CN113493446A - 一种基于咔唑基的有机电致发光化合物及有机电致发光器件 - Google Patents
一种基于咔唑基的有机电致发光化合物及有机电致发光器件 Download PDFInfo
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- CN113493446A CN113493446A CN202010258801.3A CN202010258801A CN113493446A CN 113493446 A CN113493446 A CN 113493446A CN 202010258801 A CN202010258801 A CN 202010258801A CN 113493446 A CN113493446 A CN 113493446A
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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Abstract
Description
技术领域
本发明涉及有机电致发光技术领域,具体涉及一种基于咔唑基的有机电致发光化合物及有机电致发光器件。
背景技术
有机电致发光器件(Organic Light-emitting Devices,OLED)是利用如下原理的自发性发光器件:当施加电场时,荧光物质通过正极注入的空穴和负极注入的电子的重新结合而发光。这种自发光器件,具有电压低、亮度高、视角宽、响应快、温度适应性好等特性,并且超薄,能制作在柔性面板上等优点,广泛应用于手机、平板电脑、电视、照明等领域。
有机电致发光器件犹如三明治的结构,包括电极材料膜层,以及夹在不同电极膜层或者自荐的有机功能材料,各种不同功能材料根据用途相互叠加在一起共同组成有机电致发光器件。作为电流器件,当对有机电致发光器件的两端电极施加电压,并通过电场作用在有机层功能材料膜层中产生正负电荷,正负电荷进一步在发光层中复合,产生光,此过程为电致发光。
对于有机电致发光器件提高性能的研究包括:降低器件的驱动电压,提高器件的发光效率,提高器件的使用寿命等。为了实现有机电致发光器件性能的不断提升,不但需要有机电致发光器件的结构和制作工艺的创新,更需要有机电致光电功能材料的不断研究和创新,创制出更高性能的有机电致功能材料。
就当前有机电致发光产业的实际需求而言,目前有机电致发光材料的发展还远远不够,落后于面板制造企业的要求。
发明内容
发明目的:针对上述技术问题,本发明提供了一种基于咔唑基的有机电致发光化合物及有机电致发光器件。
为了达到上述发明目的,本发明所采用的技术方案如下:
一种基于咔唑基的有机电致发光化合物,其结构式如下所示:
其中,R1、R2各自独立的为C6-C30的芳香族烃基,所述C6-C30的芳香族烃基中的至少一个C被N取代或非取代;
L为亚苯基、亚联苯基、亚三联苯基中的任意一种;
Ar1、Ar2各自独立的为氢、取代或未取代的C6-C30的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基;
R3、R4、R5、R6、R7、R8、R9、R10各自独立的为氢、氘、氰基、取代或未取代的C1-C30的直链或支链烷基、取代或未取代的C2-C30的直链或支链烯基、取代或未取代的C2-C30的直链或支链炔基、取代或未取代的C6-C30的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基、取代或未取代的C12-C30二芳基氨基、取代或未取代的C10-C30二杂芳基氨基、取代或未取代的C10-C30芳基杂芳基氨基;
X、Y、Z各自独立的为CH或N,且X、Y、Z中至少一个为N。
进一步地,所述有机电致发光化合物的结构式如下式(2)或式(3)所示:
其中,R1、R2各自独立的为C6-C30的芳香族烃基,所述C6-C30的芳香族烃基中的至少一个C被N取代或非取代;
Ar1、Ar2各自独立的为氢、取代或未取代的C6-C30的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基;
R3、R4、R5、R6、R7、R8、R9、R10各自独立的为氢、氘、氰基、取代或未取代的C1-C30的直链或支链烷基、取代或未取代的C2-C30的直链或支链烯基、取代或未取代的C2-C30的直链或支链炔基、取代或未取代的C6-C30的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基、取代或未取代的C12-C30二芳基氨基、取代或未取代的C10-C30二杂芳基氨基、取代或未取代的C10-C30芳基杂芳基氨基;
X、Y、Z各自独立的为CH或N,且X、Y、Z中至少一个为N。
进一步地,R1、R2各自独立的为苯基、联苯基、三联苯基、邻二苯基苯基、蒽基、萘基、菲基、三亚苯基,所述苯基、联苯基、三联苯基、邻二苯基苯基、蒽基、萘基、菲基、三亚苯基为未取代或是其中的至少一个C被N取代。
进一步地,Ar1、Ar2各自独立的为氢、苯基、联苯基、蒽基、萘基、菲基、三亚苯基、芴基、氧芴基、硫芴基、9,9-二甲基芴基、9,9'-螺二芴、9,9-二苯基芴基、咔唑基、N-苯基咔唑基;
所述苯基、联苯基、蒽基、萘基、菲基、三亚苯基、芴基、氧芴基、硫芴基、9,9-二甲基芴基、9,9'-螺二芴、9,9-二苯基芴基、咔唑基、N-苯基咔唑基为未取代的或是其中至少一个氢被氘、氘代或非氘代的C1-C4的直链或支链烷基、氘代或非氘代的苯基取代得到的基团。
进一步地,R3、R4、R5、R6、R7、R8、R9、R10各自独立的为氢、氘、氰基、甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、苯基、蒽基、萘基、菲基、三亚苯基、芴基、氧芴基、硫芴基、9,9-二甲基芴基、9,9'-螺二芴、9,9-二苯基芴基、咔唑基、N-苯基咔唑基、二苯基氨基、二吡啶氨基、二嘧啶氨基、吡啶苯基氨基、嘧啶苯基氨基;
所述甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、苯基、蒽基、萘基、菲基、三亚苯基、芴基、氧芴基、硫芴基、9,9-二甲基芴基、9,9'-螺二芴、9,9-二苯基芴基、咔唑基、N-苯基咔唑基、二苯基氨基、二吡啶氨基、二嘧啶氨基、吡啶苯基氨基、嘧啶苯基氨基为未取代的或是其中至少一个氢被氘、氘代或非氘代的C1-C4的直链或支链烷基、氘代或非氘代的苯基取代得到的基团。
进一步地,所述有机电致发光化合物为以下结构式化合物中的任意一种:
一种有机电致发光器件,包括:阳极、空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层以及阴极顺次堆积的构造;所述发光层中含有上述有机电致发光化合物中的至少一种。
进一步地,所述发光层中还含有以下化合物G1-G48中的至少一种:
一种电子显示设备,含有上述有机电致发光器件。
一种电子显示设备,含有上述有机电致发光器件。
本发明所述室温均为25±5℃。
本发明的有益效果:
本发明设计的化合物为一种应用于OLED的有机电致发光化合物,其结构在设计上具有非常大的扭曲度,该种设计使分子具有较高的刚性及空间位阻能力,有效降低分子因为旋转而损失的能量,进而提高材料分子发光效率。同时该种设计的大扭矩材料分子有效降低了分子的共平面性,进而降低了材料的结晶性,提高了材料分子的Td值,使材料具有更加优异的热稳定性能和成膜的形貌稳定性,进而提高使用该类材料制备的发光元件的寿命及良率。结构通式中的基团L用于链接供电子基(A)和吸电子基(B),该基团骨架的引入能够有效打断供电子基团(A)和吸电子基团(B)之间的共轭,可以有效提高材料分子的ET值,高的ET提高了主客体之间的能量传递,并且能够将三线态激子限制在磷光发光材料中,显著提高了OLED器件的发光效率及寿命。
供电子基团(A)吸电子基团(B)
附图说明
图1为本发明有机电致发光器件的结构示意图。
图中标号分别代表:
1-阳极、2-空穴注入层、3-空穴传输层、4-电子阻挡层、5-发光层、6-空穴阻挡层、7-电子传输层、8-电子注入层、9-阴极。
图2为有机电致发光化合物1的热失重温度曲线图,由图2可知,有机电致发光化合物1的热失重温度Td为402.36℃。
图3为应用例1和对照例1所制备的有机电致发光器件的发光寿命曲线,由图3可知,应用例1和对照例1所制备的有机电致发光器件的发光寿命T97%分别为380h、304h。
具体实施方式
以下进一步说明和描述了各个方面的实施例。应当理解,本文的描述并非旨在将权利要求书限制于所描述的特定方面。相反,旨在覆盖可包括在由所附权利要求书限定的本公开的精神和范围内的替代、修改和等同物。
如本文所用,“Ca至Cb”烃基被限定为具有碳数为“a”(包含在内)至“b”(包含在内)的烃基。如本文所用,“a和/或b”表示“a”或“b”或“a和b”。
如本文所用,在“取代的”或“未取代的”中,术语“取代的”是指该基团中的至少一个氢与烃基、烃衍生物基、卤素或氰基(-CN)重新配位。术语“未取代的”是指该基团中的至少一个氢不与烃基、烃衍生物基、卤素或氰基(-CN)重新配位。烃基或烃衍生物基团的实例可包括C1至C30烷基、C2至C30烯基、C2至C30炔基、C6至C30芳基、C5至C30杂芳基、C1至C30烷氨基、C6至C30芳氨基、C6至C30杂芳氨基、C6至C30芳基杂芳氨基等,但不限于此。
实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1:
有机电致发光化合物1的合成方法如下:
S1:
氮气保护下,将化合物1-a(4g,525.18g/mol,7.62mmol),化合物1-b(1eq,1.27g,167.21g/mol,7.62mmol)、叔丁醇钠(1.1eq,0.81g,96.1g/mol,8.38mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.35g,915g/mol,0.38mmol)、三叔丁基膦(0.05eq,0.08g,202.32g/mol,0.38mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物1-c(2.42g,56.3%),ESI-MS(m/z)(M+):理论值564.47,实测值563.89。
S2:
将化合物1-c(2g,564.47g/mol,3.54mmol)、化合物1-d(1eq,0.98g,277.09g/mol,3.54mmol)和碳酸钠(2eq,0.75g,105.99g/mol,7.08mmol)加入到乙二醇二胺醚(40g,化合物1-c的20倍质量)和水(40g,化合物1-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.054g,304.37g/mol,0.18mmol)和乙酸钯(II)(0.01eq,0.008g,224.51g/mol,0.035mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物1(1.72g,收率67.7%),ESI-MS(m/z)(M+):理论值716.83,实测值716.54。
实施例2:
有机电致发光化合物16的合成方法如下:
S1:
氮气保护下,将化合物2-a(4g,500.26g/mol,8mmol),化合物2-b(1eq,1.34g,167.21g/mol,8mmol)、叔丁醇钠(1.1eq,0.85g,96.1g/mol,8.80mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.37g,915g/mol,0.40mmol)、三叔丁基膦(0.05eq,0.08g,202.32g/mol,0.40mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物2-c(2.40g,55.5%),ESI-MS(m/z)(M+):理论值539.55,实测值539.31。
S2:
将化合物2-c(2g,539.55g/mol,3.71mmol)、化合物2-d(1eq,1.03g,277.09g/mol,3.71mmol)和碳酸钠(2eq,0.79g,105.99g/mol,7.41mmol)加入到乙二醇二胺醚(40g,化合物2-c的20倍质量)和水(40g,化合物2-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.056g,304.37g/mol,0.185mmol)和乙酸钯(II)(0.01eq,0.008g,224.51g/mol,0.037mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物16(1.75g,收率68.2%),ESI-MS(m/z)(M+):理论值691.91,实测值692.04。
实施例3:
有机电致发光化合物19的合成方法如下:
S1:
氮气保护下,将化合物3-a(4g,600.29g/mol,6.66mmol),化合物3-b(1eq,1.11g,167.21g/mol,6.66mmol)、叔丁醇钠(1.1eq,0.70g,96.1g/mol,7.33mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.30g,915g/mol,0.33mmol)、三叔丁基膦(0.05eq,0.07g,202.32g/mol,0.33mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物3-c(2.39g,56.1%),ESI-MS(m/z)(M+):理论值639.58,实测值640.21。
S2:
将化合物3-c(2g,639.58g/mol,3.13mmol)、化合物3-d(1eq,0.87g,277.09g/mol,3.13mmol)和碳酸钠(2eq,0.66g,105.99g/mol,6.25mmol)加入到乙二醇二胺醚(40g,化合物3-c的20倍质量)和水(40g,化合物3-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.048g,304.37g/mol,0.156mmol)和乙酸钯(II)(0.01eq,0.007g,224.51g/mol,0.031mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物19(1.68g,收率67.7%),ESI-MS(m/z)(M+):理论值791.94,实测值791.15。
实施例4:
有机电致发光化合物25的合成方法如下:
S1:
氮气保护下,将化合物4-a(4g,465.15g/mol,8.60mmol),化合物4-b(1eq,1.44g,167.21g/mol,8.60mmol)、叔丁醇钠(1.1eq,0.91g,96.1g/mol,9.46mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.39g,915g/mol,0.43mmol)、三叔丁基膦(0.05eq,0.09g,202.32g/mol,0.43mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物4-c(2.53g,58.3%),ESI-MS(m/z)(M+):理论值504.44,实测值503.98。
S2:
将化合物4-c(2g,504.44g/mol,3.96mmol)、化合物4-d(1eq,1.10g,277.09g/mol,3.96mmol)和碳酸钠(2eq,0.84g,105.99g/mol,7.93mmol)加入到乙二醇二胺醚(40g,化合物4-c的20倍质量)和水(40g,化合物4-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.060g,304.37g/mol,0.198mmol)和乙酸钯(II)(0.01eq,0.009g,224.51g/mol,0.040mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物25(1.74g,收率66.9%),ESI-MS(m/z)(M+):理论值656.80,实测值656.62。
实施例5:
有机电致发光化合物26的合成方法如下:
S1:
氮气保护下,将化合物5-a(4g,449.08g/mol,8.91mmol),化合物5-b(1eq,1.49g,167.21g/mol,8.91mmol)、叔丁醇钠(1.1eq,0.94g,96.1g/mol,9.8mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.41g,915g/mol,0.45mmol)、三叔丁基膦(0.05eq,0.09g,202.32g/mol,0.45mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物5-c(2.56g,58.9%),ESI-MS(m/z)(M+):理论值488.37,实测值489.14。
S2:
将化合物5-c(2g,488.37g/mol,4.10mmol)、化合物5-d(1eq,1.13g,277.09g/mol,4.10mmol)和碳酸钠(2eq,0.87g,105.99g/mol,8.19mmol)加入到乙二醇二胺醚(40g,化合物5-c的20倍质量)和水(40g,化合物5-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.062g,304.37g/mol,0.205mmol)和乙酸钯(II)(0.01eq,0.009g,224.51g/mol,0.041mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物26(1.76g,收率66.9%),ESI-MS(m/z)(M+):理论值640.73,实测值640.52。
实施例6:
有机电致发光化合物38的合成方法如下:
S1:
氮气保护下,将化合物6-a(4g,459.12g/mol,8.71mmol),化合物6-b(1eq,1.46g,167.21g/mol,8.71mmol)、叔丁醇钠(1.1eq,0.92g,96.1g/mol,9.58mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.40g,915g/mol,0.44mmol)、三叔丁基膦(0.05eq,0.09g,202.32g/mol,0.44mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物6-c(2.37g,54.7%),ESI-MS(m/z)(M+):理论值498.41,实测值499.22。
S2:
将化合物6-c(2g,498.41g/mol,4.01mmol)、化合物6-d(1eq,1.11g,277.09g/mol,4.01mmol)和碳酸钠(2eq,0.85g,105.99g/mol,8.03mmol)加入到乙二醇二胺醚(40g,化合物6-c的20倍质量)和水(40g,化合物6-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.061g,304.37g/mol,0.201mmol)和乙酸钯(II)(0.01eq,0.009g,224.51g/mol,0.040mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物38(1.73g,收率66.2%),ESI-MS(m/z)(M+):理论值650.77,实测值650.46。
实施例7:
有机电致发光化合物50的合成方法如下:
S1:
氮气保护下,将化合物7-a(4g,525.18g/mol,7.62mmol),化合物7-b(1eq,1.40g,167.21g/mol,7.62mmol)、叔丁醇钠(1.1eq,0.81g,96.1g/mol,8.38mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.35g,915g/mol,0.38mmol)、三叔丁基膦(0.05eq,0.08g,202.32g/mol,0.38mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物7-c(2.40g,55.9%),ESI-MS(m/z)(M+):理论值564.47,实测值565.13。
S2:
将化合物7-c(2g,564.47g/mol,3.54mmol)、化合物7-d(1eq,0.99g,279.06g/mol,3.54mmol)和碳酸钠(2eq,0.75g,105.99g/mol,7.09mmol)加入到乙二醇二胺醚(40g,化合物7-c的20倍质量)和水(40g,化合物7-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.054g,304.37g/mol,0.177mmol)和乙酸钯(II)(0.01eq,0.008g,224.51g/mol,0.035mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物50(1.65g,收率64.8%),ESI-MS(m/z)(M+):理论值718.80,实测值718.64。
实施例8:
有机电致发光化合物75的合成方法如下:
S1:
氮气保护下,将化合物8-a(4g,465.15g/mol,8.60mmol),化合物8-b(1eq,1.44g,167.21g/mol,8.60mmol)、叔丁醇钠(1.1eq,0.91g,96.1g/mol,9.46mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.39g,915g/mol,0.43mmol)、三叔丁基膦(0.05eq,0.09g,202.32g/mol,0.43mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物8-c(2.49g,57.3%),ESI-MS(m/z)(M+):理论值504.44,实测值505.26。
S2:
将化合物8-c(2g,504.44g/mol,3.96mmol)、化合物8-d(1eq,1.70g,429.28g/mol,3.96mmol)和碳酸钠(2eq,0.84g,105.99g/mol,7.93mmol)加入到乙二醇二胺醚(40g,化合物8-c的20倍质量)和水(40g,化合物8-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.060g,304.37g/mol,0.200mmol)和乙酸钯(II)(0.01eq,0.009g,224.51g/mol,0.040mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物75(2.20g,收率68.5%),ESI-MS(m/z)(M+):理论值808.99,实测值808.58。
实施例9:
有机电致发光化合物87的合成方法如下:
S1:
氮气保护下,将化合物9-a(4g,409.06g/mol,9.78mmol),化合物9-b(1eq,1.85g,167.21g/mol,9.78mmol)、叔丁醇钠(1.1eq,1.03g,96.1g/mol,10.76mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.45g,915g/mol,0.49mmol)、三叔丁基膦(0.05eq,0.10g,202.32g/mol,0.49mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物9-c(2.53g,57.7%),ESI-MS(m/z)(M+):理论值448.35,实测值449.53。
S2:
将化合物9-c(2g,448.35g/mol,4.46mmol)、化合物9-d(1eq,1.92g,430.27g/mol,4.46mmol)和碳酸钠(2eq,0.95g,105.99g/mol,8.92mmol)加入到乙二醇二胺醚(40g,化合物9-c的20倍质量)和水(40g,化合物9-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.068g,304.37g/mol,0.223mmol)和乙酸钯(II)(0.01eq,0.010g,224.51g/mol,0.045mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物87(2.33g,收率69.4%),ESI-MS(m/z)(M+):理论值753.89,实测值753.97。
实施例10:
有机电致发光化合物98的合成方法如下:
S1:
氮气保护下,将化合物10-a(4g,525.18g/mol,7.62mmol),化合物10-b(1eq,2.54g,333.38g/mol,7.62mmol)、叔丁醇钠(1.1eq,0.81g,96.1g/mol,8.38mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.35g,915g/mol,0.38mmol)、三叔丁基膦(0.05eq,0.08g,202.32g/mol,0.38mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物10-c(3.01g,54.1%),ESI-MS(m/z)(M+):理论值730.65,实测值731.44。
S2:
将化合物10-c(2g,730.65g/mol,2.74mmol)、化合物10-d(1eq,0.76g,277.09g/mol,2.74mmol)和碳酸钠(2eq,0.58g,105.99g/mol,5.47mmol)加入到乙二醇二胺醚(40g,化合物10-c的20倍质量)和水(40g,化合物10-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.042g,304.37g/mol,0.137mmol)和乙酸钯(II)(0.01eq,0.006g,224.51g/mol,0.027mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物98(1.73g,收率71.3%),ESI-MS(m/z)(M+):理论值883.00,实测值884.09。
实施例11:
有机电致发光化合物100的合成方法如下:
S1:
氮气保护下,将化合物11-a(4g,525.18g/mol,7.62mmol),化合物11-b(1eq,2.43g,319.40g/mol,7.62mmol)、叔丁醇钠(1.1eq,0.81g,96.1g/mol,8.38mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.35g,915g/mol,0.38mmol)、三叔丁基膦(0.05eq,0.08g,202.32g/mol,0.38mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物11-c(2.99g,54.8%),ESI-MS(m/z)(M+):理论值716.66,实测值717.42。
S2:
将化合物11-c(2g,716.66g/mol,2.79mmol)、化合物11-d(1eq,0.77g,277.09g/mol,2.79mmol)和碳酸钠(2eq,0.59g,105.99g/mol,5.58mmol)加入到乙二醇二胺醚(40g,化合物11-c的20倍质量)和水(40g,化合物11-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.042g,304.37g/mol,0.140mmol)和乙酸钯(II)(0.01eq,0.006g,224.51g/mol,0.028mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物100(1.71g,收率70.4%),ESI-MS(m/z)(M+):理论值869.02,实测值870.40。
实施例12:
有机电致发光化合物145的合成方法如下:
S1:
氮气保护下,将化合物12-a(4g,282.90g/mol,14.14mmol),化合物12-b(1eq,7.13g,504.58g/mol,14.14mmol)、叔丁醇钠(1.1eq,1.49g,96.1g/mol,15.55mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.65g,915g/mol,0.71mmol)、三叔丁基膦(0.05eq,0.14g,202.32g/mol,0.71mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物12-c(5.14g,55.1%),ESI-MS(m/z)(M+):理论值659.58,实测值660.32。
S2:
将化合物12-c(2g,659.58g/mol,3.03mmol)、化合物12-d(1eq,0.84g,277.09g/mol,3.03mmol)和碳酸钠(2eq,0.64g,105.99g/mol,6.06mmol)加入到乙二醇二胺醚(40g,化合物12-c的20倍质量)和水(40g,化合物12-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.046g,304.37g/mol,0.152mmol)和乙酸钯(II)(0.01eq,0.007g,224.51g/mol,0.030mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物145(1.70g,收率68.9%),ESI-MS(m/z)(M+):理论值811.93,实测值811.84。
实施例13:
有机电致发光化合物146的合成方法如下:
S1:
氮气保护下,将化合物13-a(4g,282.90g/mol,14.14mmol),化合物13-b(1eq,7.13g,409.48g/mol,14.14mmol)、叔丁醇钠(1.1eq,1.49g,96.1g/mol,15.55mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.65g,915g/mol,0.71mmol)、三叔丁基膦(0.05eq,0.14g,202.32g/mol,0.71mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物13-c(4.37g,54.7%),ESI-MS(m/z)(M+):理论值564.47,实测值565.25。
S2:
将化合物13-c(2g,564.47g/mol,3.54mmol)、化合物13-d(1eq,0.98g,277.09g/mol,3.54mmol)和碳酸钠(2eq,0.75g,105.99g/mol,7.09mmol)加入到乙二醇二胺醚(40g,化合物13-c的20倍质量)和水(40g,化合物13-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.054g,304.37g/mol,0.177mmol)和乙酸钯(II)(0.01eq,0.008g,224.51g/mol,0.035mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物146(1.76g,收率69.3%),ESI-MS(m/z)(M+):理论值716.83,实测值716.46。
实施例14:
有机电致发光化合物170的合成方法如下:
S1:
氮气保护下,将化合物14-a(4g,525.18g/mol,7.62mmol),化合物14-b(1eq,1.27g,167.21g/mol,7.62mmol)、叔丁醇钠(1.1eq,0.81g,96.1g/mol,8.38mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.35g,915g/mol,0.38mmol)、三叔丁基膦(0.05eq,0.08g,202.32g/mol,0.38mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物14-c(2.40g,55.9%),ESI-MS(m/z)(M+):理论值564.47,实测值565.38。
S2:
将化合物14-c(2g,564.47g/mol,3.54mmol)、化合物14-d(1eq,0.98g,276.10g/mol,3.54mmol)和碳酸钠(2eq,0.75g,105.99g/mol,7.09mmol)加入到乙二醇二胺醚(40g,化合物14-c的20倍质量)和水(40g,化合物14-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.054g,304.37g/mol,0.177mmol)和乙酸钯(II)(0.01eq,0.008g,224.51g/mol,0.035mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物170(1.78g,收率70.2%),ESI-MS(m/z)(M+):理论值715.84,实测值715.91。
实施例15:
有机电致发光化合物195的合成方法如下:
S1:
氮气保护下,将化合物15-a(4g,465.15g/mol,8.60mmol),化合物15-b(1eq,1.44g,167.21g/mol,8.60mmol)、叔丁醇钠(1.1eq,0.91g,96.1g/mol,9.46mmol)、三(二亚苄基丙酮)二钯(0.05eq,0.39g,915g/mol,0.43mmol)、三叔丁基膦(0.05eq,0.09g,202.32g/mol,0.43mol)、甲苯(40ml)加入反应瓶中,加料完毕后升温至回流反应5h,反应完毕后降至室温后加入水(40ml),搅拌15min后过滤得滤液,滤液经由硅藻土过滤后分液得有机相,有机相使用无水硫酸镁干燥后旋干,经过柱层析提纯后得到化合物15-c(2.36g,54.4%),ESI-MS(m/z)(M+):理论值504.44,实测值505.02。
S2:
将化合物15-c(2g,504.44g/mol,3.96mmol)、化合物15-d(1eq,1.09g,275.11g/mol,3.96mmol)和碳酸钠(2eq,0.84g,105.99g/mol,7.93mmol)加入到乙二醇二胺醚(40g,化合物15-c的20倍质量)和水(40g,化合物15-c的20倍质量)中,搅拌混匀后再依次加入三(邻甲苯基)膦(0.05eq,0.060g,304.37g/mol,0.198mmol)和乙酸钯(II)(0.01eq,0.009g,224.51g/mol,0.040mmol),升温至回流反应15h后,将有机相分出,水洗后减压浓缩,得到粗品,粗品再经过柱层析后得到有机电致发光化合物195(1.76g,收率67.7%),ESI-MS(m/z)(M+):理论值654.82,实测值654.66。
上述实施例1-15中的中间体化合物和反应试剂均可以从国内化工产品市场购买或定制,例如购买自宇瑞(上海)化学有限公司、国药集团试剂公司、百灵威试剂公司。另外,本领域技术人员也可以通过公知方法合成,限于篇幅具体路线,申请人就不在此一一赘述。
材料性质测试:
测试GH-1、GH-2及本发明有机电致发光化合物1、16、19、25、26、38、50、75、87、98、100、145、146、170、195的热失重温度Td,测试结果如下表1所示。
注:热失重温度Td是在氮气气氛中失重5%的温度,在TGA N-1000热重分析仪上进行测定,测试时氮气流量为10mL/min。
表1:
项目 | 材料 | Td/℃ |
对照例1 | GH-1 | 277.25 |
对照例2 | GH-2 | 308.46 |
实施例1 | 1 | 402.36 |
实施例2 | 16 | 394.57 |
实施例3 | 19 | 413.62 |
实施例4 | 25 | 398.14 |
实施例5 | 26 | 395.80 |
实施例6 | 38 | 404.22 |
实施例7 | 50 | 392.67 |
实施例8 | 75 | 411.63 |
实施例9 | 87 | 388.34 |
实施例10 | 98 | 394.66 |
实施例11 | 100 | 405.73 |
实施例12 | 145 | 389.94 |
实施例13 | 146 | 393.81 |
实施例14 | 170 | 409.25 |
实施例15 | 195 | 415.92 |
由上述数据可知,本发明有机电致发光化合物热稳定性均优于GH-1、GH-2,说明符合本发明结构通式的有机电致发光化合物都具有优良的热稳定性,可以满足作为有机电致发光器件发光材料使用要求。
器件性能测试:
应用例1:
采用ITO作为反射层阳极基板材料,并依次用水、丙酮、N2等离子对其进行表面处理;
在ITO阳极基板上方,沉积厚度为10nm的HAT-CN形成空穴注入层(HIL);
在空穴注入层(HIL)上方蒸镀NPD形成厚度为120nm的空穴传输层(HTL);
在空穴传输层(HTL)上方真空蒸镀EB-1,形成厚度为10nm的电子阻挡层(EBL);
将本发明实施例1中的有机电致发光化合物1作为第一主体材料、G1作为第二主体材料,GD-18作为掺杂材料(第一主体材料与第二主体材料的重量比为6:4,掺杂材料用量为第一主体材料与第二主体材料总重量的5%)通过蒸镀在电子阻挡层(EBL)上形成厚度为20nm的发光层;
将HB-1蒸镀到发光层上得到厚度为15nm的空穴阻挡层(HBL);
将ETM和LiQ以1:1的比例混合蒸镀得到厚度为30nm的电子传输层(ETL),在电子传输层(ETL)上方蒸镀厚度为2nm的LiQ形成电子注入层(EIL);
此后将镁(Mg)和银(Ag)以9:1的比例混合蒸镀得到厚度为15nm的阴极,在上述阴极封口层上沉积50nm厚度的DNTPD,此外,在阴极表面以UV硬化胶合剂和含有除湿剂的封装薄膜(seal cap)进行密封,以保护有机电致发光器件不被大气中的氧气或水分所影响至此制备获得有机电致发光器件。
应用例2-15
分别以本发明实施例2-15中的有机电致发光化合物16、19、25、26、38、50、75、87、98、100、145、146、170、195作为发光层中的第一主体材料,其他部分与应用例1一致,据此制作出应用例2-15的有机电致发光器件。
对照例1、2:
与应用例1的区别在于,使用GH-1、GH-2作为发光层中的第一主体材料,其余与应用例1相同。
上述应用例制造的有机电致发光器件及对照例制造的有机电致发光器件的特性是在电流密度为10mA/cm2的条件下测定的,结果如表2所示。
表2:
实验组 | 第一主体材料 | 电流密度(mA/cm<sup>2</sup>) | 电压(V) | 发光效率(Cd/A) | 发光颜色 |
对照例1 | GH-1 | 10 | 4.36 | 113 | 绿色 |
对照例2 | GH-2 | 10 | 4.22 | 120 | 绿色 |
应用例1 | 1 | 10 | 3.94 | 146 | 绿色 |
应用例2 | 16 | 10 | 3.85 | 150 | 绿色 |
应用例3 | 19 | 10 | 3.89 | 144 | 绿色 |
应用例4 | 25 | 10 | 3.77 | 135 | 绿色 |
应用例5 | 26 | 10 | 3.92 | 143 | 绿色 |
应用例6 | 38 | 10 | 3.86 | 139 | 绿色 |
应用例7 | 50 | 10 | 3.90 | 152 | 绿色 |
应用例8 | 75 | 10 | 4.01 | 133 | 绿色 |
应用例9 | 87 | 10 | 3.83 | 146 | 绿色 |
应用例10 | 98 | 10 | 3.92 | 141 | 绿色 |
应用例11 | 100 | 10 | 3.97 | 138 | 绿色 |
应用例12 | 145 | 10 | 3.96 | 137 | 绿色 |
应用例13 | 146 | 10 | 4.04 | 142 | 绿色 |
应用例14 | 170 | 10 | 3.85 | 145 | 绿色 |
应用例15 | 195 | 10 | 3.97 | 150 | 绿色 |
由如上表2可知,本发明有机电致发光化合物应用于有机电致发光器件中,在相同电流密度下,发光效率得到了较大幅度的提升,器件的电压有所下降,器件的功耗相对降低,使得器件的寿命相应提高。
分别将对照例1、应用例1、应用例2、应用例4、应用例5所制备的有机电致发光器件进行发光寿命测试,得到发光寿命T97%数据(发光亮度降低至初始亮度97%的时间),测试设备为TEO发光器件寿命测试系统。结果如表3所示:
表3:
由上表3可知,将本发明有机电致发光化合物应用于有机电致发光器件中,在相同电流密度下,使用寿命得到较大程度提升,具有广阔的应用前景。
Claims (10)
1.一种基于咔唑基的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式如下所示:
其中,R1、R2各自独立的为C6-C30的芳香族烃基,所述C6-C30的芳香族烃基中的至少一个C被N取代或非取代;
L为亚苯基、亚联苯基、亚三联苯基中的任意一种;
Ar1、Ar2各自独立的为氢、取代或未取代的C6-C30的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基;
R3、R4、R5、R6、R7、R8、R9、R10各自独立的为氢、氘、氰基、取代或未取代的C1-C30的直链或支链烷基、取代或未取代的C2-C30的直链或支链烯基、取代或未取代的C2-C30的直链或支链炔基、取代或未取代的C6-C30的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基、取代或未取代的C12-C30二芳基氨基、取代或未取代的C10-C30二杂芳基氨基、取代或未取代的C10-C30芳基杂芳基氨基;
X、Y、Z各自独立的为CH或N,且X、Y、Z中至少一个为N。
2.如权利要求1所述的基于咔唑基的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式如下式(2)或式(3)所示:
其中,R1、R2各自独立的为C6-C30的芳香族烃基,所述C6-C30的芳香族烃基中的至少一个C被N取代或非取代;
Ar1、Ar2各自独立的为氢、取代或未取代的C6-C30的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基;
R3、R4、R5、R6、R7、R8、R9、R10各自独立的为氢、氘、氰基、取代或未取代的C1-C30的直链或支链烷基、取代或未取代的C2-C30的直链或支链烯基、取代或未取代的C2-C30的直链或支链炔基、取代或未取代的C6-C30的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基、取代或未取代的C12-C30二芳基氨基、取代或未取代的C10-C30二杂芳基氨基、取代或未取代的C10-C30芳基杂芳基氨基;
X、Y、Z各自独立的为CH或N,且X、Y、Z中至少一个为N。
3.如权利要求1所述的基于咔唑基的有机电致发光化合物,其特征在于,R1、R2各自独立的为苯基、联苯基、三联苯基、邻二苯基苯基、蒽基、萘基、菲基、三亚苯基,所述苯基、联苯基、三联苯基、邻二苯基苯基、蒽基、萘基、菲基、三亚苯基为未取代或是其中的至少一个C被N取代。
4.如权利要求1所述的基于咔唑基的有机电致发光化合物,其特征在于,Ar1、Ar2各自独立的为氢、苯基、联苯基、蒽基、萘基、菲基、三亚苯基、芴基、氧芴基、硫芴基、9,9-二甲基芴基、9,9'-螺二芴、9,9-二苯基芴基、咔唑基、N-苯基咔唑基;
所述苯基、联苯基、蒽基、萘基、菲基、三亚苯基、芴基、氧芴基、硫芴基、9,9-二甲基芴基、9,9'-螺二芴、9,9-二苯基芴基、咔唑基、N-苯基咔唑基为未取代的或是其中至少一个氢被氘、氘代或非氘代的C1-C4的直链或支链烷基、氘代或非氘代的苯基取代得到的基团。
5.如权利要求1所述的基于咔唑基的有机电致发光化合物,其特征在于,R3、R4、R5、R6、R7、R8、R9、R10各自独立的为氢、氘、氰基、甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、苯基、蒽基、萘基、菲基、三亚苯基、芴基、氧芴基、硫芴基、9,9-二甲基芴基、9,9'-螺二芴、9,9-二苯基芴基、咔唑基、N-苯基咔唑基、二苯基氨基、二吡啶氨基、二嘧啶氨基、吡啶苯基氨基、嘧啶苯基氨基;
所述甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、苯基、蒽基、萘基、菲基、三亚苯基、芴基、氧芴基、硫芴基、9,9-二甲基芴基、9,9'-螺二芴、9,9-二苯基芴基、咔唑基、N-苯基咔唑基、二苯基氨基、二吡啶氨基、二嘧啶氨基、吡啶苯基氨基、嘧啶苯基氨基为未取代的或是其中至少一个氢被氘、氘代或非氘代的C1-C4的直链或支链烷基、氘代或非氘代的苯基取代得到的基团。
7.一种有机电致发光器件,其特征在于,所述有机电致发光器件包括:阳极、空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层以及阴极顺次堆积的构造;所述发光层中含有如权利要求1-6中任一项所述的有机电致发光化合物中的至少一种。
9.一种电子显示设备,其特征在于,含有如权利要求7或8所述的有机电致发光器件。
10.一种电子显示设备,其特征在于,含有如权利要求7或8所述的有机电致发光器件。
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