CN113105440B - 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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CN113105440B
CN113105440B CN202110405830.2A CN202110405830A CN113105440B CN 113105440 B CN113105440 B CN 113105440B CN 202110405830 A CN202110405830 A CN 202110405830A CN 113105440 B CN113105440 B CN 113105440B
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CN113105440A (zh
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王辉
李小龙
李明
李建行
段伟伟
刘志远
马晓宇
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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及其制备方法和应用，属于有机光电材料领域，所述有机电致发光化合物的分子结构通式由式1表示：
Figure DDA0003022284460000011
其中，所述式Ⅰ中：X与Y各自独立地选自连接键、O或S；Ar1‑Ar2位于所在环的任意位置，独立地选自氢、氘、卤素、氰基、胺基、取代或未取代的C1‑C30的烷基、取代或未取代的C2‑C30杂环基胺基、取代或未取代的C3‑C30的环烷基胺基、取代或未取代的3元‑30元的杂环基、取代或未取代的C6‑C30芳基；取代或未取代的4元‑30元芳族杂环基、取代或未取代的C6‑C30芳基氨基；取代或未取代的C3‑C30杂芳基氨基、取代或未取代的C10‑C30的稠环基；相同分子中的两个或更多个取代基Ar1和Ar2可以具有不同含义。本发明得到的有机电致发光化合物应用于有机电致发光器件。

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
本发明属于有机光电材料领域，更具体的说是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
有机发光二极管(OLED)利用了材料在受到电流激发时的发光性能。作为阴极射线管和液晶显示器的替代品以生产平面可视显示单元，OLED尤其受到关注。包含OLED的器件由于非常紧密的构造和固有的低能耗，他们特别适用于移动应用，例如用于移动电话、笔记本电脑、照明等，由于具有自发射、响应快、亮度高、柔性可卷曲等优点，有机电致发光器件已在新一代大面积平板显示器和半导体固体照明光源领域中备受瞩目。
OLED属于注入型发光器件，其基本结构是将有机薄膜层夹在两个电极间形成的夹层式结构，有机薄膜由空穴注入层、空穴传输层、发光层、电子传输层和电子注入层组成。空穴传输层(HTL)负责调节空穴的注入速度和注入量，电子传输层(ETL)负责调节电子的注入速度和注入量。
但现阶段的空穴传输层、激子阻挡层或具备空穴传输层又具备激子阻挡层还存在迁移率不够快、能级和能量搭配不好、空穴的传输效率不高及不能很好的阻挡激子等问题，从而导致有机电致发光器件的起动电压高、效率低和器件寿命短等现象。
因此，结合上述问题，提供一种性能优良的高效有机电致发光化合物，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制备方法和应用，本发明提供的新型结构的有有机电致发光化合物，通过选择特定的杂环的配体结合，得到的有机电致发光化合物在用于有机电致发光器件后，降低了器件的启动电压，且提高了器件的发光效率和寿命。
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，其分子结构通式由式1表示：
Figure BDA0003022284450000021
其中，所述式Ⅰ中：X与Y各自独立地选自连接键、O或S；
Ar1-Ar2位于所在环的任意位置，独立地选自氢、氘、卤素、氰基、胺基、取代或未取代的C1-C30的烷基、取代或未取代的C2-C30杂环基胺基、取代或未取代的C3-C30的环烷基胺基、取代或未取代的3元-30元的杂环基、取代或未取代的C6-C30芳基；取代或未取代的4元-30元芳族杂环基、取代或未取代的C6-C30芳基氨基；取代或未取代的C3-C30杂芳基氨基、取代或未取代的C10-C30的稠环基。
优选的，所述的杂环基中的杂原子选自氧O、氮N、硫S；Ar2能与其所在的环构成芳环、芳杂环或环体系；所述m和n为整数，0≤m≤6，0≤n≤4。
优选的，所述取代所用取代基选自氘、卤素基团、腈基、羟基、羰基、酯基、甲硅烷基、硼基、经取代或未经取代的烷基、经取代或未经取代的环烷基、经取代或未经取代的烷氧基、经取代或未经取代的烯基、经取代或未经取代的烷基胺基、经取代或未经取代的杂环基胺基、经取代或未经取代的芳基胺基、经取代或未经取代的芳基和经取代或未经取代的杂环基。
一种有机电致发光化合物的制备方法，制备式Ⅰ化合物包括以下步骤：
1)Ar1为芳胺类时，其合成通式为：
Figure BDA0003022284450000022
在氮气保护下，将式Ⅱ(1)化合物、式Ⅲ(1)化合物、甲苯和叔丁醇钠混合均匀后，依次加入三(二亚苄基丙酮)二钯和50％三叔丁基膦，在110℃下回流24h，反应完成，冷却反应溶液的温度至室温，经层析、浓缩、淋洗、烘干后，得到终产品式Ⅰ(1)；
2)Ar1不为芳胺类时，其合成通式为：
Figure BDA0003022284450000031
在氮气保护下，将式Ⅱ(2)化合物、式Ⅲ(2)化合物、甲苯、无水乙醇、水和无水碳酸钾混合均匀后，加入四三苯基膦钯，在100℃下回流24h，反应完成，冷却反应溶液的温度至室温，经层析、浓缩、淋洗、烘干后，得到终产品式Ⅰ(2)；
3)Ar1同时包括为芳胺类和芳基时，其合成通式为：
Figure BDA0003022284450000032
在氮气保护下，将式Ⅱ(3)化合物、式Ⅲ(3)化合物、甲苯和叔丁醇钠混合均匀后，依次加入三(二亚苄基丙酮)二钯和50％三叔丁基膦，在110℃下回流24h，反应完成，冷却反应溶液的温度至室温，经层析、浓缩、淋洗、烘干后，得到中间体式Ⅳ；
在氮气保护下，将式Ⅳ化合物、式Ⅴ化合物、甲苯、无水乙醇、水和无水碳酸钾混合均匀后，加入四三苯基膦钯，在100℃下回流24h，反应完成，冷却反应溶液的温度至室温，经层析、浓缩、淋洗、烘干后，得到终产品式Ⅰ(3)。
优选的，所述上述式Ⅱ(1)、式Ⅱ(2)、式Ⅱ(3)、式Ⅲ(1)、式Ⅲ(2)、式Ⅲ(3)、式Ⅳ、式Ⅴ中，L选自F、Cl、Br、I中的一种或多种；上述反应步骤数为一步或多步反应，其反应步骤数与m数一致；其中P和Q分别为0、1、2、3、4、5或6，且P+Q＝m。
优选的，所述相同分子中的两个或更多个取代基Ar1和Ar2可以具有不同含义。
优选的，所述A环的结构优选如下：
Figure BDA0003022284450000041
Figure BDA0003022284450000051
优选的，其中，X1和X2为连接位置，(Ar1)m与式Ⅰ结构限定一致。
优选的，所述上述基团或取代基团的氢原子可被氘代。
优选的，所述有机电致发光化合物的具体结构式还可以表示为式Ⅰ-1至式Ⅰ-128：
Figure BDA0003022284450000061
Figure BDA0003022284450000071
Figure BDA0003022284450000081
Figure BDA0003022284450000091
Figure BDA0003022284450000101
Figure BDA0003022284450000111
Figure BDA0003022284450000121
Figure BDA0003022284450000131
Figure BDA0003022284450000141
Figure BDA0003022284450000151
Figure BDA0003022284450000161
Figure BDA0003022284450000171
Figure BDA0003022284450000181
Figure BDA0003022284450000191
Figure BDA0003022284450000201
Figure BDA0003022284450000211
一种有机电致发光化合物在有机电致发光器件中的应用，所述有机电致发光器件包括第一电极、第二电极、有机物层，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采用分子结构通式由式1表示的化合物组成。
优选的，所述有机物层设置在所述第一电极和所述第二电极之间，所述有机物层的层数≥1。
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：本发明通过选择特定的杂环组合，得到的有机电致发光化合物在用于有机电致发光器件后，可以提高空穴的传输效率，很好地阻挡了激子，使能级搭配契合，使器件中空穴和电子达到了均衡，从而可以使得降低器件的起动电压以及提高器件的发光效率和寿命，适于推广与应用。
具体实施方式
下面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
本发明实施例1公开了一种有机电致发光化合物及其制备方法，制备式Ⅰ-7，采用的技术方案如下：
Figure BDA0003022284450000221
在氮气保护体系下，称取式Ⅱ-7(20mmol,5.51g),式Ⅲ-7(20mmo1,6.06g)，碳酸钾(60mmol,6.48g)放入反应体系中,加入110mL甲苯,55mL无水乙醇，55mL纯净水，氮气保护下加入催化剂Pd(PPh3)4(0.40mmol,0.46g)回流24小时,然后冷却到25℃，将有机相过200g硅胶的硅胶漏斗，将有机相滤液旋至无液体流出，加入100ml二氯甲烷溶解，将溶液柱层析(200～300目，400g)，展开剂DCM:PE＝2:1，将接收液旋至无液体流出，加入石油醚搅拌20min，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，得到类白色粉末的中间体7(5.45g，产率为60％),其HPLC纯度大于99％。
在氮气保护体系下，称取中间体7(12mmol,5.44g),式Ⅳ-7(14mmo1,3.53g)，无水碳酸钾(36mmol,3.88g)放入反应体系中,加入110ml甲苯,55mL无水乙醇，55mL纯净水，氮气保护下加入Pd(PPh3)4(0.24mmol,0.28g)，氮气保护下100℃回流24h，然后冷却到25℃，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，将产品用150ml甲苯，加热到110℃溶解，降至25℃析出，抽滤，滤饼用石油醚淋洗，50℃真空烘干，得到所示化合物式Ⅰ-7(5.56g,产率为74％),其HPLC纯度大于99.5％。
质谱:计算值为625.72；测试值为625.24。
元素分析:计算值C:82.54；H:4.99；N:2.24；O:10.23.测试值为C:82.52；H:4.97；N:2.27；O:10.24。
核磁数据：1HNMR(500MHz,DMSO-d6)δ8.50(dd,J＝7.4,1.5Hz,1H),8.41(d,J＝1.4Hz,1H),8.12(dd,J＝7.1,1.8Hz,1H),8.00–7.95(m,1H),7.83(ddt,J＝13.5,7.4,1.6Hz,2H),7.70(d,J＝1.7Hz,1H),7.58–7.53(m,1H),7.53–7.36(m,8H),7.34(d,J＝7.5Hz,1H),7.28(t,J＝7.5Hz,1H),7.18(dd,J＝7.5,1.5Hz,1H),6.94(s,3H),6.98–6.90(m,1H),6.28(t,J＝7.5Hz,1H),6.19(dd,J＝7.5,1.5Hz,1H),4.87–4.79(m,2H),4.68(d,J＝7.0Hz,1H),4.46(d,J＝7.0Hz,1H),3.52–3.45(m,1H),3.34–3.26(m,1H)。
热失重(TG)：514.2℃。
实施例2
本发明实施例2公开了一种有机电致发光化合物及其制备方法，制备式Ⅰ-35，采用的技术方案如下：
Figure BDA0003022284450000241
在氮气保护体系下，称取式Ⅱ-35(20mmol,7.03g),式Ⅲ-35(24mmo1,3.82g)，叔丁醇钠(60mmol,5.76g)放入反应体系中,加入140ml甲苯，氮气保护下催化剂Pd2(dba)3(0.6mmol,0.55g)和P(t-Bu)3(1.2mmol，0.24g)，氮气保护下110℃回流24h，然后冷却到25℃，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，将产品用150ml甲苯，加热到110℃溶解，降至25℃析出，抽滤，滤饼用石油醚淋洗，50℃真空烘干，得到所示化合物式Ⅰ-35(6.02g,产率为70％),其HPLC纯度大于99.5％。
质谱:计算值为429.58；测试值为429.46。
元素分析:计算值C:83.88；H:5.40；N:3.26；S:7.46.测试值为C:83.89；H:5.42；N:3.24；S:7.45。
核磁数据：1H NMR(500MHz,DMSO-d6)δ8.63(tt,J＝1.6,0.7Hz,1H),8.40(t,J＝1.4Hz,1H),8.09(dd,J＝6.4,1.7Hz,2H),7.96–7.89(m,2H),7.56(td,J＝7.5,1.7Hz,1H),7.50(td,J＝7.5,1.6Hz,1H),7.24(dd,J＝10.8,6.2Hz,1H),6.50(dtd,J＝10.8,7.0,1.3Hz,1H),6.31(ddt,J＝10.7,6.0,0.9Hz,1H),6.15–6.06(m,2H),6.03–5.95(m,2H),5.85(dtdd,J＝11.0,7.0,1.8,0.9Hz,1H),4.60–4.51(m,1H),3.75(dd,J＝21.0,6.1Hz,1H),3.68(dd,J＝21.1,6.2Hz,1H),3.43(ddd,J＝20.9,7.0,1.0Hz,1H),3.31(ddd,J＝21.1,7.0,1.1Hz,1H),2.30(tdd,J＝7.0,2.7,1.0Hz,2H)。
热失重(TG)：518.1℃。
实施例3
本发明实施例3公开了一种有机电致发光化合物及其制备方法，制备式Ⅰ-70，采用的技术方案如下：
Figure BDA0003022284450000251
在氮气保护体系下，称取式Ⅱ-70(20mmol,6.39g),式Ⅲ-70(20mmo1,4.26g)，叔丁醇钠(60mmol,5.76g)放入反应体系中,加入130mL甲苯,氮气保护下加入催化剂Pd2(dba)3(0.6mmol,0.55g)和P(t-Bu)3(1.2mmol，0.24g)回流24小时,然后冷却到25℃，将有机相过200g硅胶的硅胶漏斗，将有机相滤液旋至无液体流出，加入100ml二氯甲烷溶解，将溶液柱层析(200～300目，400g)展开剂DCM:PE＝1:1，将接收液旋至无液体流出，加入石油醚搅拌20min，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，得到类白色粉末的中间体70(5.78g，产率为64％),其HPLC纯度大于99％。
在氮气保护体系下，称取中间体70(12mmol,5.42g),式Ⅳ-70(14mmo1,4.94g)，无水碳酸钾(36mmol,3.89g)放入反应体系中,加入110ml甲苯，55mL无水乙醇，55mL纯净水，氮气保护下加入Pd(PPh3)4(0.24mmol,0.28g)，氮气保护下100℃回流24h，然后冷却到25℃，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，将产品用150ml甲苯，加热到110℃溶解，降至25℃析出，抽滤，滤饼用石油醚淋洗，50℃真空烘干，得到所示化合物式Ⅰ-70(4.18g,产率为48％),其HPLC纯度大于99.5％。
质谱:计算值为724.96；测试值为724.63。
元素分析:计算值C:81.18；H:6.12；N:3.86；O:4.41；S:4.42.测试值为C:81.19；H:6.13；N:3.87；O:4.40；S:4.40。
核磁数据：1H NMR(500MHz,DMSO-d6)δ9.02(d,J＝1.4Hz,1H),8.78(d,J＝7.5Hz,1H),8.09–8.04(m,1H),8.00–7.94(m,1H),7.79(d,J＝7.5Hz,1H),7.63–7.57(m,2H),7.57–7.51(m,1H),7.50–7.40(m,2H),7.33(ddd,J＝12.6,7.3,1.4Hz,3H),7.32–7.26(m,1H),7.17(dd,J＝7.5,1.5Hz,1H),7.07(td,J＝7.5,1.6Hz,1H),7.03(dd,J＝7.5,1.6Hz,1H),6.89(dt,J＝7.5,1.0Hz,1H),6.61(q,J＝1.1Hz,1H),6.44(dd,J＝7.5,1.5Hz,1H),5.73(qd,J＝4.2,2.5Hz,2H),4.44(t,J＝7.0Hz,1H),4.20(d,J＝7.1Hz,1H),3.93–3.83(m,1H),3.63(qt,J＝7.0,3.5Hz,2H),2.81–2.68(m,7H),2.33–2.24(m,2H),2.08–1.94(m,2H),1.86(td,J＝7.0,2.7Hz,2H),1.79–1.67(m,4H)。
热失重(TG)：511.8℃。
实施例4
本发明实施例4公开了一种有机电致发光化合物及其制备方法，制备式Ⅰ-73，采用的技术方案如下：
Figure BDA0003022284450000261
氮气保护体系下，称取式Ⅱ-73(20mmol,5.46g),式Ⅲ-73(50mmo1,16.07g)，叔丁醇钠(60mmol,5.76g)放入反应体系中,加入110ml甲苯，氮气保护下催化剂Pd2(dba)3(0.6mmol,0.55g)和P(t-Bu)3(1.2mmol，0.24g)，氮气保护下110℃回流24h，然后冷却到25℃，将有机相过200g硅胶的硅胶漏斗，将有机相滤液旋至无液体流出，加入100ml二氯甲烷溶解，将溶液柱层析(200～300目，400g)展开剂DCM:PE＝3:1，将接收液旋至无液体流出，加入石油醚搅拌20min，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，得到所示化合物式Ⅰ-73(9.36g,产率为58％),其HPLC纯度大于99.5％。
质谱:计算值为807.01；测试值为807.34。
元素分析:计算值C:89.30；H:5.25；N:3.47；O:1.98.测试值为C:89.32；H:5.26；N:3.44；O:1.98。
核磁数据：1H-NMR(500MHz,DMSO-d6):δ8.01–7.97(m,1H),7.69–7.63(m,8H),7.61–7.54(m,9H),7.48–7.32(m,14H),7.22–7.14(m,9H),6.52(d,J＝1.4Hz,1H)。
热失重(TG)：519.7℃。
实施例5
本发明实施例5公开了一种有机电致发光化合物及其制备方法，制备式Ⅰ-76，采用的技术方案如下：
Figure BDA0003022284450000271
在氮气保护体系下，称取式Ⅱ-76(20mmol,6.63g),式Ⅲ-76(20mmo1,3.38g)，叔丁醇钠(60mmol,5.76g)放入反应体系中,加入130mL甲苯,氮气保护下加入催化剂Pd2(dba)3(0.6mmol,0.55g)和P(t-Bu)3(1.2mmol，0.24g)回流24小时,然后冷却到25℃，将有机相过200g硅胶的硅胶漏斗，将有机相滤液旋至无液体流出，加入100ml二氯甲烷溶解，将溶液柱层析(200～300目，400g)展开剂DCM:PE＝1:1，将接收液旋至无液体流出，加入石油醚搅拌
20min，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，得到类白色粉末的中间体76(5.62g，产率为67％),其HPLC纯度大于99％。
在氮气保护体系下，称取中间体76(13mmol,6.63g)，式Ⅳ-76(15.6mmo1,6.55g)，叔丁醇钠(39mmol,3.75g)放入反应体系中,加入130mL甲苯,氮气保护下加入催化剂Pd2(dba)3(0.39mmol,0.37g)和P(t-Bu)3(0.78mmol，0.16g)回流24小时,然后冷却到25℃，将有机相过200g硅胶的硅胶漏斗，将有机相滤液旋至无液体流出，加入100ml二氯甲烷溶解，将溶液柱层析(200～300目，400g)展开剂DCM:PE＝1:1，将接收液旋至无液体流出，加入石油醚搅拌20min，抽滤，滤饼用石油醚淋洗，将滤饼真空烘干，得到所示化合物式Ⅰ-76(6.35g，产率为72％),其HPLC纯度大于99％。
质谱:计算值为678.84；测试值为678.32。
元素分析:计算值C:88.47；H:5.05；N:4.13；O:2.36.测试值为C:88.49；H:5.08；N:4.10；O:2.34。
核磁数据：1H NMR(500MHz,DMSO-d6)δ8.02(dt,J＝7.4,1.8Hz,1H),7.95–7.87(m,2H),7.85–7.76(m,3H),7.66–7.55(m,3H),7.57–7.51(m,3H),7.47(dddd,J＝10.5,9.0,7.3,1.7Hz,3H),7.45–7.36(m,3H),7.39–7.33(m,3H),7.33–7.24(m,7H),7.17(ddd,J＝6.6,2.3,1.5Hz,1H),7.09(ddt,J＝14.1,7.3,1.4Hz,7H),6.78(d,J＝1.7Hz,1H).
热失重(TG)：513.2℃。
其他化合物的合成方法与上述相同，其合成实施例质谱或分子式如下表1所示：
表1
Figure BDA0003022284450000281
Figure BDA0003022284450000291
利用本发明实施例提供的有机电致发光化合物，制备出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。
为了更进一步的描述本发明，以下列举更具体的实施例。
实施例16
本发明实施例16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：
(1)将涂层厚度为
Figure BDA0003022284450000292
的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30min，用蒸馏水反复清洗2次，超声波洗涤10min，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5min，接着，将ITO衬底安装在真空气相沉积设备的衬底夹持器上。将HI001引入到所述真空气相沉积设备的单元中，并且随后将所述设备的腔室中的压力控制为10-7托，此后，向所述单元施加电流以蒸发上述引入的材料，由此在ITO衬底上形成厚度为
Figure BDA0003022284450000293
的第一空穴注入层。接着，将HAT-CN引入所述真空气相沉积设备的另一单元中，且通过向所述单元施加电流蒸发，由此在第一空穴注入层上形成厚度为
Figure BDA0003022284450000294
的第二空穴注入层。接着，将如下的化合物HT001引入到真空气相沉积设备的另一单元中，且通过向所述单元施加电流蒸发，由此在第二空穴注入层上形成厚度为
Figure BDA0003022284450000295
的第一空穴传输层。接着，将化合物式Ⅰ-3引入到真空气相沉积设备的另一单元中，且通过向所述单元施加电流蒸发，由此在第一空穴传输层上形成厚度为
Figure BDA0003022284450000296
的第二空穴传输层。此后，将化合物RH001引入到真空气相沉积设备的一个单元中作为主体，并且将化合Ir(piq)2acac中的一种引入到另一个单元中作为掺杂剂。两种材料以不同速率蒸发且以按主体和掺杂剂的总量计重量3％的掺杂量沉积以在第二空穴传输层上形成厚度为
Figure BDA0003022284450000301
的发光层。随后，将ET001引入到一个单元中，并且Liq引入到另一单元中。使两种材料以相同速率蒸发，并且各自以50重量％的掺杂量沉积，以在发光层上形成厚度为
Figure BDA0003022284450000302
的电子输送层。随后，将Liq在电子传输层上沉积成厚度为
Figure BDA0003022284450000303
的电子注入层之后，通过另一个真空气相沉积设备在电子注入层上沉积厚度为
Figure BDA0003022284450000304
的Al阴极。由此，即可得到有机电致发光器件。用于制造OLED装置的所有材料在使用之前都通过在10-4托下真空升华而纯化。
其中，第一空穴注入层化合物HI001和第二空穴注入层化合物HAT-CN结构式为：
Figure BDA0003022284450000305
其中，第一空穴传输层化合物HT001结构式为；
Figure BDA0003022284450000306
其中，主体物质化合物RH001和掺杂物质化合物Ir(piq)2acac的结构式为：
Figure BDA0003022284450000311
其中，电子传输层ET001和电子传输层和电子注入层Liq的化合物结构式为：
Figure BDA0003022284450000312
参照上述实施例16提供的方法，分别选用化学结构式为式I-7、I-11、I-31、I-35、I-45、I-56、I-60、I-70、I-73、I-76、I-80、I-96、I-98、I-126的有机电致发光化合物替代结构式为式I-3的有机发光材料进行蒸镀，并制备得到相应的有机电致发光器件，记为实施例17～30。
对比例1
该对比例提供了一种有机电致发光器件，该有机电致发光器件的制备方法与实施例16的唯一区别在于，该有机电致发光器件是采用现有的有机化合物HT002替代式I-3进行蒸镀。
其中HT002化合物的结构式为：
Figure BDA0003022284450000321
将上述实施例16-30和对比例1得到的有机电致发光器件分别采用KEITHLEY2400型源测量单元和PR670分光辐射亮度计及寿命测试仪测试其驱动电压、发光效率以及T95寿命等性能，其测试结果如下表2所示。
表2实施例13～24和对比例1测试结果
Figure BDA0003022284450000322
表2可以看出，使用本发明提供有机电致发光化合物做的有机电致发光器件与使用比较化合物对比例1做的有机电致发光器件相比，驱动电压明显降低，电流效率和寿命得到显著提高。
本领域的技术人员将明显看到，在不脱离本发明的精神和范围下，本发明可以有许多修改和变化。因此可以预期到，本发明覆盖在附带权利要求的范围及其相当范围内提供的本发明修改和变化。
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 (4)

1.一种有机电致发光化合物，其特征在于，其分子结构通式由式1表示：
Figure FDA0003802064510000011
其中，所述式Ⅰ中：X与Y各自独立地选自O或S；
所述式I的结构如下：
Figure FDA0003802064510000012
Figure FDA0003802064510000021
Figure FDA0003802064510000031
2.一种权利要求1所述的有机电致发光化合物的制备方法，其特征在于，制备式Ⅰ化合物包括以下步骤：
1)Ar1为芳胺类时，其合成通式为：
Figure FDA0003802064510000041
在氮气保护下，将式Ⅱ(1)化合物、式Ⅲ(1)化合物、甲苯和叔丁醇钠混合均匀后，依次加入三(二亚苄基丙酮)二钯和50％三叔丁基膦，在110℃下回流24h，反应完成，冷却反应溶液的温度至室温，经层析、浓缩、淋洗、烘干后，得到终产品式Ⅰ(1)；
2)Ar1不为芳胺类时，其合成通式为：
Figure FDA0003802064510000042
在氮气保护下，将式Ⅱ(2)化合物、式Ⅲ(2)化合物、甲苯、无水乙醇、水和无水碳酸钾混合均匀后，加入四三苯基膦钯，在100℃下回流24h，反应完成，冷却反应溶液的温度至室温，经层析、浓缩、淋洗、烘干后，得到终产品式Ⅰ(2)；
3)Ar1同时包括为芳胺类和芳基时，其合成通式为：
Figure FDA0003802064510000043
在氮气保护下，将式Ⅱ(3)化合物、式Ⅲ(3)化合物、甲苯和叔丁醇钠混合均匀后，依次加入三(二亚苄基丙酮)二钯和50％三叔丁基膦，在110℃下回流24h，反应完成，冷却反应溶液的温度至室温，经层析、浓缩、淋洗、烘干后，得到中间体式Ⅳ；
在氮气保护下，将式Ⅳ化合物、式Ⅴ化合物、甲苯、无水乙醇、水和无水碳酸钾混合均匀后，加入四三苯基膦钯，在100℃下回流24h，反应完成，冷却反应溶液的温度至室温，经层析、浓缩、淋洗、烘干后，得到终产品式Ⅰ(3)；
所述上述式Ⅱ(1)、式Ⅱ(2)、式Ⅱ(3)、式Ⅲ(1)、式Ⅲ(2)、式Ⅲ(3)、式Ⅳ、式Ⅴ中，L选自F、Cl、Br、I中的一种或多种；上述反应步骤数为一步或多步反应，其反应步骤数与m数一致；其中P和Q分别为0、1、2、3、4、5或6，且P+Q＝m。
3.一种权利要求1所述的有机电致发光化合物在有机电致发光器件中的应用，其特征在于，所述有机电致发光器件包括第一电极、第二电极、有机物层，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采用分子结构通式由式1表示的化合物组成。
4.根据权利要求3所述的一种有机电致发光化合物在有机电致发光器件中的应用，其特征在于，所述有机物层设置在所述第一电极和所述第二电极之间，所述有机物层的层数≥1。
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