CN114105815A - 一种具有对称结构的有机化合物及其应用、一种有机电致发光器件 - Google Patents

一种具有对称结构的有机化合物及其应用、一种有机电致发光器件 Download PDF

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CN114105815A
CN114105815A CN202110991095.8A CN202110991095A CN114105815A CN 114105815 A CN114105815 A CN 114105815A CN 202110991095 A CN202110991095 A CN 202110991095A CN 114105815 A CN114105815 A CN 114105815A
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phenyl
substituted
benzo
compound
pyrimidinyl
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CN114105815B (zh
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贾学艺
吕瑶
范洪涛
李鑫
秦大山
吴卫娜
王帅
陈稳
冯美娟
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Beijing Green Guardee Technology Co ltd
Hebei Huaqing Photoelectric Material Co ltd
Hebei University of Technology
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Beijing Green Guardee Technology Co ltd
Hebei Huaqing Photoelectric Material Co ltd
Hebei University of Technology
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Abstract

本发明涉及有机电致发光器件领域,公开了一种具有对称结构的有机化合物及其应用、一种有机电致发光器件,该化合物具有式(I)所示的结构。本发明的化合物能够实现含有该有机化合物的器件具有优异的发光效率。

Description

一种具有对称结构的有机化合物及其应用、一种有机电致发 光器件
技术领域
本发明涉及有机电致发光器件领域,具体涉及一种具有对称结构的有机化合物及其应用、一种有机电致发光器件。
背景技术
有机电致发光现象是1963年Pope等人最早发现的,他们发现蒽的单层晶体在高达400V以上电压的驱动下,可以发出微弱的蓝光,但驱动电压高,单晶蒽厚度大,因此没有引起人们的广泛关注。
直到1987年柯达公司的邓青云博士等人报道了基于荧光效率高、电子传输性好的8-羟基喹啉铝和空穴传输性良好的芳香二胺两种有机半导体材料,通过真空热蒸镀制备了器件为三明治型的OLED,在驱动电压小于10V的器件亮度达到1000cd/m2,外量子效率达到了1%,使得有机电致发光材料及器件具有了实用性的可能,从此大大推动了OLED材料及器件的研究。
有机发光二极管按照出光方式分为底发射器件和顶发射器件,底发射器件所采用的阳极是透明的,一般是透明的铟锡氧化物(ITO)或铟锌氧化物(IZO)通过溅射的方式生长在透明的玻璃基板上形成透明的阳极,再将各有机功能材料通过蒸镀或其他的制备方式依次生长在透明阳极上,在选择合适的阴极制备成有机电致发光器件,发光层发出的光通过ITO和玻璃基板发射出来。
采用底发射的方式制备显示屏,由于驱动电压和显示区域要同时制作在玻璃基板上,导致显示区域的面积相对减少,进而导致显示屏的开口率降低。
与底发射器件比,顶发射器件由于本身的特点,光从顶部电极射出,在有源驱动OLED中,像素驱动电路、总线等可以制作在显示区域的下方,显示区域面积相对增大,显示屏的开口率增加。
由于顶发射器件制作的显示屏具有分辨率高、信息含量高等优点,这都使得顶发射有机电致发光器件受到越来越多的关注,成为研究的热点。
对于顶发射OLED器件,光需要通过半透明的金属阴极射出,半透明的金属电极的厚度不但影响电极的导电性也极大地影响着光的透光率、反射率及光的吸收率,厚度太薄影响电极的导电率,厚度太厚则影响光的透过率。
早在20世纪60年代,就发现金属薄层的光透过率可以通过在金属薄层表面覆盖介电层物质来实现提高或者降低(A.Vasicek,Optics of Thin Films,North-Holland,Amsterdam,1960)。
2001年柯达的研究者将此现象应用在OLED器件中,发现通过在金属阴极表面溅射一层高折射率的无机材料可使半透明阴极的光透过率从没有使用覆盖层材料的30%左右,提高到75%左右,这就大大提高了OLED器件的光取出性能(Hung et al.Appl.Phys.Lett.,2001,78,544),从中可以发现具有高折射率的介电覆盖层材料能够有效的减少光能在光学元件表面的反射,从而提高半透明金属电极的光透过率。
目前,OLED器件或屏体仍然存在驱动电压高、使用寿命短、电流效率和亮度均低的缺陷,为了改善这些缺陷,一方面器件结构需要进一步优化,另一方面也需要改进各功能层及发光材料的性能,其中,CPL材料可提高阴极的透过率,从而提高了器件的发光效率,电子传输材料可提高电子的注入能力和电子的传输能力,进而提高器件的发光效率及降低器件的驱动电压。
因此,开发新型的CPL材料和优异的电子传输材料具有十分重要的意义。
发明内容
本发明的目的是为了提供一种具有较高的玻璃化转变温度、分解温度及高折射率的有机化合物,以期实现含有该有机化合物的器件具有优异的发光效率。
为了实现上述目的,本发明的第一方面提供一种具有对称结构的有机化合物,该化合物具有式(I)所示的结构;
Figure BDA0003232426630000031
其中,在式(I)中,
A为O、S、-C(CH3)2-、-C(Ph2)2-、-N(Ph)-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基、苯并菲基、
Figure BDA0003232426630000032
基、芘基、吡啶基、吡嗪基、三嗪基、异喹啉基、喹喔啉基。
本发明第二方面提供第一方面中所述的化合物在有机电致发光器件中的应用。
本发明的第三方面提供一种含有前述第一方面中所述的化合物中的一种或两种以上的化合物的有机电致发光器件,所述化合物存在于该有机电致发光器件的电子注入层、电子传输层和覆盖层的至少一层中。
本发明提供的前述具有对称结构的有机化合物具有较高的玻璃化转变温度、分解温度及高折射率,应用于器件上的覆盖层时,能够提高阴极的光取出效率,进而提高了器件的发光效率;同时本发明所提供的前述有机化合物作为电子传输材料时,能够提高电子的注入能力及提高电子的迁移速率,应用于有机电致发光器件的电子传输层时,可降低器件的驱动电压及提高器件的发光效率。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本发明针对“L选自苯基、萘基”表示的是,L作为连接基团,苯基和萘基的任意两个能够被取代的位置均可以与母核结构中的相应基团连接,例如,苯基和萘基在母核结构中可以具有如下所述的连接方式(波浪线表示连接位点):
Figure BDA0003232426630000041
本发明定义“苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基、苯并菲基、
Figure BDA0003232426630000052
基、芘基、吡啶基、吡嗪基、三嗪基、异喹啉基、喹喔啉基”等,表示的是,Ar中任意能够被取代的位置均能够与母核结构中的相应基团连接。
“苯基取代的喹唑啉基”表示喹唑啉基直接与母核结构中的相应基团连接,且该喹唑啉基上含有至少一个苯基。其余类似命名的基团具有与此相似的解释。
本发明式(I)所示的母核结构中,碳氮双键与苯环的连接关系可以为苯环上任意能够连接的位置。
如前所述,本发明的第一方面中提供了一种具有对称结构的有机化合物,该化合物具有式(I)所示的结构;
Figure BDA0003232426630000051
其中,在式(I)中,
A为O、S、-C(CH3)2-、-C(Ph2)2-、-N(Ph)-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基、苯并菲基、
Figure BDA0003232426630000053
基、芘基、吡啶基、吡嗪基、三嗪基、异喹啉基、喹喔啉基。
更优选地,在式(I)中,
A为O、S、-C(CH3)2-、-C(Ph2)2-、-N(Ph)-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基。
根据一种优选的具体实施方式,在式(I)中,
A为-C(CH3)2-或-C(Ph2)2-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基。
更优选地,在上述优选的具体实施方式中,式(I)所示的化合物选自权利要求3中优选情况下列举的具体化合物中的任意一种。
根据另一种优选的具体实施方式,在式(I)中,
A为O;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基。
更优选地,在上述优选的具体实施方式中,式(I)所示的化合物选自权利要求4中优选情况下列举的具体化合物中的任意一种。
根据另一种优选的具体实施方式,在式(I)中,
A为S;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基。
更优选地,在上述优选的具体实施方式中,式(I)所示的化合物选自权利要求5中优选情况下列举的具体化合物中的任意一种。
根据一种优选的具体实施方式,在式(I)中,
A为-N(Ph)-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基;
更优选地,在上述优选的具体实施方式中,式(I)所示的化合物选自权利要求6中优选情况下列举的具体化合物中的任意一种。
根据另一种优选的具体实施方式,式(I)所示的化合物选自权利要求7中列举的具体化合物中的任意一种。
本发明对制备前述化合物的具体方法没有特别的限制,本领域技术人员可以根据本发明提供的具体结构式,结合有机合成领域内的已知工艺路线获得本发明前述的化合物,并且,本发明的后文中示例性地列举了几个实例以说明本发明的化合物的制备方法,本领域技术人员也可以根据本发明的后文中的化合物的制备方法,通过替换原料的种类获得其余所有化合物的具体制备方法。本发明不再对全部化合物的制备方法进行详述,本领域技术人员不应理解为对本发明的限制。
如前所述,本发明的第二方面提供了前述第一方面中所述的化合物在有机电致发光器件中的应用。
如前所述,本发明的第三方面提供了一种含有前述第一方面中所述的化合物中的一种或两种以上的化合物的有机电致发光器件,所述化合物存在于该有机电致发光器件的电子注入层、电子传输层和覆盖层的至少一层中。
特别地,将本发明所述的有机化合物,特别是前述具体实施方式中的有机化合物用于有机电致发光器件中,例如用作覆盖在金属阴极表面的覆盖层材料或用作电子传输材料时,能够显著提高有机电致发光器件的光电性能。
因此,根据一种优选的具体实施方式,所述化合物存在于该有机电致发光器件的阴极表面的覆盖层中。
因此,根据另一种优选的具体实施方式,所述化合物存在于该有机电致发光器件的电子传输层中。
优选情况下,所述有机电致发光器件包括依次层叠设置的阳极、空穴注入层、空穴传输层、任选的电子阻挡层、发光层、任选的空穴阻挡层、电子传输层、电子注入层、阴极和覆盖层。
本发明的所述空穴注入层(HIL)、空穴传输层(HTL)、任选的电子阻挡层(EBL)、发光层(EML)、任选的空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)中的任意一种或者两种以上一起构成有机电致发光器件的有机材料层,在所述有机电致发光器件中,,有机材料层的数量可以为一个或者两个以上。
形成所述阳极的阳极材料,通常优选具有大功函数的材料,从而能够降低空穴注入势垒,例如能够在本发明中使用的阳极材料选自以下材料的一种或多种,金属,如钒、铬、铜和金,或其他合金:金属氧化物,如:氧化锌、氧化铟、氧化铟锡、氧化铟锌和二氧化锡,金属和氧化物的组合,如:氧化锌:铝,但不限于此。
形成所述空穴注入层的材料例如为空穴注入材料,作为空穴注入材料优选的化合物要具有传输空穴的能力,因此,具有注入阳极中的空穴效应,对发光层或发光材料具有优异的空穴注入效应,防止发光层中产生的激子移动至电子注入层或电子注入材料,此外,具有优异的薄膜形成能力。
空穴注入材料的HOMO优选在阳极材料的功函数与周围有机材料层的HOMO之间。
形成所述空穴传输层的材料例如为空穴传输材料,能够接收来自阳极或空穴注入层的空穴、使空穴移动至发光层并对空穴具有高迁移率的材料。
所述空穴注入材料和空穴传输材料包括芳香族胺衍生物(例如NPB、SqMA1)、六氮杂苯并菲衍生物(例如HACTN)、吲哚并咔唑衍生物、导电聚合物(例如PEDOT/PSS),酞菁或卟啉衍生物、二苯并茚并芴胺、螺二芴胺中的至少一种,但不限于此。
以上所述空穴注入层和空穴传输层例如可采用如下通式的芳香族胺衍生物形成:
Figure BDA0003232426630000091
上述通式中的R1至R9的基团各自独立地选自单键、氢、氘、烷基、苯、二联苯、三联苯、萘、蒽、菲、苯并菲、芘、芴、二甲基芴、螺二芴、咔唑、噻吩、苯并噻吩、二苯并噻吩、呋喃、苯并呋喃、二苯并呋喃、吲哚、吲哚咔唑、茚并咔唑、吡啶、嘧啶、咪唑、噻唑、喹啉、异喹啉、喹喔啉、喹唑啉、卟啉、咔啉、吡嗪、哒嗪或三嗪。
电子阻挡层的形成材料不受特别限制,一般情况下,能够具备如下第1或/和第2个条件的化合物均可考虑采用:
第1:具备较高的LUMO能级,其目的就是减少离开发光层的电子数目,从而提高电子和空穴在发光层的复合几率。
第2:具备较大的三线态能量,其目的就是减少离开发光层的激子数量,从而提高激子转换发光的效率。
形成所述电子阻挡层的材料包括但不限于芳香族胺衍生物(例如NPB)、螺二芴胺(例如SpMA2),其中部分电子阻挡材料和空穴注入材料和空穴传输材料的结构类似。
发光层的发光材料是能够通过接收分别来自空穴传输层和电子传输层的空穴和电子并使空穴和电子结合而发出可见光区域内的光的材料,并且优选对荧光或磷光有良好的量子效率的材料。
发光层可以包含主体材料和掺杂剂材料。
所述的主体材料可以包括蒽类衍生物、咔唑类衍生物、芴类衍生物、芳胺类衍生物、有机硅类衍生物、咔唑-三嗪类衍生物、磷氧基类衍生物,但不限于此。
优选地,所述蒽类衍生物具有如下所示的通式:
Figure BDA0003232426630000111
优选地,所述磷氧基类衍生物具有如下所示的通式:
Figure BDA0003232426630000112
在前述蒽类衍生物和磷氧基类衍生物的通式中,R11、R12、R13、R14、R15和R16各自独立地选自单键、氢、氘、烷基、苯、二联苯、三联苯、四联苯、萘、苯基萘、蒽、菲、苯并菲、芘、芴、咔唑、噻吩、苯并噻吩、二苯并噻吩、呋喃、苯并呋喃、二苯并呋喃、吲哚、吲哚咔唑、茚并咔唑、吡啶、嘧啶、咪唑、噻唑、喹啉、异喹啉、喹喔啉、喹唑啉、卟啉、咔啉、吡嗪、哒嗪或三嗪,以及它们的取代物表示的基团。
客体材料优选为经由磷光、荧光、TADF(热激活延迟荧光)、MLCT(金属到配体电荷转移)、HLCT(具有杂化CT态)和三线态-三线态消灭方法中的至少一种方法产生发射的化合物。
发光层中的客体材料中可以包括苝的衍生物、蒽的衍生物、芴类衍生物、二苯乙烯基芳类衍生物、芳胺类衍生物、有机硅类衍生物、有机硼类衍生物、咔唑-三嗪类衍生物、吖啶类衍生物、含有酮类衍生物、砜基类衍生物、氰基衍生物和氧杂蒽类衍生物,但不限于此。
优选地,所述砜基类衍生物具有如下所示的通式:
Figure BDA0003232426630000113
优选地,所述酮类衍生物具有如下所示的通式:
Figure BDA0003232426630000121
在前述砜基类衍生物和酮类衍生物的通式中,R20、R21、R22和R23各自独立地选自单键、氢、氘、烷基、苯、二联苯、三联苯、四联苯、萘、苯基萘、蒽、菲、苯并菲、芘、芴、咔唑、噻吩、苯并噻吩、二苯并噻吩、呋喃、苯并呋喃、二苯并呋喃、吲哚、吲哚咔唑、茚并咔唑、吡啶、嘧啶、咪唑、噻唑、喹啉、异喹啉、喹喔啉、喹唑啉、卟啉、咔啉、吡嗪、哒嗪或三嗪,以及它们的取代物表示的基团。
空穴阻挡层的材料优选为具备如下第1和/或第2个条件的化合物:
第1:具备较高的HOMO能级,其目的就是减少离开发光层的空穴数目,从而提高电子和空穴在发光层的复合几率。
第2:具备较大的三线态能量,其目的就是减少离开发光层的激子数量,从而提高激子转换发光的效率。
形成所述空穴阻挡层的材料可以包括含有菲啰啉衍生物(例如Bphen,BCP),苯并菲衍生物,苯并咪唑衍生物,但不限于此。
电子传输层是接收来自电子注入层的电子并将电子传至发光层的层,并且作为电子传输材料,能够接收来自阴极的电子、使电子移动至发光层并对电子具有高迁移率的材料是合适的。电子传输材料中例如还可以包括8-羟基喹啉的Al配合物;包含Alq3的配合物;有机自由基化合物;羟基黄酮-金属配合物等,但不限于此。
电子注入层是注入来自电极的电子的层,并且电子注入材料优选为这样的化合物:其具有传输电子的能力,具有注入来自阴极的电子的效应,具有将电子注入发光层或发光材料的优异效应,防止发光层中产生的激子移动至空穴注入层,此外还具有优异的薄膜形成能力。电子注入层材料中例如还可以包括LiF、CsF、Cs2CO3、LiQ,但不限于此。
形成所述阴极材料通常优选具有小功函数的材料,可以使电子顺利注入有机材料层,能够在本公开内容中使用的阴极材料可以选自以下材料的一种或多种,Al、Mg和Ag中的一种或多种。
本发明至少具有如下具体的优点:
1、本发明的具有对称结构的化合物相较于现有技术中的化合物具有更高的折射率,改善阴极的光透过率,从而增加器件的发光效率及亮度。
2、本发明的化合物具有良好的热稳定性,不易形成结晶或发生相变,应用于有机电致发光器件时,能够增加器件的发光效率及使用寿命。
3、本发明的有机化合物具有良好的热分解温度,蒸镀时升高温度不易发生分解,能够提高生产产能。
4、本发明的化合物应用于有机电致发光器件时,在保证亮度的前提下可降低的电流密度和增加使用寿命。
以下将通过实例对本发明进行详细描述。以下实例中,在没有特别说明的情况下,使用的原料均为普通市售品。
在没有特别说明的情况下,下文所述的室温均表示25±1℃。
实施例1
Figure BDA0003232426630000131
化合物1的合成:将苯甲醛(0.12mol)和乙醇(130ml)配置为1号溶液。在1L三口瓶中,加入9,9-二甲基-9H-芴-2,7-二胺(0.12mol)和乙醇(270ml),搅拌均匀后加入乙酸(40ml),通入氮气5min后,加入1号溶液,加热搅拌,升温至85℃,反应5.5h后,HPLC检测原料反应完毕。将反应液降至室温过滤,得到粗品用乙醇和二氯甲烷冲洗,烘干,得到白色固体(收率:90.6%)。
质谱:C29H24N2,理论值:400.19,实测值:400.2。1H-NMR(400MHz,CDCl3)(ppm)δ=1.68~1.70(6H,s),7.48~7.49(1H,m),7.51~7.59(7H,m),7.70~7.71(2H,m),7.74~7.78(4H,m),7.88~7.92(2H,m),8.59~8.61(1H,s),8.66~8.67(1H,s)。
实施例2
Figure BDA0003232426630000141
中间体43-1的合成:在500ml三口瓶中,加入对溴苯甲醛(0.1mol),1-萘硼酸(0.1mol),异丙醇(150ml)和水(50ml)的混合溶液,无水碳酸钾(0.25mol)及双(三苯基膦)二氯化钯(1mmol),开始搅拌,加热至80℃回流反应4h。将反应降至室温分液,有机相加入饱和氯化钠水洗至中性,有机相过硅胶柱,洗脱剂为甲苯,用甲苯淋洗,过柱后的有机相用旋转蒸发仪蒸除溶剂得到白色固体(收率:82.6%)。
化合物43的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:89.7%)。
质谱:C49H36N2,理论值:652.29,实测值:652.3。1H-NMR(400MHz,CDCl3)(ppm)δ=1.68~1.70(6H,s),7.30~7.50(6H,m),7.64~7.69(6H,m),7.73~7.80(4H,m),7.87~7.96(8H,m),8.46~8.54(2H,m),8.59~8.61(1H,s),8.66~8.67(1H,s),8.93~8.97(2H,m)。
实施例3
Figure BDA0003232426630000151
化合物57的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:90.6%)。
质谱:C47H32N2,理论值:624.26,实测值:624.3。1H-NMR(400MHz,CDCl3)(ppm)δ=7.07~7.30(10H,m),7.47~7.61(6H,m),7.79~7.97(10H,m),8.45~8.49(2H,m),8.57~8.61(3H,m),8.65~8.67(1H,s)。
实施例4
Figure BDA0003232426630000152
化合物80的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:92.3%)。
质谱:C38H26N2O,理论值:526.20,实测值:526.2。1H-NMR(400MHz,CDCl3)(ppm)δ=7.36~7.55(10H,m),7.57~7.61(2H,m),7.64~7.70(4H,m),7.72~7.78(4H,m),7.89~7.95(4H,m),8.59~8.61(1H,s),8.65~8.67(1H,s)。
实施例5
Figure BDA0003232426630000153
化合物114的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:91.4%)。
质谱:C46H30N2O,理论值:626.24,实测值:626.2。1H-NMR(400MHz,CDCl3)(ppm)δ=7.32~7.42(4H,m),7.47~7.52(4H,m),7.66~7.69(4H,m),7.75~7.80(4H,m),7.87~7.94(6H,m),7.96~7.98(2H,m),8.48~8.52(2H,m),8.59~8.61(1H,s),8.65~8.67(1H,s),8.93~8.96(2H,m)。
实施例6
Figure BDA0003232426630000161
化合物136的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:88.3%)。
质谱:C26H18N2S,理论值:390.12,实测值:390.2。1H-NMR(400MHz,CDCl3)(ppm)δ=7.47~7.63(8H,m),7.72~7.81(6H,m),8.04~8.08(2H,m),8.59~8.61(1H,s),8.65~8.67(1H,s)。
实施例7
Figure BDA0003232426630000162
化合物173的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:89.7%)。
质谱:C38H22N2S3,理论值:602.09,实测值:602.1。1H-NMR(400MHz,CDCl3)(ppm)δ=7.27~7.35(2H,m),7.45~7.60(4H,m),7.67~7.72(2H,m),7.83~7.89(4H,m),8.08~8.13(2H,m),8.22~8.25(2H,m),8.42~8.48(4H,m),8.57~8.59(1H,s),8.65~8.67(1H,s)。
实施例8
Figure BDA0003232426630000171
中间体182-1的合成:合成方法同中间体43-1的合成方法相同,得到白色固体(收率:85.6%)。
化合物182的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:85.6%)。
实施例9
Figure BDA0003232426630000172
中间体189-1的合成:合成方法同中间体43-1的合成方法相同,得到白色固体(收率:86.3%)。
化合物189的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:91.6%)。
质谱:C52H35N3,理论值:701.28,实测值:701.3。1H-NMR(400MHz,CDCl3)(ppm)δ=6.95~7.00(1H,m),7.35~7.41(2H,m),7.46~7.53(2H,m),7.54~7.69(15H,m),7.80~7.83(1H,m),7.90~8.12(12H,m),8.59~8.61(1H,s),8.65~8.67(1H,s)。
实施例10
Figure BDA0003232426630000181
化合物217的合成:合成方法同化合物1的合成方法相同,得到白色固体(收率:92.5%)。
质谱:C32H23N3,理论值:449.19,实测值:449.2。1H-NMR(400MHz,CDCl3)(ppm)δ=7.03~7.08(1H,m),7.38~7.41(1H,m),7.48~7.66(13H,m),7.72~7.80(4H,m),8.21~8.25(1H,m),8.59~8.61(1H,s),8.65~8.67(1H,s),8.68~8.71(1H,m)。
制备有机发光器件
制备例1:
清洗透明OLED器件基板,分别用去离子水、丙酮、乙醇超声清洗各15分钟,然后在等离子体清洗器中处理2分钟。
将上述基板置于真空腔内,抽真空至1×10-4Pa,在基板上真空蒸镀Ag作为反射电极层,蒸镀速率为0.1nm/s,蒸镀总膜厚为100nm。
在反射电极层上蒸镀HAT-CN作为空穴注入层,蒸镀速率为0.1nm/s,蒸镀总膜厚为10nm;接着蒸镀HT-1作为空穴传输层,蒸镀速率为0.1nm/s,蒸镀总膜厚为80nm;接着蒸镀TCTA作为电子和激子阻挡层,蒸镀速率为0.1nm/s,蒸镀厚度为40nm。
在空穴层上真空蒸镀器件的发光层,发光层包括主体材料和客体材料,利用多源共蒸的方式,调节主体材料ADN蒸镀速率为0.1nm/s,设定客体BD蒸镀速率为主体材料的蒸镀速率的5%,蒸镀总膜厚为30nm;
在发光层上蒸镀TPBI作为空穴和激子阻挡层,蒸镀速率为0.1nm,厚度为5nm;然后蒸镀电子传输层,利用多源共蒸的方法,调节ET-2和ET-1的蒸镀速率均为0.1nm/s,蒸镀总膜厚为30nm。
在电子注入上蒸镀阴极材料,利用多源共蒸的方法,调节Mg蒸镀速率为0.1nm/s,设定Ag蒸镀速率为Mg的蒸镀速率的20%,蒸镀总膜厚为2nm;随后在其之上蒸镀Ag,蒸镀速率均为0.1nm/s,蒸镀总膜厚为15nm。
在阴极之上蒸镀化合物1作为覆盖层,蒸镀速率为0.1nm/s,蒸镀总膜厚为60nm,由此完成有机发光器件的制造。
Figure BDA0003232426630000191
Figure BDA0003232426630000201
制备例2~23
制备例2~23采用与制备例1相似的方法制备有机发光器件,所不同的是,将制备例1中的化合物1替换成表1中相应的化合物。
对比例1~11
对比例1~11采用与制备例1相似的方法制备有机发光器件,所不同的是,将制备例1中的化合物1替换成化合物M-1~M-11。
Figure BDA0003232426630000202
Figure BDA0003232426630000211
对比例12
对比例12采用与制备例1相似的方法制备有机发光器件,所不同的是,本对比例中,在阴极之上不蒸镀覆盖层。
测试例
在亮度1000cd/m2下,测定制备例和对比例中制备得到的有机电致发光器件的电流效率,结果见表1。
表1
Figure BDA0003232426630000212
Figure BDA0003232426630000221
由上述结果可知,本发明的有机化合物应用于有电致发光器件时能够使光取出率明显提高,在相同的亮度下,器件的发光效率得到了提高。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。

Claims (10)

1.一种具有对称结构的有机化合物,其特征在于,该化合物具有式(I)所示的结构;
Figure FDA0003232426620000011
其中,在式(I)中,
A为O、S、-C(CH3)2-、-C(Ph2)2-、-N(Ph)-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基、苯并菲基、
Figure FDA0003232426620000012
基、芘基、吡啶基、吡嗪基、三嗪基、异喹啉基、喹喔啉基。
2.根据权利要求1所述的化合物,其中,在式(I)中,
A为O、S、-C(CH3)2-、-C(Ph2)2-、-N(Ph)-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基。
3.根据权利要求2所述的化合物,其中,在式(I)中,
A为-C(CH3)2-或-C(Ph2)2-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基;
优选地,式(I)所示的化合物选自以下中的任意一种:
Figure FDA0003232426620000021
Figure FDA0003232426620000031
Figure FDA0003232426620000041
4.根据权利要求2所述的化合物,其中,在式(I)中,
A为O;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基;
优选地,式(I)所示的化合物选自以下中的任意一种:
Figure FDA0003232426620000051
Figure FDA0003232426620000061
Figure FDA0003232426620000071
5.根据权利要求2所述的化合物,其中,在式(I)中,
A为S;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基;
优选地,式(I)所示的化合物选自以下中的任意一种:
Figure FDA0003232426620000072
Figure FDA0003232426620000081
Figure FDA0003232426620000091
6.根据权利要求2所述的化合物,其中,在式(I)中,
A为-N(Ph)-;
L选自苯基、萘基;或者L不存在;
Ar选自苯基、萘基、9,9-二甲基-9H-芴基、二苯并呋喃基、二苯并噻吩基、9-苯基-9H-咔唑基、咔唑基、菲基、嘧啶基、苯基取代的三嗪基、甲基取代的嘧啶基、喹唑啉基、苯基取代的喹唑啉基、苯并[d]恶唑基、苯并[d]噻唑基、1,10-菲咯啉基、吡啶基取代的苯基、苯基取代的嘧啶基、1-苯基-1H-苯并[d]咪唑基、9,9-二苯基-9H-芴基、喹啉基;
优选地,式(I)所示的化合物选自以下中的任意一种:
Figure FDA0003232426620000101
Figure FDA0003232426620000111
Figure FDA0003232426620000121
7.根据权利要求1或2所述的化合物,其中,式(I)所示的化合物选自以下中的任意一种:
Figure FDA0003232426620000122
Figure FDA0003232426620000131
Figure FDA0003232426620000141
Figure FDA0003232426620000151
Figure FDA0003232426620000161
Figure FDA0003232426620000171
Figure FDA0003232426620000181
Figure FDA0003232426620000191
Figure FDA0003232426620000201
Figure FDA0003232426620000211
8.权利要求1-7中任意一项所述的化合物在有机电致发光器件中的应用。
9.一种含有权利要求1-7中任意一项所述的化合物中的一种或两种以上的化合物的有机电致发光器件,其特征在于,所述化合物存在于该有机电致发光器件的电子注入层、电子传输层和覆盖层的至少一层中;
优选地,所述化合物存在于该有机电致发光器件的阴极表面的覆盖层中;和/或
所述化合物存在于该有机电致发光器件的电子传输层中。
10.根据权利要求9所述的有机电致发光器件,其中,所述有机电致发光器件包括依次层叠设置的阳极、空穴注入层、空穴传输层、任选的电子阻挡层、发光层、任选的空穴阻挡层、电子传输层、电子注入层、阴极和覆盖层。
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