CN112479901B - 一种以茚并蒽衍生物为核心的有机化合物及其应用 - Google Patents

一种以茚并蒽衍生物为核心的有机化合物及其应用 Download PDF

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CN112479901B
CN112479901B CN201910860879.XA CN201910860879A CN112479901B CN 112479901 B CN112479901 B CN 112479901B CN 201910860879 A CN201910860879 A CN 201910860879A CN 112479901 B CN112479901 B CN 112479901B
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李崇
吴逸
王芳
赵四杰
张兆超
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Abstract

本发明涉及一种以茚并蒽衍生物为核心的有机化合物及其应用,属于半导体技术领域,本发明提供化合物的结构如通式(1)所示:
Figure DDA0002199719730000011
本发明提供的化合物具有较高的空穴迁移率,高的空穴传输速率能够降低器件的起始电压,提高有机电致发光器件的效率;因本发明化合物以茚并蒽衍生物为核心,搭配长支链结构,具有较强的刚性,分子间不易结晶,不易聚集,具有良好的成膜性的特点。因此本发明化合物作为OLED发光器件的发光功能层材料使用时,搭配本发明范围内的支链可有提升器件的使用寿命和效率。

Description

一种以茚并蒽衍生物为核心的有机化合物及其应用
技术领域
本发明涉及半导体技术领域,尤其涉及一种以茚并蒽衍生物为核心的有机化合物及其应用。
背景技术
有机电致发光(OLED:Organic Light Emission Diodes)器件技术既可以用来制造新型显示产品,也可以用于制作新型照明产品,有望替代现有的液晶显示和荧光灯照明,应用前景十分广泛。OLED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之间的有机功能材料,各种不同功能材料根据用途相互叠加在一起共同组成OLED发光器件。作为电流器件,当对OLED发光器件的两端电极施加电压,并通过电场作用有机层功能材料膜层中的正负电荷,正负电荷进一步在发光层中复合,即产生OLED电致发光。
当前,OLED显示技术已经在智能手机,平板电脑等领域获得应用,进一步还将向电视等大尺寸应用领域扩展,但是,和实际的产品应用要求相比,OLED器件的发光效率,使用寿命等性能还需要进一步提升。对于OLED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OLED器件的性能的不断提升,不但需要从OLED器件结构和制作工艺的创新,更需要OLED光电功能材料不断研究和创新,创制出更高性能OLED的功能材料。
应用于OLED器件的OLED光电功能材料从用途上可划分为两大类,即电荷注入传输材料和发光材料,进一步,还可将电荷注入传输材料分为电子注入传输材料、电子阻挡材料、空穴注入传输材料和空穴阻挡材料,还可以将发光材料分为主体发光材料和掺杂材料。
为了制作高性能的OLED发光器件,要求各种有机功能材料具备良好的光电特性,譬如,作为电荷传输材料,要求具有良好的载流子迁移率,高玻璃化转化温度等,作为发光层的主体材料要求材料具有良好双极性,适当的HOMO/LUMO能阶等。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构,产业上应用的OLED器件结构,则包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层等多种膜层,也就是说应用于OLED器件的光电功能材料至少包含空穴注入材料,空穴传输材料,发光材料,电子传输材料等,材料类型和搭配形式具有丰富性和多样性的特点。另外,对于不同结构的OLED器件搭配而言,所使用的光电功能材料具有较强的选择性,相同的材料在不同结构器件中的性能表现,也可能完全迥异。
因此,针对当前OLED器件的产业应用要求,以及OLED器件的不同功能膜层,器件的光电特性需求,必须选择更适合,具有高性能的OLED功能材料或材料组合,才能实现器件的高效率、长寿命和低电压的综合特性。就当前OLED显示照明产业的实际需求而言,目前OLED材料的发展还远远不够,落后于面板制造企业的要求,作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
针对现有技术存在的上述问题,本发明提供了一种以茚并蒽衍生物为核心的有机化合物及其在有机电致发光器件上的应用。本发明提供的有机化合物具有良好的热稳定性和较高的玻璃化温度,同时具有合适的HOMO能级,采用本发明提供的有机化合物的器件通过结构优化,可有效提升OLED器件的光电性能以及OLED器件的寿命。
具体技术方案如下:
一种以茚并蒽衍生物为核心的有机化合物,其特征在于,该化合物的结构如通式(1)所示:
Figure BDA0002199719710000021
通式(1)中,所示虚线表示虚线两端的基团通过单键连接或者不连接;
所述R2、R3分别独立的表示为氢原子、氕原子、氘原子、氚原子,甲氧基、C1-10烷基、C3-20的环烷基、取代或未取代的C6-30芳基、取代或未取代的含有一个或多个杂原子的5至30元杂芳基或通式(3)所示结构,且R2和R3至少有一个表示为通式(3)所示结构;
所述R1表示为氢原子或通式(2)所示结构;
Figure BDA0002199719710000022
所述通式(2)通过X1-X2、X2-X3或X3-X4标注的相邻位点与通式(1)并环连接;
所述通式(3)中,Ar1和Ar2分别独立的表示为取代或未取代的C6-30芳基、含有一个或多个杂原子的取代或未取代的5~30元杂芳基中的一种;
所述L1至L3分别独立的表示为单键、取代或未取代的C6-30亚芳基、含有一个或多个杂原子的取代或未取代的5~30元亚杂芳基;
所述可取代基团的取代基任选自氘原子、甲氧基、氰基、卤素原子、C1-20的烷基、C3-20的环烷基、C6-30芳基、含有一个或多个杂原子5至30元杂芳基中的一种或多种;
所述杂原子任选自氧原子、硫原子或氮原子中的一种或多种。
进一步改进,通式(1)所示结构,可表示为通式(1-1)至通式(1-6)所示结构中任一种:
Figure BDA0002199719710000023
进一步改进,所述L1至L3分别独立的表示为取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的亚二联苯基、取代或未取代的亚吡啶基、取代或未取代的亚咔唑基、取代或未取代的亚呋喃基、取代或未取代的亚嘧啶基、取代或未取代的亚吡嗪基、取代或未取代的亚哒嗪基、取代或未取代的亚二苯并呋喃基、取代或未取代的亚9,9-二甲基芴基、取代或未取代的亚N-苯基咔唑基、取代或未取代的亚喹啉基、取代或未取代的亚异喹啉基或者取代或未取代的亚萘啶基中的一种;
所述R2、R3分别独立的表示为氢原子、氕原子、氘原子、氚原子、卤素、氰基、甲基、乙基、丙基、异丙基、叔丁基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的蒽基、取代或未取代的吡啶基、取代或未取代的咔唑基、取代或未取代的呋喃基、取代或未取代的嘧啶基、取代或未取代的吡嗪基、取代或未取代的哒嗪基、取代或未取代的噻吩基、取代或未取代的二苯并呋喃基、取代或未取代的9,9-二甲基芴基、取代或未取代的N-苯基咔唑基、取代或未取代的喹啉基、取代或未取代的异喹啉基、取代或未取代的萘啶基、取代或未取代的恶唑基、取代或未取代的咪唑基、取代或未取代的苯并恶唑基或者取代或未取代的苯并咪唑基或通式(3)所示结构,且R2和R3至少有一个表示为通式(3)所示结构;
所述Ar1至Ar2分别独立的表示为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的蒽基、取代或未取代的吡啶基、取代或未取代的咔唑基、取代或未取代的呋喃基、取代或未取代的嘧啶基、取代或未取代的吡嗪基、取代或未取代的哒嗪基、取代或未取代的噻吩基、取代或未取代的二苯并呋喃基、取代或未取代的9,9-二甲基芴基、取代或未取代的N-苯基咔唑基、取代或未取代的喹啉基、取代或未取代的异喹啉基、取代或未取代的萘啶基、取代或未取代的恶唑基、取代或未取代的咪唑基、取代或未取代的苯并恶唑基或者取代或未取代的苯并咪唑基中的一种;
所述可取代基团的取代基任选自氘原子、氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、戊基、苯基、萘基、联苯基、吡啶基、苯并呋喃基、咔唑基、苯并噻吩基或呋喃基中的一种或多种。
进一步改进,所述R2表示为氢原子或叔丁基,所述R3表示为通式(3)所示结构。
进一步改进,所述R2表示为氢原子或叔丁基,所述R3表示为通式(3)所示结构,所述通式(2)通过X2-X3与通式(1)并环连接。
进一步改进,所述R2表示为氢原子或叔丁基,所述R2表示为通式(3)所示结构,所述R3表示为氢原子。
进一步改进,所述以茚并蒽衍生物为核心的有机化合物的具体结构式为以下结构中的任一种:
Figure BDA0002199719710000031
Figure BDA0002199719710000041
Figure BDA0002199719710000051
Figure BDA0002199719710000061
Figure BDA0002199719710000071
Figure BDA0002199719710000081
Figure BDA0002199719710000091
Figure BDA0002199719710000101
Figure BDA0002199719710000111
Figure BDA0002199719710000121
本发明的第二个方面是提供上述以茚并蒽衍生物为核心的有机化合物在制备有机电致发光器件中的应用。
本发明的第三个方面是提供一种有机电致发光器件,具有这样的特征,上述有机电致发光器件包括至少一层功能层,上述功能层含有上述以茚并蒽衍生物为核心的有机化合物。
本发明的第四个方面是提供一种有机电致发光器件,包括空穴传输层,具有这样的特征,上述空穴传输层含有上述以茚并蒽衍生物为核心的有机化合物。
本发明的第五个方面是提供一种有机电致发光器件,包括电子阻挡层,具有这样的特征,上述电子阻挡层含有上述以茚并蒽衍生物为核心的有机化合物。
本发明的第六个方面是提供一种有机电致发光器件,包括空穴传输层和电子阻挡层,具有这样的特征,上述空穴传输层和电子阻挡层含有上述以茚并蒽衍生物为核心的有机化合物。
本发明的第七个方面是提供一种照明或显示元件,具有这样的特征,包括上述的有机电致发光器件。
上述方案的有益效果是:
本发明提供的化合物以茚并蒽衍生物为母核,具有较强的空穴迁移率,高的空穴传输速率能够降低器件的起始电压,提高有机电致发光器件的效率;连接长支链,具有很强的刚性,具有分子间不易结晶,不易聚集的特点,具有较高的膜层稳定性;同时,本发明提供的化合物具有较适中分子量,具有更高的玻璃化转变温度,适宜的分解温度,通过对母核和支链进行不同的搭配,可对蒸镀温度进行调控,具有更宽的可加工窗口。
本发明化合物在恰当的HOMO能级下,提升了空穴注入和传输性能;在合适的LUMO能级下,又起到了电子阻挡的作用,提升激子在发光层中的复合效率。
本发明的化合物在OLED器件应用时,通过器件结构优化,可保持高的膜层稳定性,可有效提升OLED器件的光电性能以及OLED器件的寿命。本发明化合物在OLED发光器件中具有良好的应用效果和产业化前景。
附图说明
图1为本发明所列举的材料应用于OLED器件的结构示意图;
附图中:1为透明基板层,2为ITO阳极层,3为空穴注入层,4为空穴传输,5为电子阻挡层,6为发光层,7为电子传输或空穴阻挡层,8为电子注入层,9为阴极反射电极层。
具体实施方式
下面将结合本发明实施例中的附图,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作出创造性劳动的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。
需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。下面结合附图和具体实施例对本发明作进一步说明,但不作为本发明的限定。
实施例1:中间体B的合成:
Figure BDA0002199719710000131
T2和T3分别表示为溴原子或氢原子,且T2和T3中至少一个表示为溴原子。
(1)250毫升三口瓶中,加入0.045mol镁屑,5毫升干燥的四氢呋喃,加入3mmol二溴乙烷引发反应后,保持回流下滴加0.04mol原料A的15毫升四氢呋喃溶液,加毕接着回流30分钟,降至室温,倾出清液备用。
(2)另一500毫升三口瓶,氮气保护下,加入0.05mol原料B,20毫升干燥的甲苯,0.2mmol的1,3-双二苯基膦丙烷氯化镍,控制温度30℃滴加上步制备的清液,加毕于30℃接着搅拌5小时,停止反应,加入氯化铵溶液水解,有机层水洗后硅胶柱层析分离,石油醚∶正己烷体积比=1∶1洗脱,洗脱液浓缩得到中间体A。
(3)500毫升三口瓶中,加入0.03mol中间体A,30毫升干燥的四氢呋喃,氮气保护下降温至-78℃,缓慢滴加5ml丁基锂的正己烷溶液(2.4mol/L),加毕于-78℃保温反应30分钟,再缓慢滴入0.04mol原料C,缓慢升至25℃反应2小时,停止,加入氯化铵水溶液水解,有机层硫酸钠干燥后,浓缩至干,再加入20毫升二氯甲烷溶解,将此二氯甲烷溶液转移至250毫升三口瓶,氮气下于0℃向其中缓慢滴加0.02mol甲烷磺酸,加毕在25℃下反应1小时,加水分液,有机层硅胶柱层析分离,石油醚洗脱,洗脱液浓缩得到产物中间体B。
此类以中间体B1的合成为例:
Figure BDA0002199719710000141
(1)250毫升三口瓶中,加入0.045mol镁屑,5毫升干燥的四氢呋喃,加入3mmol二溴乙烷引发反应后,保持回流下滴加0.04mol原料A的15毫升四氢呋喃溶液,加毕接着回流30分钟,降至室温,倾出清液备用。
(2)另一500毫升三口瓶,氮气保护下,加入0.05mol原料B-1,20毫升干燥的甲苯,0.2mmol的1,3-双二苯基膦丙烷氯化镍,控制温度30℃滴加上步制备的清液,加毕于30℃接着搅拌5小时,停止反应,加入氯化铵溶液水解,有机层水洗后硅胶柱层析分离,石油醚∶正己烷体积比=1∶1洗脱,洗脱液浓缩得到中间体A-1,HPLC纯度99.2%,收率75.4%。
元素分析结构(分子式C18H11Br):理论值C,70.38;H,3.61;Br,26.01;测试值:C,70.36;H,3.67;Br,26.03。ESI-MS(m/z)(M+):理论值为306.00,实测值为306.07。
(3)500毫升三口瓶中,加入0.03mol中间体A-1,30毫升干燥的四氢呋喃,氮气保护下降温至-78℃,缓慢滴加5ml丁基锂的正己烷溶液(2.4mol/L),加毕于-78℃保温反应30分钟,再缓慢滴入0.04mol原料C-1,缓慢升至25℃反应2小时,停止,加入氯化铵水溶液水解,有机层硫酸钠干燥后,浓缩至干,再加入20毫升二氯甲烷溶解,将此二氯甲烷溶液转移至250毫升三口瓶,氮气下于0℃向其中缓慢滴加0.02mol甲烷磺酸,加毕在25℃下反应1小时,加水分液,有机层硅胶柱层析分离,石油醚洗脱,洗脱液浓缩得到产物中间体B1,HPLC纯度99.2%,收率45.4%。
元素分析结构(分子式C31H17Br):理论值C,79.33;H,3.65;Br,17.02;测试值:C,79.36;H,3.67;Br,17.04。ESI-MS(m/z)(M+):理论值为468.05,实测值为468.07。
实施例中所需的中间体B的合成参考中间体B1的合成,合成原料如表1:
表1
Figure BDA0002199719710000142
Figure BDA0002199719710000151
实施例2化合物1的合成
Figure BDA0002199719710000161
在250ml的三口瓶中,通氮气保护下,加入0.01mol中间体B1,0.012mol原料D1,150ml甲苯搅拌混合,然后加入5×10-5molPd2(dba)3,5×10-5mol P(t-Bu)3,0.03mol叔丁醇钠,加热至105℃,回流反应24小时,取样点板,显示无溴代物剩余,反应完全;自然冷却至室温,过滤,滤液旋蒸至无馏分,过中性硅胶柱,得到目标产物,HPLC纯度99.34%,收率72.4%。元素分析结构(分子式C58H39N):理论值:C,92.89;H,5.24;N,1.87;测试值C,92.87;H,5.25;N,1.83。ESI-MS(m/z)(M+):理论值为749.31,实测值为749.35。
1H NMR(500MHz,Chloroform-d)δ8.32(t,2H),8.16–8.03(m,1H),7.92–7.79(m,2H),7.76(dt,1H),7.65(d,1H),7.62–7.53(m,1H),7.53–7.26(m,20H),7.26–7.09(m,3H),7.00–6.73(m,2H),1.56(d,6H).
实施例3化合物2的合成
Figure BDA0002199719710000162
按实施例2中化合物1的合成方法制备,不同点在于用原料D2代替原料D1;元素分析结构(分子式C64H43N):理论值:C,93.06;H,5.25;N,1.70;测试值C,93.04;H,5.27N,1.72。ESI-MS(m/z)(M+):理论值为825.34,实测值为825.36。
1H NMR(500MHz,Chloroform-d)δ8.34(t,2H),8.19–7.97(m,1H),7.91–7.79(m,2H),7.76(ddd,2H),7.74–7.68(m,1H),7.64(d,1H),7.60–7.51(m,4H),7.51–7.26(m,18H),7.26–7.13(m,4H),6.95–6.77(m,2H),1.57(d,6H).
实施例4化合物3的合成
Figure BDA0002199719710000163
按实施例2中化合物1的合成方法制备,不同点在于用原料D3代替原料D1;元素分析结构(分子式C64H43N):理论值:C,93.06;H,5.25;N,1.70;测试值C,93.05;H,5.23;N,1.76。ESI-MS(m/z)(M+):理论值为825.34,实测值为825.38。
1H NMR(500MHz,Chloroform-d)δ8.34(t,2H),8.19–8.00(m,1H),7.91–7.80(m,3H),7.76(dt,1H),7.64(d,1H),7.62–7.52(m,4H),7.52–7.24(m,19H),7.24–7.08(m,4H),6.93–6.76(m,2H),1.56(d,6H).
实施例5化合物4的合成
Figure BDA0002199719710000171
按实施例2中化合物1的合成方法制备,不同点在于用原料D4代替原料D1;元素分析结构(分子式C61H38N2):理论值:C,91.70;H,4.79;N,3.51;测试值C,91.75;H,4.72;N,3.56。ESI-MS(m/z)(M+):理论值为798.30,实测值为798.33。
1H NMR(500MHz,Chloroform-d)δ8.32(d,2H),8.19–8.02(m,2H),7.89(d,1H),7.87–7.78(m,2H),7.76(dt,1H),7.65(d,1H),7.63–7.54(m,2H),7.54–7.46(m,3H),7.46–7.22(m,20H),7.22–7.15(m,1H),6.96(dd,1H),6.93(d,1H),6.87(dd,1H).
实施例6化合物45的合成
Figure BDA0002199719710000172
按实施例2中化合物1的合成方法制备,不同点在于用原料D5代替原料D1;用中间体B2代替中间体B1;元素分析结构(分子式C65H40N2):理论值:C,91.95;H,4.75;N,3.30;测试值C,91.94;H,4.77;N,3.33。ESI-MS(m/z)(M+):理论值为848.32,实测值为848.36。
1H NMR(500MHz,Chloroform-d)δ8.34(d,2H),8.08–7.98(m,1H),7.89(dt,1H),7.88–7.81(m,3H),7.81–7.73(m,3H),7.64(d,1H),7.62–7.54(m,3H),7.54–7.24(m,21H),7.22(dd,1H),7.21–7.15(m,1H),7.10(dd,1H),6.87(dd,2H).
实施例7化合物46的合成
Figure BDA0002199719710000173
按实施例2中化合物1的合成方法制备,不同点在于用原料D6代替原料D1;用中间体B2代替中间体B1;元素分析结构(分子式C65H40N2):理论值:C,91.95;H,4.75;N,3.30;测试值C,91.94H,4.75;N,3.31。ESI-MS(m/z)(M+):理论值为848.32,实测值为848.12。
1H NMR(500MHz,Chloroform-d)δ8.34(t,2H),8.19–8.01(m,2H),7.89(dt,1H),7.87–7.81(m,3H),7.81–7.73(m,2H),7.64(d,1H),7.63–7.58(m,2H),7.58–7.53(m,1H),7.53–7.45(m,3H),7.45–7.13(m,21H),6.97–6.80(m,2H).
实施例8化合物47的合成
Figure BDA0002199719710000181
按实施例2中化合物1的合成方法制备,不同点在于用原料D7代替原料D1;用中间体B2代替中间体B1;元素分析结构(分子式C65H40N2):理论值:C,91.95;H,4.75;N,3.30;测试值C,91.97;H,4.74;N,3.34。ESI-MS(m/z)(M+):理论值为848.32,实测值为848.37。
1H NMR(500MHz,Chloroform-d)δ8.34(t,2H),8.18–8.03(m,2H),7.89(dt,1H),7.88–7.81(m,3H),7.81–7.72(m,2H),7.64(d,1H),7.60(dd,2H),7.58–7.53(m,1H),7.50(d,1H),7.47–7.21(m,19H),7.21–7.12(m,3H),7.05(dt,1H),6.97–6.80(m,2H).
实施例9化合物48的合成
Figure BDA0002199719710000182
按实施例2中化合物1的合成方法制备,不同点在于用原料D8代替原料D1;用中间体B2代替中间体B1;元素分析结构(分子式C71H44N2):理论值:C,92.18;H,4.79;N,3.03;测试值C,92.16;H,4.74;N,3.07。ESI-MS(m/z)(M+):理论值为924.35,实测值为924.38。
1H NMR(500MHz,Chloroform-d)δ8.34(d,2H),8.22–8.06(m,1H),7.89(dt,1H),7.88–7.81(m,4H),7.81–7.73(m,2H),7.71–7.62(m,3H),7.62–7.52(m,6H),7.50(d,1H),7.47–7.21(m,20H),7.21–7.14(m,1H),6.93(dd,1H),6.90(d,1H),6.87(dd,1H).
实施例10化合物89的合成
Figure BDA0002199719710000183
按实施例2中化合物1的合成方法制备,不同点在于用原料D9代替原料D1;用中间体B3代替中间体B1;元素分析结构(分子式C71H44N2):理论值:C,92.18;H,4.79;N,3.03;测试值C,92.15;H,4.77;N,3.07。ESI-MS(m/z)(M+):理论值为924.35,实测值为924.36。
1H NMR(500MHz,Chloroform-d)δ8.34(d,2H),8.09(d,1H),8.08–8.01(m,1H),7.99(d,1H),7.90(dt,1H),7.87–7.72(m,6H),7.69–7.62(m,3H),7.62–7.14(m,26H),7.10(dd,1H),6.87(dd,2H).
实施例11化合物90的合成
Figure BDA0002199719710000191
按实施例2中化合物1的合成方法制备,不同点在于用原料D10代替原料D1;用中间体B3代替中间体B1;元素分析结构(分子式C69H42N2):理论值:C,92.18;H,4.71;N,3.12;测试值C,92.15;H,4.75;N,3.13。ESI-MS(m/z)(M+):理论值为898.33,实测值为898.36。
1H NMR(500MHz,Chloroform-d)δ8.34(t,2H),8.09(d,1H),8.04(dd,1H),7.99(d,1H),7.97–7.79(m,8H),7.76(dt,1H),7.64(d,1H),7.62–7.10(m,25H),6.87(dd,2H).
实施例12化合物91的合成
Figure BDA0002199719710000192
按实施例2中化合物1的合成方法制备,不同点在于用原料D11代替原料D1;用中间体B3代替中间体B1;元素分析结构(分子式C59H35NO):理论值:C,91.56;H,4.56;N,1.81;O,2.07;测试值C,91.53;H,4.56;N,1.83。ESI-MS(m/z)(M+):理论值为773.27,实测值为773.25。
1H NMR(500MHz,Chloroform-d)δ8.32(d,2H),8.10(d,1H),7.99(dd,1H),7.95(d,1H),7.90(dt,1H),7.88–7.79(m,5H),7.76(dt,1H),7.65(d,1H),7.60–7.25(m,16H),7.24(dd,1H),7.21–7.14(m,1H),7.06(d,1H),6.95(d,1H),6.93–6.81(m,2H).
实施例13化合物92的合成
Figure BDA0002199719710000193
按实施例2中化合物1的合成方法制备,不同点在于用原料D12代替原料D1;用中间体B3代替中间体B1;元素分析结构(分子式C59H35NO):理论值:C,91.56;H,4.56;N,1.81;O,2.07;测试值C,91.57;H,4.53;N,1.85。ESI-MS(m/z)(M+):理论值为773.27,实测值为773.25。
1H NMR(500MHz,Chloroform-d)δ8.40–8.27(m,2H),8.10(d,1H),8.02(dd,1H),7.95(d,1H),7.90(dt,1H),7.88–7.79(m,4H),7.76(dt,1H),7.65(d,1H),7.62–7.40(m,8H),7.40–7.25(m,10H),7.25–7.16(m,2H),7.13(dd,1H),6.93–6.75(m,2H).
实施例14化合物133的合成
Figure BDA0002199719710000201
按实施例2中化合物1的合成方法制备,不同点在于用原料D13代替原料D1;用中间体B4代替中间体B1;元素分析结构(分子式C59H35NO):理论值:C,91.56;H,4.56;N,1.81;O,2.07;测试值C,91.54;H,4.58;N,1.83。ESI-MS(m/z)(M+):理论值为773.27,实测值为773.26。
1H NMR(500MHz,Chloroform-d)δ8.38–8.27(m,3H),8.02(dd,1H),7.98–7.90(m,1H),7.90–7.81(m,3H),7.78(dq,2H),7.72(dd,1H),7.66(d,1H),7.58(dd,1H),7.52(td,1H),7.44(tdd,4H),7.41–7.26(m,12H),7.23(dd,1H),7.21–7.14(m,2H),6.91(dd,1H),6.74(d,1H).
实施例15化合物134的合成
Figure BDA0002199719710000202
按实施例2中化合物1的合成方法制备,不同点在于用原料D14代替原料D1;用中间体B4代替中间体B1;元素分析结构(分子式C65H39NO):理论值:C,91.85;H,4.62;N,1.65;O,1.88;测试值C,91.88;H,4.64;N,1.68。ESI-MS(m/z)(M+):理论值为849.30,实测值为849.37。
1H NMR(500MHz,Chloroform-d)δ8.42–8.27(m,3H),8.00(dd,1H),7.89(dt,1H),7.84(ddt,3H),7.81–7.71(m,2H),7.64(d,1H),7.61–7.25(m,22H),7.22(dd,1H),7.20–7.15(m,3H),6.91(dd,2H).
实施例16化合物135的合成
Figure BDA0002199719710000203
按实施例2中化合物1的合成方法制备,不同点在于用原料D15代替原料D1;用中间体B4代替中间体B1;元素分析结构(分子式C65H39NO):理论值:C,91.85;H,4.62;N,1.65;O,1.88;测试值C,91.87;H,4.64;N,1.67。ESI-MS(m/z)(M+):理论值为849.30,实测值为849.34。
1H NMR(500MHz,Chloroform-d)δ8.42–8.27(m,3H),8.02(ddd,2H),7.89(dt,1H),7.87–7.80(m,3H),7.80–7.72(m,2H),7.64(d,1H),7.61–7.54(m,4H),7.52(td,17H),7.25–7.13(m,4H),6.91(dd,2H).
实施例17化合物136的合成
Figure BDA0002199719710000211
按实施例2中化合物1的合成方法制备,不同点在于用原料D16代替原料D1;用中间体B4代替中间体B1;元素分析结构(分子式C63H39N):理论值:C,93.42;H,4.85;N,1.73;测试值C,93.46;H,4.87;N,1.76。ESI-MS(m/z)(M+):理论值为809.31,实测值为809.35。
1H NMR(500MHz,Chloroform-d)δ8.42–8.24(m,3H),8.04–7.92(m,2H),7.92–7.80(m,4H),7.78(q,1H),7.77(q,1H),7.72–7.61(m,2H),7.61–7.48(m,7H),7.48–7.26(m,13H),7.26–7.11(m,4H),7.03–6.84(m,2H).
实施例18化合物265的合成
Figure BDA0002199719710000212
按实施例2中化合物1的合成方法制备,不同点在于用原料D17代替原料D1;用中间体B5代替中间体B1;元素分析结构(分子式C55H35N3S):理论值:C,85.80;H,4.58;N,5.46;S,4.16;测试值C,85.85;H,4.53;N,5.45;S,4.13。ESI-MS(m/z)(M+):理论值为769.26,实测值为769.25。
1H NMR(500MHz,Chloroform-d)δ8.62(d,1H),8.32(d,2H),8.08(dd,1H),7.91(ddd,2H),7.89–7.83(m,1H),7.81(dt,1H),7.76(dt,1H),7.59–7.38(m,7H),7.38–7.24(m,11H),7.24–7.17(m,2H),7.17–7.10(m,2H),7.08(dt,1H),7.03(t,1H),6.96(dt,1H),6.88(dd,1H).
实施例19化合物266的合成
Figure BDA0002199719710000213
按实施例2中化合物1的合成方法制备,不同点在于用原料D18代替原料D1;用中间体B5代替中间体B1;元素分析结构(分子式C53H35N):理论值:C,92.81;H,5.14;N,2.04;测试值C,92.85;H,5.16;N,2.03。ESI-MS(m/z)(M+):理论值为685.28,实测值为685.24。
1H NMR(500MHz,Chloroform-d)δ8.42–8.25(m,2H),8.09(dd,1H),7.92–7.75(m,4H),7.73(dd,1H),7.62–7.53(m,1H),7.52–7.36(m,6H),7.36–7.17(m,15H),7.17–7.08(m,2H),7.05(dt,1H),7.02–6.86(m,2H).
实施例20化合物267的合成
Figure BDA0002199719710000221
按实施例2中化合物1的合成方法制备,不同点在于用原料D19代替原料D1;用中间体B5代替中间体B1;元素分析结构(分子式C64H45N):理论值:C,92.83;H,5.48;N,1.69;测试值C,92.86;H,5.44;N,1.66。ESI-MS(m/z)(M+):理论值为827.36,实测值为827.34。
1H NMR(500MHz,Chloroform-d)δ8.34(t,2H),8.08(dd,1H),7.94–7.84(m,1H),7.82(dt,1H),7.76(dt,1H),7.64–7.51(m,4H),7.51–7.36(m,8H),7.36–7.20(m,13H),7.20–7.16(m,3H),7.16–7.09(m,2H),7.03(dt,1H),6.99–6.90(m,2H),1.56(d,6H).
实施例21化合物268的合成
Figure BDA0002199719710000222
按实施例2中化合物1的合成方法制备,不同点在于用原料D20代替原料D1;用中间体B5代替中间体B1;元素分析结构(分子式C63H41N3):理论值:C,90.08;H,4.92;N,5.00;测试值C,90.03;H,4.96;N,5.04。ESI-MS(m/z)(M+):理论值为839.33,实测值为839.36。
1H NMR(500MHz,Chloroform-d)δ8.41–8.33(m,3H),8.31(s,1H),8.28(s,1H),8.08(dd,1H),7.82(dt,1H),7.76(dt,1H),7.65–7.57(m,4H),7.57–7.50(m,1H),7.50–7.14(m,25H),7.14–7.07(m,2H),6.92(dt,1H).
实施例22化合物332的合成
Figure BDA0002199719710000223
按实施例2中化合物1的合成方法制备,不同点在于用原料D21代替原料D1;用中间体B9代替中间体B1;元素分析结构(分子式C61H40TN):理论值:C,92.74;H,5.49;N,1.77;测试值C,92.76;H,5.45;N,1.74。ESI-MS(m/z)(M+):理论值为789.33,实测值为789.32。
1H NMR(500MHz,Chloroform-d)δ8.32(s,2H),8.09(dd,1H),7.99–7.79(m,3H),7.70–7.53(m,8H),7.49(dd,1H),7.47–7.41(m,4H),7.41–7.22(m,12H),7.22–7.10(m,5H),7.10–7.03(m,2H),7.03–6.94(m,2H).
实施例23化合物333的合成
Figure BDA0002199719710000231
按实施例2中化合物1的合成方法制备,不同点在于用原料D22代替原料D1;用中间体B10代替中间体B1;元素分析结构(分子式C62H40BrN):理论值:C,84.73;H,4.59;Br,9.09;N,1.59;测试值C,84.77;H,4.54;Br,9.05;N,1.57。ESI-MS(m/z)(M+):理论值为877.23,实测值为877.24。
1H NMR(500MHz,Chloroform-d)δ8.34(t,2H),8.08–7.80(m,3H),7.80–7.74(m,2H),7.72(dd,1H),7.63(t,2H),7.60–7.53(m,2H),7.53–7.27(m,16H),7.24(ddd,2H),7.21–7.15(m,1H),6.97(d,1H),6.91(d,1H),6.53(dd,1H),1.56(d,6H).
实施例19化合物341的合成
Figure BDA0002199719710000232
按实施例2中化合物1的合成方法制备,不同点在于用原料D18代替原料D1;用中间体B6代替中间体B1;元素分析结构(分子式C57H37N):理论值:C,93.03;H,5.07;N,1.90;测试值C,93.04;H,5.01N,1.94。ESI-MS(m/z)(M+):理论值为735.29,实测值为735.23。
1H NMR(500MHz,Chloroform-d)δ8.32(d,2H),7.93–7.66(m,8H),7.64–7.52(m,1H),7.50–7.24(m,19H),7.24–7.16(m,2H),7.16–7.08(m,2H),7.06(dt,1H),6.96(dd,2H).
实施例20化合物342的合成
Figure BDA0002199719710000233
按实施例2中化合物1的合成方法制备,不同点在于用原料D19代替原料D1;用中间体B7代替中间体B1;元素分析结构(分子式C68H47N):理论值:C,93.01;H,5.40;N,1.60;测试值C,93.02;H,5.43;N,1.61。ESI-MS(m/z)(M+):理论值为877.37,实测值为877.33。
1H NMR(500MHz,Chloroform-d)δ8.34(t,2H),8.09(d,1H),8.02–7.95(m,1H),7.90(ddd,1H),7.87–7.83(m,2H),7.81(ddd,1H),7.76(dt,1H),7.64–7.36(m,13H),7.36–7.16(m,14H),7.16–7.09(m,2H),7.04(dt,1H),6.96(t,1H),6.92(dt,1H),1.56(d,6H).
实施例21化合物343的合成
Figure BDA0002199719710000241
按实施例2中化合物1的合成方法制备,不同点在于用原料D20代替原料D1;用中间体B8代替中间体B1;元素分析结构(分子式C67H43N3):理论值:C,90.41;H,4.87;N,4.72;测试值C,90.44;H,4.85;N,4.73。ESI-MS(m/z)(M+):理论值为889.35,实测值为889.37。
1H NMR(500MHz,Chloroform-d)δ8.41–8.30(m,5H),8.28(s,1H),7.90(dt,1H),7.85(dt,1H),7.78(ddd,2H),7.66–7.57(m,4H),7.57–7.48(m,2H),7.48–7.15(m,24H),7.15–7.08(m,2H),6.98(dt,1H).
本发明化合物在发光器件中使用,可以作为电子阻挡层材料或空穴传输层材料使用。对本发明上述实施例制备的化合物分别进行热性能、T1能级、HOMO能级的测试,检测结果如表2所示:
表2
Figure BDA0002199719710000242
注:三线态能级T1是由Horiba的Fluorolog-3系列荧光光谱仪测试,材料的测试条件为2*10-5mol/L的甲苯溶液;玻璃化转变温度Tg由示差扫描量热法(DSC,德国耐驰公司DSC204F1示差扫描量热仪)测定,升温速率10℃/min;热失重温度Td是在氮气气氛中失重1%的温度,在日本岛津公司的TGA-50H热重分析仪上进行测定,氮气流量为20mL/min;最高占据分子轨道HOMO能级是由电离能量测试系统(IPS-3)测试,测试为大气环境。
由上表数据可知,本发明的有机化合物具有较为合适的HOMO能级,可应用于空穴传输层或电子阻挡层,本发明的有机化合物具有较高的热稳定性,使得所制作的含有本发明有机化合物的OLED器件效率和寿命均得到提升。
以下通过器件实施例1-30和比较例1详细说明本发明合成的OLED材料在器件中的应用效果。本发明器件实施例2-30和器件比较例1与实施例1相比器件的制作工艺完全相同,并且所采用了相同的基板材料和电极材料,电极材料的膜厚也保持一致,所不同的是对器件中的空穴注入层材料、空穴传输层材料或电子阻挡层材料做了更换。各实施例所得器件的性能测试结果如表4所示。
器件实施例1
具体制备过程如下:
如图1所示,透明基板层1,对ITO阳极层2(膜厚为150nm)进行洗涤,即依次进行碱洗涤、纯水洗涤、干燥,再进行紫外线-臭氧洗涤以清除透明ITO表面的有机残留物。在进行了上述洗涤之后的ITO阳极层2上,利用真空蒸镀装置,蒸镀膜厚为10nm的化合物1和P-1作为空穴注入层3,化合物1和P-1的质量比为98:2。接着蒸镀55nm厚度的化合物1作为空穴传输层4。随后蒸镀10nm厚度的EB-1作为电子阻挡层5。上述电子阻挡材料蒸镀结束后,制作OLED发光器件的发光层6,其结构包括OLED发光层6所使用BH作为主体材料,BD作为掺杂材料,掺杂材料掺杂比例为3%重量比,发光层膜厚为20nm。在上述发光层6之后,继续真空蒸镀ET-1和Liq,ET-1和Liq质量比为1:1,膜厚为35nm,此层为空穴阻挡/电子传输层7。在空穴阻挡/电子传输层7上,通过真空蒸镀装置,制作膜厚为1nm的Yb层,此层为电子注入层8。在电子注入层8上,通过真空蒸镀装置,制作膜厚为80nm的Mg:Ag电极层,Mg、Ag质量比为1:9,此层为阴极层9。
相关材料的分子结构式如下所示:
Figure BDA0002199719710000251
表3
Figure BDA0002199719710000261
Figure BDA0002199719710000271
Figure BDA0002199719710000281
所得电致发光器件的检测数据见表4所示。
表4
Figure BDA0002199719710000282
Figure BDA0002199719710000291
注:电压、电流效率和色坐标是使用IVL(电流-电压-亮度)测试系统(苏州弗士达科学仪器有限公司)测试的,测试时的电流密度为10mA/cm2;寿命测试系统为日本系统技研公司EAS-62C型OLED器件寿命测试仪;LT95指的是在特定亮度(蓝光:1000nits)下,器件亮度衰减到95%所用时间。
由表4的结果可以看出本发明有机化合物可应用于OLED发光器件制作,并且与比较例相比,无论是效率还是寿命均比已知OLED材料获得较大改观,特别是器件的使用寿命获得较大的提升。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (10)

1.一种以茚并蒽衍生物为核心的有机化合物,其特征在于,该有机化合物的结构如通式(1)所示:
Figure FDA0004072732240000011
通式(1)中,所示虚线表示虚线两端的基团通过单键连接或者不连接;
所述R2、R3分别独立的表示为氢原子、氘原子、氚原子或通式(3)所示结构,且R2和R3至少有一个表示为通式(3)所示结构;
所述R1表示为氢原子或通式(2)所示结构;
Figure FDA0004072732240000012
所述通式(2)通过X2-X3或X3-X4标注的相邻位点与通式(1)并环连接;
所述通式(3)中,Ar1和Ar2分别独立的表示为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的蒽基、取代或未取代的吡啶基、取代或未取代的咔唑基、取代或未取代的呋喃基、取代或未取代的嘧啶基、取代或未取代的吡嗪基、取代或未取代的哒嗪基、取代或未取代的噻吩基、取代或未取代的二苯并呋喃基、取代或未取代的9,9-二甲基芴基、取代或未取代的N-苯基咔唑基、取代或未取代的喹啉基、取代或未取代的异喹啉基、取代或未取代的萘啶基、取代或未取代的恶唑基、取代或未取代的咪唑基、取代或未取代的苯并恶唑基或者取代或未取代的苯并咪唑基中的一种;
所述L1至L3分别独立的表示为单键、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的亚二联苯基、取代或未取代的亚吡啶基、取代或未取代的亚嘧啶基、取代或未取代的亚吡嗪基、取代或未取代的亚哒嗪基、取代或未取代的亚异喹啉基或者取代或未取代的亚萘啶基;
所述可取代基团的取代基任选自氘原子、甲氧基、氰基、氟原子、甲基、乙基、丙基、异丙基、叔丁基、戊基、苯基、萘基、联苯基、吡啶基、苯并呋喃基、咔唑基、苯并噻吩基或呋喃基中的一种或多种。
2.根据权利要求1所述的有机化合物,其特征在于,通式(1)所示结构,可表示为通式(1-1)、通式(1-3)、通式(1-4)、通式(1-5)、通式(1-7)或通式(1-8)所示结构中任一种:
Figure FDA0004072732240000013
Figure FDA0004072732240000021
3.根据权利要求1所述的有机化合物,其特征在于,所述R2表示为氢原子,所述R3表示为通式(3)所示结构。
4.根据权利要求1所述的有机化合物,其特征在于,所述R2表示为氢原子,所述R3表示为通式(3)所示结构,所述通式(2)通过X2-X3与通式(1)并环连接。
5.根据权利要求1所述的有机化合物,其特征在于,所述R2表示为氢原子,所述R3表示为通式(3)所示结构,所述R1表示为氢原子。
6.根据权利要求1所述的有机化合物,其特征在于,所述有机化合物的具体结构式为以下结构中的任一种:
Figure FDA0004072732240000022
Figure FDA0004072732240000031
Figure FDA0004072732240000041
Figure FDA0004072732240000051
Figure FDA0004072732240000061
Figure FDA0004072732240000071
Figure FDA0004072732240000081
Figure FDA0004072732240000091
Figure FDA0004072732240000101
Figure FDA0004072732240000111
7.一种以茚并蒽衍生物为核心的有机化合物,其特征在于,所述有机化合物的具体结构式为以下结构中的任一种:
Figure FDA0004072732240000112
8.一种有机电致发光器件,其特征在于,所述有机电致发光器件至少一层功能层含有权利要求1-7任一项所述的以茚并蒽衍生物为核心的有机化合物。
9.一种有机电致发光器件,其特征在于,包括电子阻挡层或空穴传输层,所述电子阻挡层或空穴传输层材料含有权利要求1-7任一项所述的以茚并蒽衍生物为核心的有机化合物。
10.一种照明或显示元件,其特征在于,包括权利要求8或9任一项所述的有机电致发光器件。
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