C15-C26杂芳基或三芳胺基。
优选地，所述Ar1、Ar2各自独立的选自取代或未经取代C10-C14芳基、取代或未经取代的C18-C22杂芳基或三苯胺基。
优选地，所述X为连接键。
优选地，L为苯或氘代苯。
优选地，所述R5-R13各自独立的选自取代或未经取代的C1-C30烷基、取代或未经取代C6-C30芳基、取代或未经取代的C3-C30杂芳基；或，R5-R13各自独立的与相邻取代基连接形成单环或多环。
优选地，所述R1-R13各自独立的与相邻取代基连接形成的单环或多环为C3-C30的脂环族环或C3-C30的芳香族环。
优选地，所述Ar1和Ar2各自独立的与相邻取代基连接形成单环或多环为C3-C30脂肪族环或3元到30元芳香族环，且所述脂肪族环或芳香族环至少一个碳原子可置换为氮、氧或硫。
优选的，上述有机电致发光化合物的结构式为以下结构式中的任一种：
Figure BDA0002688626490000031
Figure BDA0002688626490000041
上述所述一种有机电致发光化合物的制备方法，包括如下步骤：
(1)在氮气保护下，将原料2溶于四氢呋喃中，降温至-78℃，然后加入2.5mol/L的正丁基锂反应2h，反应完成后加入原料1，升温至25℃，搅拌10h后，再经过淬灭、萃取、干燥、去除溶剂、柱色谱法纯化，得到中间体1；
(2)在所述中间体1中加入冰乙酸，升温至80℃，再依次加入浓硫酸、蒸馏水，析出固体即为中间体2；
(3)将所述中间体2和原料3溶于甲苯溶液中，在氮气保护下加入钯催化剂和碳酸钾，搅拌均匀，升温至95℃反应10h，反应结束后，再经过萃取、干燥、去除溶剂、柱色谱法纯化，即得化学式1所示化合物；
或，
将所述中间体2、原料4溶于甲苯溶液后，在氮气保护下加入钯催化剂、三叔丁基膦和叔丁醇钠，搅拌均匀，升温至110℃反应8h，反应结束后，再经过萃取、干燥、去除溶剂、柱色谱法纯化，即得化学式2所示化合物；所述制备方法的合成路线如下所示：
Figure BDA0002688626490000051
优选地，步骤(1)中所述原料2、所述正丁基锂和所述原料1的摩尔比为44.6:44.6:37，所述原料2与所述四氢呋喃的摩尔体积比为44.6mol:100ml。优选地，步骤(2)所述中间体1、所述冰乙酸、所述浓硫酸和所述蒸馏水的体积比为1:20:1:20。
优选地，步骤(3)中所述中间体2和所述原料3的摩尔比为1:1；所述中间体2、所述原料4、所述钯催化剂、所述三叔丁基膦和所述叔丁醇钠的摩尔比为18.1:21.8:0.181:0.905:36.2。
优选地，步骤(1)中所述淬灭、萃取、干燥、去除溶剂、柱色谱法纯化的具体方法为：搅拌完成后，将蒸馏水缓慢添加到反应溶液中进行淬灭反应，并且用二氯甲烷萃取反应溶液；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；用二氯甲烷和石油醚(1：6)析出固体获得中间体1。
优选地，步骤(3)中所述萃取、干燥、去除溶剂、柱色谱法纯化的具体方法为：搅拌完成后，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，即获得所述化学式1和2所示的化合物。
上述所述一种有机电致发光化合物的应用，上述所述的有机电致发光化合物或上述所述制备方法制备的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，包括：第一电极、第二电极以及至少一层设置在所述第一电极和所述第二电极之间的有机物层；其特征在于，所述有机物层包含权利要求1-4任一所述的有机电致发光化合物或权利要求5-8任一所述制备方法制备的有机电致发光化合物。
优选的，所述有机物层包括第一空穴传输层、第二空穴传输层或激子阻挡层，所述空穴传输层和激子阻挡层包含所述有机电致发光化合物。
经由上述的技术方案可知，与现有技术相比，本发明的有益效果如下：本发明有机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；并且，本发明提供的有机电致发光器件具有量子效率高、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
本实施例提供了一种有机电致发光化合物，其化学结构式为发明内容中的化合物1，该有机发光化合物的制备方法的反应路线如下：
Figure BDA0002688626490000071
其具体的制备方法包括以下步骤：
1)在反应容器中加入原料2(44.6mmol)和100mlTHF，用氮气置换空气3次降温至-78℃，在氮气保护下加入2.5mol/L n-BuLi(17.8ml，44.6mmol)搅拌2h，加入原料1(37mmol)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(12g，产率为70.6％，MW:457.96)；
2)将中间体1(26.2mmol)加入到反应瓶中，加入冰乙酸240ml，升温至80℃，滴加浓硫酸12ml，滴加完毕即反应完毕，接着加入240ml蒸馏水，固体析出，烘干获得中间体2(8g，产率为69.5％，MW:439.35)；
3)将中间体2(18.1mmol)和原料4(21.8mmol)加入到甲苯溶液中，接着换气3次，氮气保护下加入钯催化剂(0.181mmol)、三叔丁基膦(0.905mmol)及叔丁醇钠(36.2mmol)，搅拌均匀，升温至110℃，反应10h，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(DCM：PE＝1：11)纯化剩余物质，获得化合物1(9.2g，产率为88.8％，MW:572.71)。
实施例2
本实施例提供了一种有机电致发光化合物，其化学结构式为发明内容中的化合物8，该有机发光化合物的制备方法的反应路线如下：
Figure BDA0002688626490000081
其具体的制备方法包括以下步骤：
1)在反应容器中加入原料2(44.6mmol)和100mlTHF，氮气置换空气3次降温至-78℃，在氮气氛围下加入2.5mol/L n-BuLi(17.8ml，44.6mmol)搅拌2h，加入原料1(37mmol)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(12.5g，产率为73.5％，MW:457.30)；
2)将中间体1(26.2mmol)加入到反应瓶中，加入冰乙酸240ml，升温至80℃，滴加浓硫酸12ml，滴加完毕即反应完毕，接着加入240ml蒸馏水，固体析出，烘干获得中间体2(9g，产率为78.3％，MW:439.88)3
3)将中间体2(18.1mmol)和原料4(21.8mmol)加入到甲苯溶液中，接着换气3次，氮气保护下加入钯催化剂(0.181mmol)、三叔丁基膦(0.905mmol)及叔丁醇钠(36.2mmol)，搅拌均匀，升温至110℃，反应10h，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(DCM：PE＝1：11)纯化剩余物质，获得化合物8(10g，产率为72.1％，MW:766.80)。
实施例3
本实施例提供了一种有机电致发光化合物，其化学结构式为发明内容中的化合物21，该有机发光化合物的制备方法的反应路线如下：
Figure BDA0002688626490000091
其具体的制备方法包括以下步骤：
1)在反应容器中加入原料2(44.6mmol)和100mlTHF，氮气置换空气3次降温至-78℃，在氮气氛围下加入2.5mol/L n-BuLi(17.8ml，44.6mmol)搅拌2h，加入原料1(37mmol)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(12.8g，产率为75.3％，MW:457.25)；
2)将中间体1(26.2mmol)加入到反应瓶中，加入冰乙酸240ml，升温至80℃，滴加浓硫酸12ml，滴加完毕即反应完毕，接着加入240ml蒸馏水，固体析出，烘干获得中间体2(9.5g，产率82.6％，MW:439.28)；
3)将中间体2(15mmol)和原料3(15mmol)加入到甲苯乙醇和水的混合溶液中，接着换气3次，氮气保护下加入钯催化剂和碳酸钾，搅拌均匀，升温至95℃，反应10h，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获得化合物21(8.1g，产率为83.5％，MW:648.31)。
实施例4
本实施例提供了一种有机电致发光化合物，其化学结构式为发明内容中的化合物35，该有机发光化合物的制备方法的反应路线如下：
Figure BDA0002688626490000101
其具体的制备方法包括以下步骤：
1)在反应容器中加入原料2(44.6mmol)和100mlTHF，氮气置换空气3次降温至-78℃，在氮气氛围下加入2.5mol/L n-BuLi(17.8ml，44.6mmol)搅拌2h，加入原料1(37mmol)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(13g，产率为76.5％，MW:457.43)；
2)将中间体1(26.2mmol)加入到反应瓶中，加入冰乙酸240ml，升温至80℃，滴加浓硫酸12ml，滴加完毕即反应完毕，接着加入240ml蒸馏水，固体析出，烘干获得中间体2(10g，产率76.9％，MW:495.13)；
3)将中间体2(15mmol)和原料3(15mmol)加入到甲苯乙醇和水的混合溶液中，接着换气3次，氮气保护下加入钯催化剂和碳酸钾，搅拌均匀，升温至95℃，反应10h，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获得化合物35(9.0g，产率为63.4％，MW:946.35)。
因结构通式为发明内容中的式I的其他化合物的制备方法的合成路线和原理均与上述所列举的实施例1～4的相同，所以在此不再穷举，本发明又选取4个化合物(发明内容中的化合物31、33、37、40)作为实施例，其对应质谱测试值和分子式如下表1所示。
表1化合物31、33、37、40的质谱测试值和分子式表
化合物 分子式 质谱计算值 质谱测试值
化合物31 C<sub>62</sub>H<sub>48</sub>N<sub>2</sub> 820.38 820.33
化合物33 C<sub>68</sub>H<sub>52</sub>N<sub>2</sub> 896.41 896.45
化合物37 C<sub>71</sub>H<sub>52</sub>N<sub>2</sub> 932.41 932.43
化合物40 C<sub>69</sub>H<sub>48</sub>N<sub>2</sub>O 920.38 920.37
本发明实施例还提供了一种采用上述实施例提供的有机电致发光化合物制备得到的有机电致发光器件，其中，该有机电致发光器件包括第一电极、第二电极以及至少一层设置在所述第一电极与第二电极之间的有机物层。
其中，有机物层可包含空穴注入层，空穴传输层、激子阻挡层、发光层、空穴阻挡层、电子传输层及电子注入层中一种或多种。
根据所使用的材料，本发明实施例提及的有机电致发光器件可为顶部发光型、底部发光型或双面发光型。另外，本发明实施例提供的有机电致发光化合物还可用于利用与有机电致发光器件相似的原理的有机电子器件，譬如有机太阳能电池、有机光导体、有机晶体管等。
具体的，上述有机电致发光器件的制备方法可参照实施例5。
实施例5
该实施例提供了一种有机电致发光器件的制备方法，其包括以下步骤：
将涂层厚度为
Figure BDA0002688626490000121
的ITO玻璃基板放在蒸馏水中清洗3次，超声波洗涤30分钟，用蒸馏水反复清洗3次，超声波洗涤15分钟，蒸馏水清洗结束后，异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里。将已经准备好的ITO透明电极上蒸镀厚度为45nm的4,4',4”-三[2-萘基苯基氨基]三苯基胺(2-TNATA)作为空穴注入层。然后将实施例1制备的化合物1在形成的空穴注入层上面真空蒸镀厚度为35nm的空穴传输层。然后在上述空穴传输层上蒸镀厚度为25nm的蓝色主体材料9,10-二(2-萘基)蒽(AND)和掺杂材料N1,N1,N6,N6-四苯基芘-1,6-二胺(TPPDA)。主体材料和掺杂材料的重量比为95：5。接着在上述发光层上真空蒸镀厚度为10nm的双(2-甲基-8-羟基喹啉-N1)-(1,1’-联苯-4-羟基)铝(BAlq)作为空穴阻挡层。在上述空穴阻挡层上真空蒸镀厚度为40nm的Alq3作为电子传输层。在上述电子传输层上真空蒸镀厚度为0.5nm氟化锂(LiF)，作为电子注入层。最后蒸镀厚度为150nm的铝作为阴极，以此完成了有机电致发光器件的制备。
参照上述实施例5提供的方法，分别选用化学物8,21,31,33,35,37,40的有机电致发光化合物替代化合物1的有机发光化合物进行蒸镀，并制备得到相应的有机电致发光器件实施例6-12。
对比例1
该对比例提供了一种有机电致发光器件，将空穴传输层的材料由化合物1置换为NPB，化学式如下：
Figure BDA0002688626490000122
NPB
对上述制备的有机电致发光器件加以正向直流偏置电压，利用Photo Res earch公司的PR-650光度测量设备测定有机电致发光特性，并在5000cd/m2的基准灰度下利用McScience公司的寿命测定装置测定了T95的寿命，其测试结果如下表2所示。
表2实施例5-12和对比例1测试结果
Figure BDA0002688626490000131
从上表可知：由本发明提供的有机电致发光化合物作为空穴传输层制备的有机电致发光器件相对于由NPB作为空穴传输层制备的有机电致发光器件，具有更低的启动电压，发光效率和寿命得到了显著的提高。
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (3)

1.一种有机电致发光化合物，其特征在于，所述化合物的结构通式如下所示：
Figure FDA0003038347000000011
2.一种有机电致发光化合物的应用，其特征在于，权利要求1所述的有机电致发光化合物在制备有机电致发光器件中的应用。
3.一种有机电致发光器件，包括：第一电极、第二电极以及至少一层设置在所述第一电极和所述第二电极之间的有机物层；其特征在于，所述有机物层包含权利要求1所述的有机电致发光化合物制备的有机电致发光化合物。
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