CN108586289B - 丙二腈取代的芳基蒽菲类有机电致发光材料及其制备方法和应用 - Google Patents

丙二腈取代的芳基蒽菲类有机电致发光材料及其制备方法和应用 Download PDF

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CN108586289B
CN108586289B CN201810418858.8A CN201810418858A CN108586289B CN 108586289 B CN108586289 B CN 108586289B CN 201810418858 A CN201810418858 A CN 201810418858A CN 108586289 B CN108586289 B CN 108586289B
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malononitrile
organic electroluminescent
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substituted aryl
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CN108586289A (zh
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王会
罗添友
栾新军
林智双
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Xi'an Oder Photoelectricity Material Co ltd
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Northwestern University
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Abstract

本发明公开了一种丙二腈取代的芳基蒽菲类有机电致发光材料及其制备方法和应用，上述有机电致发光材料以丙二腈取代的芳基蒽菲为母核，其结构式如式（I）所示。本发明提供的丙二腈取代的芳基蒽菲类有机电致发光材料制备工艺简单，HOMO和LUMO能级电子云可有效分离，单线态‑三线态能隙(ΔEST)小，三线态激子可以通过反向系间窜跃(RIST)转变成单线态激子发光，具有热激活延迟荧光性质；将本发明提供的丙二腈取代的芳基蒽菲类发光材料应用于OLED发光器件中得到了高的器件效率。

Description

丙二腈取代的芳基蒽菲类有机电致发光材料及其制备方法和 应用
技术领域
本发明涉及一种丙二腈取代芳基蒽菲类有机电致发光材料及其制备方法和应用，属于有机电致发光材料技术领域。
背景技术
1987年，美国柯达公司的C.W.Tang等人首次报道了利用真空蒸镀法制备的双层有机小分子薄膜器件，该器件的亮度大于1000 cd/m2，操作电压低于10 V。该发现是OLED领域的一项突破性进展，使人们看到了OLED技术走向商业化市场的无限潜力。有机电致发光是指有机材料在电流或电场的激发作用下发光的现象，通常将利用有机小分子或高分子作为电致发光材料制成的器件称为有机电致发光器件，简称OLED。OLED相比传统的无机电致发光器件而言，具有材料可选范围宽、可实现全彩显示、驱动电压低(3-10 V)、发光亮度和发光效率高、视角宽、响应速度快(~1μs)、可实现柔性显示等诸多优点。在过去的近30年时间里，为进一步加快OLED技术的可行化和实用化，企业和学术界在开发新型的OLED材料和优化器件结构两方面做出了很大努力，也取得了一些进展。特别是一些3G产品如手机、数码相机出现以来OLED产品的商业优势日益突显出来，越来越多的OLED平板显示、大面积柔性显示以及高效率白光的成功研制，进一步证实了有机电致发光器件在下一代显示和照明领域的主流地位。
根据自旋统计估算，在电激发条件下，空穴和电子结合形成25％的单线态激子和75％的三线态激子。对传统荧光染料而言，由于它只能利用单线态激子，因而制备的有机电致发光器件(OLEDs)的最大内量子效率仅为25％；而基于贵金属配合物的磷光染料通过利用重原子效应，提高了分子自旋。轨道耦合，能充分利单线态和三线态激子，制得的有机电致磷光器件(PHOLEDs)可以实现100％的内量子效率。然而，由于磷光染料大多含贵金属如Ir、Pt或Os等，成本较高，开发它们的替代物引起人们的越来越多的关注。其中，基于有机小分子的热激活延迟荧光(TADF)材料有望替代贵金属配合物。该类材料一般具有小的单线态-三线态能级差(△EST)，三线态激子可以通过反系间窜越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子，器件的内量子效率可以达到100％。同时，材料结构可控，性质稳定，价格便宜无需贵重金属，在OLEDs领域的应用前景广阔。
虽然理论上TADF材料可以实现100％的激子利用率，但实际上大多数TADF材料仍存在难以同时兼具高激子利用率和高荧光辐射效率的问题。就当前OLED显示照明产业的实际需求而言，开发更高性能的有机功能材料显得尤为重要。
发明内容
针对现有的OLED材料存在的上述问题，现提供一种丙二腈取代的芳基蒽菲类有机电致发光材料及其制备方法和应用，旨在提供一种具有良好光电性能的有机电致发光材料，以制备高效率的有机电致发光器件。
具体技术方案如下：
结构通式(I)所示的化合物，
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其中R选自( 1 )至( 20 )中所示化合物，
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其中Y选自
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中的1种；m=1或2，n=0或1；且m=1时n只能为 1；当m=2时n只能为0。
具体地说，当m=1时，n= 1, 通式I表示为
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，
其中Y选自
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中的一种；
当m=2时n只能为0，通式（I）所示化合物为
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。
更具体地，所述化合物选自式(I-1)至式(I-50)、式( II-1)至式( II-185)所示结构化合物中的一种：
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。
上述化合物的制备方法，其合成步骤包括：
Figure 1
将A与B混合，加入反应溶剂，再加入催化剂和碱，在氮气或氩气氛围下，将上述反应物的混合溶液于80-200摄氏度反应8-24小时，停止反应后经冷却、过滤、柱层析，得到所述有机电致发光材料。
在上述制备方法中，X为氯或溴，R选自下述( 1 )至( 20 )中的一种; Y选自
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中的一种；m为1或2；n为0或1；且m=1时n只能为 1；当m=2时n只能为0；且所述A与B的摩尔比为1:2.5-3.5，
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。
在上述制备方法中，所述催化剂选自Pd (PPh3)4、Pd(dppf)Cl2、Pd(OAc)2与叔丁基膦、CuI与1,10-邻菲罗啉中的一种，并且，所述催化剂与二卤代丙二腈芳基蒽菲化合物的摩尔比为0 .012-0 .03:1。
在上述制备方法中，所述碱选自碳酸钠、碳酸钾、碳酸氢钠、碳酸铯、叔丁醇钠或叔丁醇钾中的一种，并且，所述碱与所述二卤代丙二腈芳基蒽菲化合物的摩尔比为2.0-4.0:1。
在上述制备方法中，所述反应溶剂选自甲苯、二甲苯、均三甲苯、氮氮二甲基甲酰胺、四氢呋喃或二氯乙烷中的一种。
上述化合物作为有机电致发光器件中的有机发光染料的应用，所述有机电致发光器件的结构为：基片/ 阳极/ 空穴传输层/ 有机发光层/ 电子传输层/ 阴极；基片为玻璃、聚酯类、聚酞亚胺类化合物中的一种材料；阳极为氧化铟锡、氧化锌、氧化锡锌、金、银、铜、聚噻吩/ 聚乙烯基苯磺酸钠、聚苯胺中的一种材料；阴极为锂、镁、钙、锶、铝或铟，或它们中的一种与铜、金或银的合金，或上述金属或合金与金属氟化物交替形成的电极层；空穴传输层为三芳胺类材料；电子传输层为氮杂环类材料；有机发光层的发光染料为式（I）所示的丙二腈取代芳基蒽菲类有机电致发光材料。
本发明有益效果：本发明提供的丙二腈取代的芳基蒽菲类有机电致发光材料具有热激活延迟荧光性质，HOMO和LUMO能级电子云可有效分离，进而实现较小的S1-T1态能隙，并有效提高激子利用率和高荧光辐射效率，并有助于提高器件效率、改善器件性能；本发明所提供的丙二腈取代的芳基蒽菲类有机电致发光材料应用于OLED发光器件制作中，均获得了高的功率效率、外量子效率和好的色纯度。
附图说明
图1为本发明的有机电致发光器件的结构示意图；
图2为本发明所制备的化合物II-40的热激活延迟性质，（a）化合物在不同温度下的瞬态荧光光谱；(b)化合物在没有时间延迟和8 us时间延迟情况下的荧光发光光谱。
具体实施方式
为了使本发明的内容更容易被清楚地理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明。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
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250mL 圆底烧瓶中，加入2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈，4-二苯氨基苯硼酸，Pd(PPh3)4 , 进行抽真空，鼓氩气处理。加入无氧混合溶剂（甲苯，乙醇，饱和Na2CO3溶液），搅拌加热回流12 h。取样点板，反应完全，停止加热。使用饱和NH4Cl溶液淬灭反应，使用二氯甲烷（DCM）萃取三次。组合有机相，使用无水Na2SO4干燥，抽滤，将滤液旋干，进行柱色谱分离，得到目标产物。
元素分析结构(分子式:C56H34N6)：理论值：C 85.04；H 4.33；N 10.63，测试值：C85.03；H 4.30；N 10.67。质谱分析得到相对分子质量为：790.29。
实施例2
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实施例2制备方法与实施例1制备方法相同，将4-二苯氨基苯硼酸换成4-（N-咔唑基）苯硼酸即可。
元素分析结构(分子式:C56H30N6)：理论值：C 85.48；H 3.84；N 10.68，测试值：C85.40；H 3.81；N 10.79。质谱分析得到相对分子质量为：786.95。
实施例3
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实施例3制备方法与实施例1制备方法相同，将4-二苯氨基苯硼酸换成9,9-二苯基芴硼酸酯即可。
元素分析结构(分子式:C70H40N4)：理论值：C 89.72；H 4.30；N 5.98，测试值：C89.71；H 4.27；N 6.02。质谱分析得到相对分子质量为：936.35。
实施例4
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250mL 圆底烧瓶中，加入2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈，咔唑，CuI，1,10-邻菲罗啉，无水NaCO3，进行抽真空，鼓氩气处理。加入无水无氧DMF，搅拌加热回流3d。取样点板，反应完全，停止加热。使用饱和NH4Cl溶液淬灭反应，使用DCM萃取三次。组合有机相，使用无水Na2SO4干燥，抽滤，将滤液旋干，进行柱色谱分离，得到目标产物。
元素分析结构(分子式:C44H22N6)：理论值：C 83.26；H 3.49；N 13.24，测试值：C83.25；H 3.47；N 13.27。质谱分析得到相对分子质量为：634.20。
实施例5
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实施例5制备方法与实施例1制备方法相同，将4-二苯氨基苯硼酸换成N-（3-咔唑基）苯硼酸即可。
元素分析结构(分子式:C58H38N6)：理论值：C 85.06；H 4.68；N 10.26，测试值：C85.04；H 4.64；N 10.32。质谱分析得到相对分子质量为：818.40。
实施例6
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实施例6制备方法与实施例1制备方法相同，将4-二苯氨基苯硼酸换成9,9-二甲基芴硼酸即可。
元素分析结构(分子式:C50H32N4)：理论值：C 87.18；H 4.66；N 8.13，测试值：C87.18；H 4.65；N 8.14。质谱分析得到相对分子质量为：688.25。
实施例7
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250mL 圆底烧瓶中，加入2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈，9,9-二苯基吖啶，Pd(OAc)2，叔丁醇钠，进行抽真空，鼓氩气处理。加入三叔丁基膦的戊烷溶液，以无水无氧甲苯为溶剂，搅拌加热回流24h。取样点板，反应完全，停止加热。使用饱和NH4Cl溶液淬灭反应，使用DCM萃取三次。组合有机相，使用无水Na2SO4干燥，抽滤，将滤液旋干，进行柱色谱分离，得到目标产物。
元素分析结构(分子式:C70H42N6)：理论值：C 86.93；H 4.38；N 8.69，测试值：C86.93；H 4.35；N 8.72。质谱分析得到相对分子质量为：966.34。
实施例8
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实施例8制备方法与实施例7制备方法相同，将9,9-二甲基吖啶换成10H-螺[吖啶-9,9'-芴]即可。
元素分析结构(分子式:C70H38N6)：理论值：C 87.30；H 3.98；N 8.73，测试值：C87.29；H 3.95；N 8.76。质谱分析得到相对分子质量为：962.30。
实施例9
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实施例9制备方法与实施例7制备方法相同，将9,9-二苯基吖啶换成9,9-二甲基吖啶即可。
元素分析结构(分子式:C50H34N6)：理论值：C 83.54；H 4.77；N 11.69，测试值：C83.53；H 4.73；N 11.74。质谱分析得到相对分子质量为：718.30。
实施例10
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实施例10制备方法与实施例7制备方法相同，将9,9-二甲基吖啶换成10H-吩噁嗪即可。
元素分析结构(分子式:C44H22N6O2)：理论值：C 79.27；H 3.33；N 12.61；O 4.80，测试值：C 79.26；H 3.30；N 12.64；O 4.80。质谱分析得到相对分子质量为：666.15。
实施例11
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实施例10制备方法与实施例7制备方法相同，将9,9-二甲基吖啶换成10H-吩噻嗪即可。
元素分析结构(分子式:C44H22N6S2)：理论值：C 75.62；H 3.17；N 12.03；O 9.18，测试值：C 79.63；H 3.15；N 12.05；O 9.17。质谱分析得到相对分子质量为：698.14。
实施例12
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实施例12制备方法与实施例1制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2,2'-(2,7-二溴菲-9,10-二亚甲基)丙二腈即可。
元素分析结构(分子式:C56H34N4)：理论值：C 85.04；H 4.33；N 10.63，测试值：C85.03；H 4.30；N 10.67。质谱分析得到相对分子质量为：790.30。
实施例13
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实施例13制备方法与实施例12制备方法相同，将4-二苯氨基苯硼酸换成4-（N-咔唑基）苯硼酸即可。
元素分析结构(分子式:C56H30N6)：理论值：C 85.48；H 3.84；N 10.68，测试值：C85.46；H 3.82；N 10.72。质谱分析得到相对分子质量为：786.30。
实施例14
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实施例14制备方法与实施例12制备方法相同，将4-二苯氨基苯硼酸换成N-（3-咔唑基）苯硼酸即可。
元素分析结构(分子式:C56H30N6)：理论值：C 85.48；H 3.84；N 10.68，测试值：C85.47；H 3.82；N 10.71。质谱分析得到相对分子质量为：786.27。
实施例15
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实施例15制备方法与实施例4制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2,2'-(2,7-二溴菲-9,10-二亚甲基)丙二腈即可。
元素分析结构(分子式:C44H22N6)：理论值：C 83.26；H 3.49；N 13.24，测试值：C83.25；H 3.47；N 13.27。质谱分析得到相对分子质量为：634.20。
实施例16
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实施例16制备方法与实施例1制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2,2`-(2,6-二溴蒽-9,10-二亚甲基)丙二腈即可。
元素分析结构(分子式:C55H44N4)：理论值：C 86.81；H 5.83；N 7.36，测试值：C86.80；H 5.79；N 7.41。质谱分析得到相对分子质量为：760.40。
实施例17
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实施例17制备方法与实施例21制备方法相同，将4-二苯氨基苯硼酸换成4-（N-咔唑基）苯硼酸即可。
元素分析结构(分子式:C56H30N6)：理论值：C 85.48；H 3.84；N 10.68，测试值：C85.46；H 3.82；N 10.72。质谱分析得到相对分子质量为：786.30。
实施例18
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实施例18制备方法与实施例21制备方法相同，将4-二苯氨基苯硼酸换成4-（N-咔唑基）苯硼酸即可。
元素分析结构(分子式:C56H30N6)：理论值：C 85.48；H 3.84；N 10.68，测试值：C85.46；H 3.82；N 10.72。质谱分析得到相对分子质量为：786.30。
实施例19
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实施例19制备方法与实施例21制备方法相同，将4-二苯氨基苯硼酸换成9,9-二苯基芴硼酸即可。
元素分析结构(分子式:C70H40N4)：理论值：C 89.72；H 4.30；N 5.98，测试值：C89.71；H 4.27；N 6.02。质谱分析得到相对分子质量为：936.35。
实施例20
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实施例20制备方法与实施例4制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2,2`-(2,6-二溴蒽-9,10-二亚甲基)丙二腈即可。
元素分析结构(分子式:C44H22N6)：理论值：C 83.26；H 3.49；N 13.24，测试值：C83.25；H 3.47；N 13.27。质谱分析得到相对分子质量为：634.20。
实施例21
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实施例21制备方法与实施例21制备方法相同，将4-二苯氨基苯硼酸换成9,9-二甲基芴硼酸即可。
元素分析结构(分子式:C50H32N4)：理论值：C 87.18；H 4.66；N 8.13，测试值：C87.18；H 4.65；N 8.14。质谱分析得到相对分子质量为：688.24。
实施例22
Figure 788417DEST_PATH_IMAGE058
实施例22制备方法与实施例9制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2,2`-(2,6-二溴蒽-9,10-二亚甲基)丙二腈即可。
元素分析结构(分子式:C50H34N6)：理论值：C 83.54；H 4.77；N 11.69，测试值：C83.53；H 4.73；N 11.74。质谱分析得到相对分子质量为：718.30。
实施例23
Figure 430751DEST_PATH_IMAGE059
实施例23制备方法与实施例1制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2,2`-(2,7-二溴蒽-9,10-二亚甲基)丙二腈即可。
元素分析结构(分子式:C56H34N4)：理论值：C 85.04；H 4.33；N 10.63，测试值：C85.03；H 4.30；N 10.67。质谱分析得到相对分子质量为：790.30。
实施例24
Figure 34908DEST_PATH_IMAGE060
实施例24制备方法与实施例4制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2,2`-(2,7-二溴蒽-9,10-二亚甲基)丙二腈即可。
元素分析结构(分子式:C44H22N6)：理论值：C 83.26；H 3.49；N 13.24，测试值：C83.25；H 3.47；N 13.27。质谱分析得到相对分子质量为：634.20。
实施例25
Figure 471705DEST_PATH_IMAGE061
实施例25制备方法与实施例1制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2,6-二氯-10-甲基吖啶-9(10H)-亚甲基)丙二腈即可。
元素分析结构(分子式:C53H37N5)：理论值：C 85.57；H 5.01；N 9.41，测试值：C85.56；H 4.98；N 9.46。质谱分析得到相对分子质量为：743.31。
实施例26
Figure 912045DEST_PATH_IMAGE062
实施例26制备方法与实施例4制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2,6-二氯-10-甲基吖啶-9(10H)-亚甲基)丙二腈即可。
元素分析结构(分子式:C41H25N5)：理论值：C 83.79；H 4.29；N 11.92，测试值：C83.79；H 4.30；N 11.91。质谱分析得到相对分子质量为：587.20。
实施例27
Figure 92490DEST_PATH_IMAGE063
实施例27制备方法与实施例9制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2,6-二氯-10-甲基吖啶-9(10H)-亚甲基)丙二腈即可。
元素分析结构(分子式:C47H37N5)：理论值：C 84.02；H 5.55；N 10.42，测试值：C84.01；H 5.57；N 10.41。质谱分析得到相对分子质量为：671.32。
实施例28
Figure 551154DEST_PATH_IMAGE064
实施例28制备方法与实施例25制备方法相同，将对4-二苯氨基苯硼酸换成9,9-二苯基芴硼酸即可。
元素分析结构(分子式:C47H35N3)：理论值：C 87.96；H 5.50；N 6.55，测试值：C89.95；H 5.46；N 6.59。质谱分析得到相对分子质量为：641.30。
实施例29
Figure 893273DEST_PATH_IMAGE065
实施例29制备方法与实施例1制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2,6-二溴-9H-占吨-9-亚甲基)丙二腈即可。
元素分析结构(分子式:C52H34N4O)：理论值：C 85.46；H 4.69；N 7.67；O 2.19，测试值：C 85.44；H 4.66；N 7.71；O 2.19。质谱分析得到相对分子质量为：730.30。
实施例30
Figure 817979DEST_PATH_IMAGE066
实施例30制备方法与实施例4制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2,6-二溴-9H-占吨-9-亚甲基)丙二腈即可。
元素分析结构(分子式:C40H22N4O)：理论值：C 83.61；H 3.86；N 9.75；O 2.78，测试值：C 83.59；H 3.87；N 9.75；O 2.79。质谱分析得到相对分子质量为：574.20。
实施例31
Figure 536537DEST_PATH_IMAGE067
实施例31制备方法与实施例29制备方法相同，将4-二苯氨基苯硼酸换成9,9-二甲基芴硼酸即可。
元素分析结构(分子式:C46H32N2O)：理论值：C 87.87；H 5.13；N 4.46；O 2.54，测试值：C 87.86；H 5.09；N 4.50；O 2.55。质谱分析得到相对分子质量为：628.26。
实施例32
Figure 115286DEST_PATH_IMAGE068
实施例32制备方法与实施例1制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2,6-二溴-9H-噻蒽-9-亚甲基)丙二腈即可。
元素分析结构(分子式:C52H34N4S)：理论值：C 83.62；H 4.59；N 7.50；S 4.29，测试值：C 83.61；H 4.56；N 7.54；S 4.29。质谱分析得到相对分子质量为：746.26。
实施例33
Figure 893886DEST_PATH_IMAGE069
实施例33制备方法与实施例7制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2,6-二溴-9H-噻蒽-9-亚甲基)丙二腈即可。
元素分析结构(分子式:C46H34N4S)：理论值：C 81.87；H 5.08；N 8.30；S 4.75，测试值：C 81.87；H 5.09；N 8.29；S 4.75。质谱分析得到相对分子质量为：674.27。
实施例34
Figure 574397DEST_PATH_IMAGE070
实施例34制备方法与实施例1制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2，6-二溴-9-芴-9-二亚甲基)丙二腈即可。
元素分析结构(分子式:C52H34N4)：理论值：C 87.37；H 4.79；N 7.84，测试值：C87.31；H 4.70；N 7.87。质谱分析得到相对分子质量为：714.28。
实施例35
Figure 96645DEST_PATH_IMAGE071
实施例35制备方法与实施例7制备方法相同，将2,2'-(3,6-二溴菲-9,10-二亚甲基)丙二腈换成2-(2，6-二溴-9-芴-9-二亚甲基)丙二腈即可。
元素分析结构(分子式:C46H34N4)：理论值：C 85.95；H 5.33；N 8.72，测试值：C85.91；H 5.36；N 8.75。质谱分析得到相对分子质量为：642.81。
有机电致发光器件实施例
本发明的实施例I-VIIII中以部分上述有机电致发光材料制备获得器件1-9，应当理解，器件实施过程与结果，只是为了更好地解释本发明，并非对本发明的限制，上述有机电致发光器件的制备方法如下：
将涂布了ITO 透明导电层的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮和乙醇的混合溶剂中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光清洗机照射1~100 分钟，并用低能阳离子束轰击表面；
把上述带有阳极的玻璃基片置于真空腔内，抽真空至1×10-5～ 9×10-3 Pa，在上述阳极层膜上先蒸镀CuPc 1~15 nm，继续蒸镀NPB 作为空穴传输层，蒸镀速率控制在0.1 ~0.5 nm/s，蒸镀膜厚为50~75 nm ；
在空穴传输层之上，继续蒸镀一层发光层，发光层以主体材料和本发明式（I）所示的丙二腈取代的芳基蒽菲类有机电致发光材料掺杂而成，主体材料和丙二腈取代的芳基蒽菲类有机电致发光材料的蒸镀速率比为100 ：1，在本发明中丙二腈芳基蒽菲类有机电致发光材料的掺杂浓度为x，x 为5~15wt％，其蒸镀总速率为0.1 nm/s，蒸镀总膜厚为30 nm ；
再继续蒸镀一层TPBI 作为器件的电子传输层，其蒸镀速率为0.l nm/s，蒸镀总膜厚为35 nm ；
最后，在上述电子传输层之上依次蒸镀LiF 层和Mg ：Ag 合金层作为器件的阴极层，其中LiF 层的厚度为0.5 nm，Mg ：Ag 合金层的蒸镀速率为2.0 ～ 3.0 nm/s，厚度为100 nm。
上述有机电致发光器件的制备方法中，TAPC、Ir(piq)2acac、TPBI、CBP、mCP的结构式如下，特别需要指出的是化合物2,6- 二芘-9,10- 二烯-11,11,12,12- 四氰基蒽醌。为专利（CN 102786438 A）中提及的化合物，以其作为对比制备器件：
Figure 529900DEST_PATH_IMAGE072
如上完成器件1-10后，用公知的驱动电路将阳极和阴极连接起来，测量器件的功率效率、外量子效率及CIE参数，器件1-10的主要结构层及测试结果，如下表所示：
Figure 479402DEST_PATH_IMAGE073
由上表分析可知，应用本发明所提供的丙二腈取代的芳基蒽菲类有机电致发光材料由于其特有的热激活延迟荧光性质，所制备的OLED发光器件的效率及色纯度均高于已知发明报道的2,6- 二芘-9,10- 二烯-11,11,12,12- 四氰基蒽醌。本发明所提供的丙二腈取代的芳基蒽菲类有机电致发光材料以其优异的热激活延迟荧光性质在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
由于化合物II-40同时具备以下两种性质：（1）延迟时间下荧光光谱与未延迟情况下的荧光光谱重叠；（2）随着温度的增加，热激活延迟荧光部分的寿命延长，说明化合物II-40是热激活荧光化合物。通过进一步的类似表征，本发明的所有其他化合物均具有热激活延迟荧光活性。
以上所述仅为本发明较佳的实施例，并非因此限制本发明的实施方式及保护范围，对于本领域技术人员而言，应当能够意识到凡运用本发明说明书及图示内容所作出的等同替换和显而易见的变化所得到的方案，均应当包含在本发明的保护范围内。

Claims (10)

1.结构通式(I)所示的化合物，
Figure FDA0002761899560000011
其中R选自(1)至(20)所示化合物，
Figure FDA0002761899560000012
Y选自
Figure FDA0002761899560000013
中的一种；m＝1或2，n＝0或1；且m＝1时n只能为1；当m＝2时n只能为0。
2.根据权利要求1所述化合物，其特征在于：
当m＝1时，n＝1,通式I表示为
Figure FDA0002761899560000014
其中Y选自
Figure FDA0002761899560000015
中的一种；
当m＝2时n只能为0，通式(I)所示化合物为
Figure FDA0002761899560000021
3.根据权利要求1或2所述化合物，其特征在于所述化合物选自如下所示化合物的一种或多种：
Figure FDA0002761899560000031
Figure FDA0002761899560000041
Figure FDA0002761899560000051
Figure FDA0002761899560000061
Figure FDA0002761899560000071
Figure FDA0002761899560000081
Figure FDA0002761899560000091
Figure FDA0002761899560000101
Figure FDA0002761899560000111
Figure FDA0002761899560000121
Figure FDA0002761899560000131
4.根据权利要求1-3任一项所述化合物的制备方法，其合成步骤包括：
Figure FDA0002761899560000132
其中X为氯或溴，R、m、n如权利要求1-3中任一项所定义，
将A与B混合，加入反应溶剂，再加入催化剂和碱，在氮气或氩气氛围下，将上述反应物的混合溶液于80-200摄氏度反应8-24小时，停止反应后经冷却、过滤、柱层析，得到所述化合物。
5.根据权利要求4所述的制备方法，其特征在于，所述A与B的摩尔比为1:2.5-3.5。
6.根据权利要求4所述的制备方法，其特征在于，所述催化剂选自Pd(PPh3)4、Pd(dppf)Cl2、Pd(OAc)2与叔丁基膦、CuI与1,10-邻菲罗啉中的一种，并且，所述催化剂与化合物A的摩尔比为0.012-0.03:1。
7.根据权利要求4所述的制备方法，其特征在于，所述碱选自碳酸钠、碳酸钾、碳酸氢钠、碳酸铯、叔丁醇钠或叔丁醇钾中的一种，并且，所述碱与化合物A的摩尔比为2.0-4.0:1。
8.根据权利要求4所述的制备方法，其特征在于，所述反应溶剂选自甲苯、二甲苯、均三甲苯、N，N’-二甲基甲酰胺、四氢呋喃或二氯乙烷中的一种。
9.权利要求1所述化合物作为有机电致发光器件中的有机发光染料的应用。
10.根据权利要求9所述应用，其特征在于，所述有机电致发光器件的结构为：基片/阳极/空穴传输层/有机发光层/电子传输层/阴极；基片为玻璃、聚酯类、聚酞亚胺类化合物中的一种材料；阳极为氧化铟锡、氧化锌、氧化锡锌、金、银、铜、聚噻吩/聚乙烯基苯磺酸钠、聚苯胺中的一种材料；阴极为锂、镁、钙、锶、铝或铟，或它们中的一种与铜、金或银的合金，或上述金属或合金与金属氟化物交替形成的电极层；空穴传输层为三芳胺类材料；电子传输层为氮杂环类材料；有机发光层的发光染料为式(I)所示的丙二腈取代芳基蒽菲类有机电致发光材料。
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210061934A1 (en) * 2019-08-30 2021-03-04 Johnson & Johnson Vision Care, Inc. Contact lens displaying improved vision attributes
US11543683B2 (en) * 2019-08-30 2023-01-03 Johnson & Johnson Vision Care, Inc. Multifocal contact lens displaying improved vision attributes
US11993037B1 (en) 2018-03-02 2024-05-28 Johnson & Johnson Vision Care, Inc. Contact lens displaying improved vision attributes
US10935695B2 (en) 2018-03-02 2021-03-02 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
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CN109134348A (zh) * 2018-09-30 2019-01-04 长春海谱润斯科技有限公司 一种咔唑类化合物及其有机发光器件
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CN109438469B (zh) * 2018-12-10 2021-02-12 青岛科技大学 一种含有噻吩结构的有机光电材料及其应用
US11958824B2 (en) * 2019-06-28 2024-04-16 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment
CN110437103B (zh) * 2019-08-01 2021-01-26 宁波卢米蓝新材料有限公司 一种环状化合物及其用途和电子器件
CN112552270B (zh) * 2020-11-16 2022-10-25 南京高光半导体材料有限公司 一种有机电致发光化合物及有机电致发光器件
US20240099128A1 (en) * 2021-01-12 2024-03-21 Hodogaya Chemical Co., Ltd. Compound, hole transport material, and photoelectric conversion element including same
KR102323603B1 (ko) * 2021-03-16 2021-11-10 최돈수 유기 전기 발광 소자용 발광 재료, 이를 이용한 유기 전기 발광 소자 및 유기 전기 발광 소자용 재료

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061264A1 (en) * 1981-03-13 1982-09-29 Matsushita Electric Industrial Co., Ltd. Tetracyanoanthraquinodimethane compounds and processes for the production thereof, polymers and charge-transfer complexes derived therefrom
JPS63104061A (ja) * 1986-10-22 1988-05-09 Fuji Xerox Co Ltd 有機電子材料
CN102786438A (zh) * 2011-05-16 2012-11-21 海洋王照明科技股份有限公司 一类氰基蒽醌衍生物、其制备方法和有机电致发光器件
KR20120130566A (ko) * 2011-05-23 2012-12-03 덕산하이메탈(주) 화합물 및 이를 이용한 유기전기소자, 그 전자장치
CN106832229A (zh) * 2016-12-09 2017-06-13 华南理工大学 含二苯并六元砜基稠环单元的聚合物及其应用
JP2018006700A (ja) * 2016-07-08 2018-01-11 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子、表示装置、照明装置、π共役系化合物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061264A1 (en) * 1981-03-13 1982-09-29 Matsushita Electric Industrial Co., Ltd. Tetracyanoanthraquinodimethane compounds and processes for the production thereof, polymers and charge-transfer complexes derived therefrom
JPS63104061A (ja) * 1986-10-22 1988-05-09 Fuji Xerox Co Ltd 有機電子材料
CN102786438A (zh) * 2011-05-16 2012-11-21 海洋王照明科技股份有限公司 一类氰基蒽醌衍生物、其制备方法和有机电致发光器件
KR20120130566A (ko) * 2011-05-23 2012-12-03 덕산하이메탈(주) 화합물 및 이를 이용한 유기전기소자, 그 전자장치
JP2018006700A (ja) * 2016-07-08 2018-01-11 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子、表示装置、照明装置、π共役系化合物
CN106832229A (zh) * 2016-12-09 2017-06-13 华南理工大学 含二苯并六元砜基稠环单元的聚合物及其应用

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