CN105481672A - 一系列荧光oled材料 - Google Patents

一系列荧光oled材料 Download PDF

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CN105481672A
CN105481672A CN201510996303.8A CN201510996303A CN105481672A CN 105481672 A CN105481672 A CN 105481672A CN 201510996303 A CN201510996303 A CN 201510996303A CN 105481672 A CN105481672 A CN 105481672A
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replacement
phenyl
group
formula
unsubstituted
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曹建华
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Abstract

本发明公开了一系列荧光OLED材料。该荧光OLED材料结构如式I所示。该式I所示材料具有延迟荧光性能，利用该材料制备的有机电致发光器件可得到深蓝光的有机发光二极管，其可以代替贵金属的磷光材料使用，大大降低了OLED器件的制造成本，并且材料合成以及提纯的方法简单适于大规模生产等特点，是作为有机电致发光器件发光材料的理想选择。

Description

一系列荧光OLED材料
技术领域
本发明属于有机电致发光显示技术领域，涉及一系列荧光OLED材料。
背景技术
有机电致发光(简称OLED)及相关的研究早在1963年pope等人首先发现了有机化合物单晶蒽的电致发光现象。1987年美国的柯达公司用蒸镀有机小分子的方法制成了一种非晶膜型器件，将驱动电压降到了20V以内。这类器件由于具有超轻薄、全固化、自发光、亮度高、视角宽、响应速度快、驱动电压低、功耗小、色彩鲜艳、对比度高、工艺过程简单、温度特性好、可实现柔软显示等优点，可广泛应用于平板显示器和面光源，因此得到了广泛地研究、开发和使用。
经过二十几年的发展，有机EL材料已经全面实现了红、蓝、绿色发光，应用领域也从小分子扩展到了高分子以及金属络合物等领域。最近几年有机电发光显示技术己趋于成熟，一些产品已进入市场，但在产业化时程中，仍有许多问题亟待解决，特别是用于制作器件的各种有机材料，其载流子注入、传输性能，材料电发光性能、使用寿命、色纯度、各种材料之间及与各电极之间的匹配等，尚有许多问题还未解决。尤其是发光器件在发光效率和使用寿命还达不到实用化要求，这大限制了OLED技术的发展。而利用三线态发光的金属配合物磷光材料具有高的发光效率，其绿光和红光材料已经达到使用要求，但是金属配合物特殊的电子结构特征，导致其蓝光材料无法达到使用要求。
介于荧光和磷光之间的热激活延迟荧光材料的出现，大大提高了荧光材料的发光效率，几乎达到磷光材料的发光效率，弥补了磷光蓝光材料的不足，同时避免了使用贵重的稀有金属，大大降低了材料成本。但是已经报道的热激活延迟荧光材料由于在固体状态下存在聚集荧光淬灭效应，只能采用掺杂的方式制备OLED器件。因此，开发出具有在固态下聚集诱导发光的热致激活延迟荧光材料是解决上述问题的一个途径。
发明内容
本发明的目的是提供一系列荧光OLED材料。
本发明提供的荧光OLED材料，其结构通式如式I所示，
式I
所述式I中：
R1和R2独立地选自氢原子、取代的或未取代的C6-C60芳基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C2-C60杂环芳基中的任意一种；
Ar1、Ar2、Ar3独立地选自取代的或未取代的C6-C60芳基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C6-C60芳硫基、取代的或未取代的C6-C60芳膦基、取代的或未取代的C6-C60芳硅基、取代的或未取代的C6-C60芳硼基、取代的或未取代的C2-C60杂环芳基中的任意一种；
且Ar1和Ar2可以相连形成
所述取代的C6-C60芳基、取代的C6-C60芳氧基、取代的C2-C60杂环芳基、取代的C6-C60芳硫基、取代的C6-C60芳膦基、取代的C6-C60芳硅基、取代的C6-C60芳硼基和取代的C2-C60杂环芳基中，取代基选自甲基、乙基、叔丁基、甲氧基、氰基、苯氧基、卤原子和含有2～8个碳原子的脂肪烃基中的任意一种；
Ar4选自如下基团中的任意一种：
上述式I中，所述C6-C60芳基选自苯基、萘基、联苯基、蒽基、联蒽基、对叔丁基苯基、2,4-二氟苯基、4-(N,N-二甲基胺基)苯基、4-(N,N-二苯基胺基)苯基、3-(N,N-二苯基胺基)苯基、芘基、并四苯基、菲基、苯并菲基、苯并蒽基、苯并芘基和芴基中的任意一种；
所述C6-C60芳氧基选自4-苯氧基苯基、二苯并[b,d]呋喃-2-基、二苯并[b,d]呋喃-4-基、苯并呋喃-2-基、苯并呋喃-5-基和苯并呋喃-7-基中的任意一种；
所述C6-C60芳硫基选自二苯并[b,d]噻吩-2-基、二苯并[b,d]噻吩-4-基、4-苯亚砜基苯基、4-苯砜基苯基、苯并噻吩-2-基、苯并噻吩-5-基和苯并噻吩-7-基中的任意一种；
所述C6-C60芳膦基选自4-(二苯基氧膦基)苯基、3-(二苯基氧膦基)苯基和二苯并[b]氧膦-5-(4-苯基)-4-基中的任意一种；
所述C6-C60芳硅基选自4-(三苯基硅基)苯基、4-(二苯基甲基硅基)苯基、3-(三苯基硅基)苯基和3-(二苯基甲基硅基)苯基中的任意一种；
所述C6-C60芳硼基选自4-(二(2,4,6-三甲基)苯基)-硼烷苯基、二苯并[b,d]硼烷-5-苯基-4-基和三苯基硼基中的任意一种；
所述C2-C60的杂环芳基选自如下式II-1至式II-15所示基团中的任意一种：
表示取代位；
所述式II-1～II-15中，Z1、Z2和Z3均独立的选自氢、氘氢、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60烷基、C2-C60烯基、C2-C60炔基、C1-C60烷氧基、C3-C60环烷烃基、C3-C60环烯烃基、C6-C60芳基、至少含有一个-F、-CN或C1-C10烷基的C6-C60芳基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C6-C60芳硫醚基、取代的或未取代的C2-C60杂环芳基中的任意一种；
x1为1～4的整数；
x2为1～3的整数；
x3为1～2的整数；
x4为1～6的整数；
x5为1～5的整数；
T1为氧或硫原子；
所述取代的C6-C60芳氧基、取代的C6-C60芳硫醚基和取代的C2-C60杂环芳基中，取代基选自甲基、乙基、叔丁基、甲氧基、氰基、苯氧基、卤原子和含有2～8个碳原子的脂肪烃基中的任意一种。
具体的，所述式I所示化合物为如下1～105化合物中的任意一种：
另外，含有上述本发明提供的式I所示化合物的有机发光二极管材料及该式I所示化合物在制备有机发光二极管材料中的应用以及该式I所示化合物作为发光层材料在制备有机电致发光器件中的应用和以式I所示化合物作为发光层的有机电致发光器件，也属于本发明的保护范围。所述有机电致发光器件的荧光发射波长具体可为430-450nm，具体可为438、442或446nm。
具体的，所述有机电致发光器件由下至上依次由透明基片、阳极、空穴注入层、空穴传输层、有机发光层、电子传输层和阴极层组成。
其中，构成所述透明基片的材料为玻璃或柔性基片；
构成所述阳极层的材料为无机材料或有机导电聚合物；其中，所述无机材料为氧化铟锡、氧化锌、氧化锡锌、金、银或铜；所述有机导电聚合物选自聚噻吩、聚乙烯基苯磺酸钠和聚苯胺中的至少一种；
构成所述空穴注入层的材料为TDATA、m-MTDATA或2-TNATA：
所述TDATA的结构式如下：
所述m-MTDATA的结构式如下：
所述2-TNATA的结构式如下：
构成所述空穴传输层的材料为NPB或TPD：
所述NPB的结构式如下：
所述TPD的结构式如下：
构成所述有机发光层的材料为所述式I所示化合物和主体材料；
其中，所述主体材料为CBP、PVK、DPEPO、TBADN、E3、ADN、dmCBP、mCP、TCzP、Slic-H117、BCPB、Slic-H065、SlimCP、mCBP所示化合物或
所述式I-所示化合物的质量与所述主体材料的质量比为1-10：90；
构成所述电子传输层的材料为Liq、Alq3、Gaq3或BAlq所示化合物；
其中，Liq所示化合物的结构式如下：
构成所述阴极层的材料选自下述元素中的任意一种或任意两种组成的合金或下述元素的氟化物：锂、镁、银、钙、锶、铝、铟、铜、金和银。
上述器件中，所述空穴注入层的厚度为30-50nm；具体为40nm；
所述空穴传输层的厚度为5-15nm；具体为10nm；
所述有机发光层的厚度为10-100nm；具体为40nm；
所述电子传输层的厚度为10-30nm；具体为50nm；
所述阴极层的厚度为90-110nm，具体为100nm。
本发明提供的式I所示有机电致发光材料，具有延迟荧光性能，克服了热激活延迟荧光材料的聚集荧光淬灭效应，具有诱导发光性质，具有较高的玻璃化温度、高的热稳定性和优良的发光性能。其合成工艺简单，提纯的方法简单适于大规模生产等特点，并可通过连接不同的基团调节产物的发光性能、热稳定性等，是作为有机电致发光器件电子传输材料的理想选择。本发明使用上述荧光材料的OLED器件，其发光层的荧光效率高、稳定性好，从而使器件的发光效率和寿命都能达到实用化的要求。
附图说明
图1为本发明式I所示化合物的制备方法流程图；
图2为本发明实施例1所得式I所示化合物17的发光谱图。
具体实施方式
下面结合具体实施例对本发明的特征和技术内容作进一步阐述，但本发明并不限于以下实施例。请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明，并非用来对本发明加以限制。所述原材料如无特别说明均能从公开商业途径而得。
本发明提供的式I所示化合物可按照图1所示方法制备而得。图1中中间产物化合物结构式中，R1、R2、Ar1、Ar2、Ar3和Ar4的定义与式I中的定义相同。
下述实施例对OLED材料及器件进行性能测试的测试仪器及方法如下：
OLED材料性能检测条件：
延迟荧光寿命τTADF和量子效率使用时间分辨荧光光谱仪F900测试；
OLED器件性能检测条件：
亮度和色度坐标：使用光谱扫描仪PhotoResearchPR-715测试；
电流密度和起亮电压：使用数字源表Keithley2420测试；
功率效率：使用NEWPORT1931-C测试。
下述实施例中所用缩写定义如下：
THF四氢呋喃
DMSO二甲基亚砜
LDA二异丙基胺基锂
Et3N三乙胺
Pd(PPh3)4四(三苯基膦)钯
Boc2O二碳酸二叔丁酯
LiTMP2,2,6,6-四甲基哌啶-1-锂
实施例1、化合物式17的制备
第一步：2-溴-4,4’-二甲基联苯的制备
36.5g(0.2mol)的4,4’-二甲基联苯溶解在360ml无水二氯甲烷中，室温下加入1粒碘，搅拌反应1小时，缓慢滴加入35.2g(0.22mol)的溴素溶于二氯甲烷的溶液，搅拌反应24小时，加入120ml的饱和亚硫酸氢钠水溶液，搅拌反应1小时，分出有机相，有机相用无水硫酸钠干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，减压浓缩干，得48g无色油状物，收率92％。
第二步：2-溴-4,4’-二溴亚甲基联苯的制备
将46g(0.176mol)2-溴-4,4’-二甲基联苯用1000ml四氯化碳溶解，加入65.8g(0.37mol)的NBS，再加入144mg(0.88mmol)自由基引发剂AIBN，升温回流搅拌反应8小时，冷却到室温，过滤，滤液用水洗三次，有机相用无水硫酸钠干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，减压浓缩干，得64g无色油状物，收率87％。
第三步：2-溴-4,4’-二(磷酸二乙酯基亚甲基)联苯的制备
将60g(0.143mol)2-溴-4,4’-二溴亚甲基联苯和119g(0.716mol)的亚磷酸三乙酯混合，加热升温回流搅拌反应8小时，高真空下减压蒸除亚磷酸三乙酯，剩余物用硅胶柱分离纯化，乙酸乙酯洗脱，得64g黄色油状物，收率84％。
第四步：2-溴-4,4’-二(2,2-二苯乙烯)联苯的制备
将20g(37.5mmol)2-溴-4,4’-二(磷酸二乙酯基亚甲基)联苯用100ml的干燥四氢呋喃溶解，加入13.7g(75mmol)的二苯甲酮，在氮气保护下，分批加入10g(90mmol)的叔丁醇钾，搅拌反应8小时，升温回流反应4小时，冷却到室温，倒入500ml的冰水中，用乙酸乙酯萃取，有机相用无水硫酸钠干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，石油醚洗脱，得14.5g黄色固体，收率65.5％。
第五步：化合物式17的制备
将10g(16.9mmol)2-溴-4,4’-二(2,2-二苯乙烯)联苯用60ml的四氢呋喃溶解，加入6.7g(20mmol)的2-(4-(硼酸频那醇酯基)苯基)喹喔啉，在氮气保护下，加入196mg(0.169mmol)的钯催化剂Pd(PPh3)4以及34ml的1M碳酸钠水溶液，升温至65℃搅拌反应8小时，冷却到室温，用乙酸乙酯萃取，有机相用无水硫酸钠干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，石油醚-乙酸乙酯洗脱，再用乙醇重结晶，得10g淡绿色固体，收率84％。
实验数据：
(1)1HNMR(δ、CDCl3)：6.99(2H,s)，7.02～7.07(5H,m)，7.23～7.26(6H,m)，7.28～7.40(25H,m)；
(2)HRMS：C54H38N2，标准分子量714.30，测试结果715.62[M+H]；
(3)τTADF：11ms；
(4)98.6％；
(5)玻璃化温度Tg：158.24℃；
(6)最大紫外吸收波长：350nm；
(7)图2为该实施例所得式I所示化合物17的荧光发光谱图，荧光发射波长：446nm。
实施例2、化合物式55的制备
第一步：化合物式20的制备
此步合成操作参照实施例1的第五步，用10g(16.9mmol)2-溴-4,4’-二(2,2-二苯乙烯)联苯和8.5g(20mmol)3,5-二苯基-4-(4-(硼酸频那醇酯基)苯基)-4H-1,2,4-三氮唑进行偶联反应，硅胶柱分离纯化，得到5.8g的黄色的固体，收率80％。
第二步：中间体4-(4”,5’-双(1-溴-2,2-二苯乙烯基)-[1,1’:2’,1”-三苯基]-4-基)-3,5-二苯基-4H-1,2,4-三氮唑的制备
5g(6.2mmol)的化合物式20和250ml四氯化碳混合，加入2.4g(13.6mmol)的NBS和10mg(0.06mmol)的自由基引发剂AIBN，升温至回流搅拌反应24小时，冷却到室温，加入100ml的水稀释，升温至回流搅拌反应30分钟，冷却到室温，过滤，滤饼用热水洗，再用热的甲醇洗，得到5.6g白色的固体，收率94％。
第三步：化合物式55的制备
将5g(5.1mmol)上步双溴中间体用50ml的四氢呋喃溶解，加入1.6g(12.9mmol)的苯硼酸，在氮气保护下，加入60mg(0.05mmol)的钯催化剂Pd(PPh3)4以及20ml的1M碳酸钠水溶液，升温回流搅拌反应8小时，冷却到室温，用乙酸乙酯萃取，有机相用无水硫酸钠干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，石油醚-乙酸乙酯洗脱，再用乙醇重结晶，得4.3g黄色固体，收率88％。
实验数据：
(1)1HNMR(δ、CDCl3)：7.01～7.08(6H,m)，7.22～7.29(30H,m)，7.31～7.38(7H,m)，7.41～7.48(8H,m)；
(2)HRMS：C72H51N3，标准分子量957.41，测试结果958.23[M+H]；
(3)τTADF：14ms；
(4)98.3％；
(5)玻璃化温度Tg：183.52℃；
(6)最大紫外吸收波长：345nm；
(7)荧光发射波长：438nm。
实施例3、化合物式95的制备
第一步：中间体9,9’-((2-溴-[1,1’-联苯]-4,4’-二基)双(亚甲叉))双(9H-芴)的制备
将20g(37.5mmol)2-溴-4,4’-二(磷酸二乙酯基亚甲基)联苯用100ml的干燥四氢呋喃溶解，加入13.5g(75mmol)的9-芴酮，在氮气保护下，分批加入10g(90mmol)的叔丁醇钾，搅拌反应8小时，升温回流反应4小时，冷却到室温，倒入500ml的冰水中，用乙酸乙酯萃取，有机相用无水硫酸钠干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，石油醚洗脱，得16.6g黄色固体，收率75％。
第二步：化合物式95的制备
10g(17mmol)的上步中间体、6.4g(20.5mmol)的(4-(2-苯基-1H-苯并[d]咪唑-1-基)苯基)硼酸、197mg(0.17mmol)的钯催化剂Pd(PPh3)4以及34ml的1M碳酸钠水溶液，再加入30ml的甲苯以及15ml的乙醇，在氮气保护下，升温回流搅拌反应8小时，冷却到室温，用乙酸乙酯萃取，有机相用无水硫酸钠干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，石油醚-乙酸乙酯洗脱，再用乙醇重结晶，得6.5g黄色固体，收率49％。
实验数据：
(1)1HNMR(δ、CDCl3)：6.98(2H,s)，7.06～7.09(2H,d)，7.22～7.41(23H,m)，7.43～7.48(3H,m)，7.84～7.92(7H,m)，8.16～8.19(1H,m)；
(2)HRMS：C59H38N2，标准分子量774.30，测试结果775.15[M+H]；
(3)τTADF：8.6ms；
(4)86.6％；
(5)玻璃化温度Tg：149.37℃；
(6)最大紫外吸收波长：358nm；
(7)荧光发射波长：442nm。
实施例4、制备器件OLED-1～OLED-4
1)将涂布了ITO导电层的玻璃基片在清洗剂中超声处理30分钟，在去离子水中冲洗，在丙酮/乙醇混合溶剂中超声30分钟，在洁净的环境下烘烤至完全干燥，用紫外光清洗机照射10分钟，并用低能阳离子束轰击表面。
2)把上述处理好的ITO玻璃基片置于真空腔内，抽真空至1×10-5～9×10-4Pa，在上述阳极层膜上蒸镀化合物2-TNATA作为空穴注入层，蒸镀速率为0.1nm/s，蒸镀膜厚为40nm；
3)在上述空穴注入层上继续蒸镀NPB为空穴传输层，蒸镀速率为0.1nm/s，蒸镀膜厚为10nm；
4)在空穴传输层上继续蒸镀DPEPO为主体材料和本发明实施例1所得化合物17为掺杂材料，DPEPO：化合物17的质量比为90:10，作为器件的有机发光层，蒸镀速率为0.1nm/s，蒸镀所得有机发光层的膜厚为40nm；
5)在有机发光层上继续蒸镀一层Liq作为器件的电子传输层，蒸镀速率为0.1nm/s，蒸镀膜厚为50nm；
6)在电子传输层之上依次蒸镀镁/银合金层作为器件的阴极层，其中镁/银合金层的蒸镀速率为2.0～3.0nm/s，蒸镀膜厚为100nm，镁和银的质量比为1：9，得到本发明提供的OLED器件OLED-1。
按照与上相同的步骤，将步骤4)中的化合物17替换为化合物50，得到本发明提供的OLED-2；
按照与上相同的步骤，将步骤4)中的化合物17替换为实施例3所得化合物95，得到本发明提供的OLED-3；
按照与上相同的步骤，将步骤4)中的化合物17替换为实施例2所得化合物55，得到本发明提供的OLED-4；
所得器件OLED-1至OLED-4的性能检测结果如表1所示。
表1、OLED-1至OLED-4的性能检测结果
由上可知，利用本发明提供的式I所示化合物制备成的器件起亮电压低，亮度保持在500cd/m2条件下，器件的功率效率均超过的6cd/A，而且在器件未封装完好的条件下，其半衰期都达到了600小时。
尽管结合优选实施例对本发明进行了说明，但本发明并不局限于上述实施例，应当理解，在本发明构思的引导下，本领域技术人员可进行各种修改和改进，所附权利要求概括了本发明的范围。

Claims (10)

1.式I所示化合物，
所述式I中：
R1和R2独立地选自氢原子、取代的或未取代的C6-C60芳基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C2-C60杂环芳基中的任意一种；
Ar1、Ar2、Ar3独立地选自取代的或未取代的C6-C60芳基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C6-C60芳硫基、取代的或未取代的C6-C60芳膦基、取代的或未取代的C6-C60芳硅基、取代的或未取代的C6-C60芳硼基、取代的或未取代的C2-C60杂环芳基中的任意一种；
且Ar1和Ar2可以相连形成
所述取代的C6-C60芳基、取代的C6-C60芳氧基、取代的C2-C60杂环芳基、取代的C6-C60芳硫基、取代的C6-C60芳膦基、取代的C6-C60芳硅基、取代的C6-C60芳硼基和取代的C2-C60杂环芳基中，取代基选自甲基、乙基、叔丁基、甲氧基、氰基、苯氧基、卤原子和含有2～8个碳原子的脂肪烃基中的任意一种；
Ar4选自如下基团中的任意一种：
2.根据权利要求1所述的化合物，其特征在于：
所述C6-C60芳基选自苯基、萘基、联苯基、蒽基、联蒽基、对叔丁基苯基、2,4-二氟苯基、4-(N,N-二甲基胺基)苯基、4-(N,N-二苯基胺基)苯基、3-(N,N-二苯基胺基)苯基、芘基、并四苯基、菲基、苯并菲基、苯并蒽基、苯并芘基和芴基中的任意一种；
所述C6-C60芳氧基选自4-苯氧基苯基、二苯并[b,d]呋喃-2-基、二苯并[b,d]呋喃-4-基、苯并呋喃-2-基、苯并呋喃-5-基、苯并呋喃-7-基中的任意一种；
所述C6-C60芳硫基选自二苯并[b,d]噻吩-2-基、二苯并[b,d]噻吩-4-基、4-苯亚砜基苯基、4-苯砜基苯基、苯并噻吩-2-基、苯并噻吩-5-基和苯并噻吩-7-基中的任意一种；
所述C6-C60芳膦基选自4-(二苯基氧膦基)苯基、3-(二苯基氧膦基)苯基和二苯并[b]氧膦-5-(4-苯基)-4-基中的任意一种；
所述C6-C60芳硅基选自4-(三苯基硅基)苯基、4-(二苯基甲基硅基)苯基、3-(三苯基硅基)苯基和3-(二苯基甲基硅基)苯基中的任意一种；
所述C6-C60芳硼基选自4-(二(2,4,6-三甲基)苯基)-硼烷苯基、二苯并[b,d]硼烷-5-苯基-4-基和三苯基硼基中的任意一种；
所述C2-C60的杂环芳基选自如下式II-1至式II-15所示基团中的任意一种：
表示取代位；
所述式II-1～II-15中，Z1、Z2和Z3均独立的选自氢、氘氢、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60烷基、C2-C60烯基、C2-C60炔基、C1-C60烷氧基、C3-C60环烷烃基、C3-C60环烯烃基、C6-C60芳基、至少含有一个-F、-CN或C1-C10烷基的C6-C60芳基、取代的或未取代的C6-C60芳氧基、取代的或未取代的C6-C60芳硫醚基、取代的或未取代的C2-C60杂环芳基中的任意一种；
x1为1～4的整数；
x2为1～3的整数；
x3为1～2的整数；
x4为1～6的整数；
x5为1～5的整数；
T1为氧或硫原子；
所述取代的C6-C60芳氧基、取代的C6-C60芳硫醚基和取代的C2-C60杂环芳基中，取代基选自甲基、乙基、叔丁基、甲氧基、氰基、苯氧基、卤原子和含有2～8个碳原子的脂肪烃基中的任意一种。
3.根据权利要求2所述的化合物，其特征在于：所述式I所示化合物为如下1～105化合物中的任意一种：
4.含有权利要求1-3任一所述式I所示化合物的有机发光二极管材料。
5.权利要求1-3任一所述式I所示化合物在制备有机发光二极管材料中的应用。
6.权利要求1-3任一所述式I所示化合物作为发光层材料在制备有机电致发光器件中的应用。
7.以权利要求1-3任一所述式I所示化合物作为发光层的有机电致发光器件。
8.根据权利要求6所述的应用或权利要求7所述的器件，其特征在于：所述有机电致发光器件由下至上依次由透明基片、阳极、空穴注入层、空穴传输层、有机发光层、电子传输层和阴极层组成。
9.根据权利要求8所述的应用或器件，其特征在于：构成所述透明基片的材料为玻璃或柔性基片；
构成所述阳极层的材料为无机材料或有机导电聚合物；其中，所述无机材料为氧化铟锡、氧化锌、氧化锡锌、金、银或铜；所述有机导电聚合物选自聚噻吩、聚乙烯基苯磺酸钠和聚苯胺中的至少一种；
构成所述空穴注入层的材料为TDATA、m-MTDATA或2-TNATA：
所述TDATA的结构式如下：
所述m-MTDATA的结构式如下：
所述2-TNATA的结构式如下：
构成所述空穴传输层的材料为NPB或TPD：
所述NPB的结构式如下：
所述TPD的结构式如下：
构成所述有机发光层的材料为所述式I所示化合物和主体材料；
其中，所述主体材料为CBP、PVK、DPEPO、TBADN、E3、ADN、dmCBP、mCP、TCzP、Slic-H117、BCPB、Slic-H065、SlimCP、mCBP所示化合物或
所述式I-所示化合物的质量与所述主体材料的质量比为1-10：90；
构成所述电子传输层的材料为Liq、Alq3、Gaq3或BAlq所示化合物；
其中，Liq所示化合物的结构式如下：
构成所述阴极层的材料选自下述元素中的任意一种或任意两种组成的合金或下述元素的氟化物：锂、镁、银、钙、锶、铝、铟、铜、金和银。
10.根据权利要求9所述的应用或器件，其特征在于：所述空穴注入层的厚度为30-50nm；具体为40nm；
所述空穴传输层的厚度为5-15nm；具体为10nm；
所述有机发光层的厚度为10-100nm；具体为40nm；
所述电子传输层的厚度为10-30nm；具体为50nm；
所述阴极层的厚度为90-110nm，具体为100nm。
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Application publication date: 20160413