CN111747892A - 一种热激活延迟荧光材料及电致发光器件 - Google Patents

一种热激活延迟荧光材料及电致发光器件 Download PDF

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CN111747892A
CN111747892A CN202010423386.2A CN202010423386A CN111747892A CN 111747892 A CN111747892 A CN 111747892A CN 202010423386 A CN202010423386 A CN 202010423386A CN 111747892 A CN111747892 A CN 111747892A
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delayed fluorescence
electron
fluorescence material
thermally activated
activated delayed
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CN111747892B (zh
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曹啸松
曾洋
杨楚罗
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Shenzhen University
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Abstract

本发明提供一种热激活延迟荧光材料及电致发光器件，所述热激活延迟荧光材料具有以下结构:
Figure DDA0002496538070000011
本发明提供的热激活延迟荧光材料的分子结构为给体‑受体型分子，其中，缺电子受体含有砜亚胺基团，与含氮杂环电子给体相连接，通过形成扭转的分子内电荷转移或空间电荷转移态，扭转角较大，前线轨道重叠减小，形成小的单重态‑三重态能级差；另外，由于砜亚胺基团分子内和/或分子间相互作用增强，分子刚性增加，无辐射衰减速率减小，发光效率增加；通过亲核功能化引入不同的吸电子功能团到缺电子的砜亚胺N取代位，合成简单，形式多样，能够达到对TADF材料发光性能的有效调控。

Description

一种热激活延迟荧光材料及电致发光器件
技术领域
本发明涉及有机电致发光材料领域，尤其涉及一种热激活延迟荧光材料及电致发光器件。
背景技术
有机发光二极管(organic light-emitting diodes，OLED)，具有自发光、响应时间短、使用温度范围宽、驱动电压低以及能耗低、轻质、高柔性等特点，在新一代平板显示技术、固态照明、柔性显示、透明显示等方面具有广阔的应用前景，因此倍受国内外科技界和产业界关注。
一般认为，注入有机材料的电子和空穴形成单线态和三线态激子的比例为1:3，处于三线态上的电子由于自旋角动量守恒而无法跃迁回基态，因此OLED的最大内量子效率(IQE)不超过25％。通常有两种方法可实现100％内量子效率：(1)室温磷光材料，即一些重金属配合物材料通过贵金属与其配体间较强的自旋-轨道耦合作用，单线态激子通过系间窜越转变为三线态激子，三线态的激子在轨道角动量的参与下跃迁回基态发出磷光，理论内量子效率可达到100％，然而磷光材料现阶段多使用铱、铂等贵金属，成本较高，且基于磷光发射的OLED在高电流下会出现效率滚降现象；(2)热激活延迟荧光(ThermallyActivated Delayed Fluorescence,TADF)材料，TADF材料具有小的单重态-三重态能级差(ΔEST)，三重态激子通过反向系间窜越(RISC)转变成单重态激子，实现100％理论内量子效率，近年来受到广泛关注。
在OLED中，TADF的发射包括4个过程：(1)电子/空穴复合产生单重态和三重态激子；(2)高激发态经由快速振动弛豫(VR)和内转换(IC)向低激发态跃迁；(3)累积在三重激发态(T1)的激子借助于热活化的RISC过程回到激发单重态(S1)；(4)S1上的单重态激子是由电激发或T1的转入产生，再由瞬时荧光(PF)机理辐射释放回到S0。反向系间窜越和辐射跃迁过程均对TADF材料发光效率具有重要影响。减小单重态和三重态之间的能级差(ΔEST)能提高RISC速率，但是较小的轨道重叠可能导致荧光辐射跃迁速率降低。因此，虽然当前的TADF材料可实现可见光区域内的全彩显示，但其发光效率遭遇瓶颈，且合成工艺复杂，大大限制了基于TADF客体的有机电致发光器件的规模化生产。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种热激活延迟荧光材料及电致发光器件，旨在解决热激活延迟荧光材料发光效率较低的问题。
本发明的技术方案如下：
一种热激活延迟荧光材料，其中，所述热激活延迟荧光材料具有以下结构通式：
Figure BDA0002496538050000021
其中，Ar1、Ar2各自独立地选自取代的C6-C60芳香环基，未取代的C6-C60芳香环基，取代的C3-C60芳香杂环基或未取代的C3-C60芳香杂环基；X1选自不成键、单键、-C(R1R2)-、-N(R1)-、-O-、-S-、-S＝O-、-SO2-、-Si(R1R2)-、-Ge(R1R2)-、-P(R1)-或-P＝O(R1)-中的一种；X2选自-R3、-SR3、-Si(R3R4R5)、-COR3、-SO2R3、-POR3R4、-CN或-SCN中的一种；Y1、Y2、R1、R2、R3、R4和R5各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代的C6-C60的芳香环基、未取代的C6-C60的芳香环基、取代的C3-C60的芳杂环基或未取代的C3-C60的芳杂环基的一种；D1为含有杂原子的给电子基团；D2为含有杂原子的给电子基团或氢。
在本发明中，还提供一种电致发光器件，包括发光层，所述发光层包括本发明所述的热激活延迟荧光材料。
有益效果：本发明提供的热激活延迟荧光材料的分子结构为给体-受体(D-A)型分子，其中缺电子受体(Acceptor)含有砜亚胺基团，与含氮杂环电子给体(Donor)相连接，通过形成扭转的分子内电荷转移或空间电荷转移态，扭转角较大，前线轨道重叠减小，形成小的单重态-三重态能级差；并且由于3CT态与局域激发三重态3LE发生能量简并，反向系间窜越速率(RISC)增加，非辐射跃迁受到抑制；另外，由于砜亚胺基团分子内和/或分子间相互作用增强，分子刚性增加，无辐射衰减速率减小，发光效率增加；通过亲核功能化引入不同的吸电子功能团到缺电子的砜亚胺N取代位，合成简单，形式多样，能够达到对TADF材料发光性能的有效调控。
附图说明
图1为化合物45、49、58的循环伏安曲线。
图2为差式扫描量热法测量的化合物45、49、58的热学性质。
图3为化合物45、49、58的热重分析。
图4为本发明提供的一种电致发光器件较佳实施例的结构示意图。
具体实施方式
本发明提供一种热激活延迟荧光材料及电致发光器件，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本实施例提供了一种热激活延迟荧光材料，所述热激活延迟荧光材料具有以下结构通式：
Figure BDA0002496538050000041
其中，Ar1、Ar2各自独立地选自取代的C6-C60芳香环基，未取代的C6-C60芳香环基，取代的C3-C60芳香杂环基或未取代的C3-C60芳香杂环基；X1选自不成键、单键、-C(R1R2)-、-N(R1)-、-O-、-S-、-S＝O-、-SO2-、-Si(R1R2)-、-Ge(R1R2)-、-P(R1)-或-P＝O(R1)-中的一种；X2选自-R3、-SR3、-Si(R3R4R5)、-COR3、-SO2R3、-POR3R4、-CN或-SCN中的一种；Y1、Y2、R1、R2、R3、R4和R5各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代的C6-C60的芳香环基、未取代的C6-C60的芳香环基、取代的C3-C60的芳杂环基或未取代的C3-C60的芳杂环基的一种；D1为含有杂原子的给电子基团；D2为含有杂原子的给电子基团或氢。
本实施例中，所述热激活延迟荧光材料的分子结构为给体-受体(D-A)型分子，其中缺电子受体(Acceptor)含有砜亚胺基团，与含氮杂环电子给体(Donor)相连接，通过形成扭转的分子内电荷转移或空间电荷转移态，扭转角较大，前线轨道重叠减小，形成小的单重态-三重态能级差；并且由于3CT态与局域激发三重态3LE发生能量简并，反向系间窜越速率(RISC)增加，非辐射跃迁受到抑制；另外，由于砜亚胺基团分子内和分子间相互作用增强，分子刚性增加，无辐射衰减速率减小，发光效率增加；通过亲核功能化引入不同的吸电子功能团到缺电子的砜亚胺N取代位，合成简单，形式多样，能够达到对TADF材料发光性能的有效调控。
因此，将上述热激活延迟荧光材料作为有机发光层材料应用于电致发光器件中能够有效提升电致发光器件的发光效率。
在一些实施方式中，所述Y1与Y2能够相互以共价键方式相连成环，R1、R2、R3、R4和R5能够以共价键方式相连成环。
在一些实施方式中，所述D1、D2独立地选自以下结构中的一种：
Figure BDA0002496538050000051
其中，X3、X4和X5各自独立地选自-O-、-S-、-S＝O-、-SO2-、-C(R8R9)-、-Si(R8R9)-、-Ge(R8R9)-、-N(R8)-、-P(R8)-、-P＝O(R8)-或不成键中的一种；R6、R7、R8、R9、Y3、Y4和Y5各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代或未取代的C6-C60芳香环基及取代或未取代的C3-C60芳杂环基中的一种；所述R6、R7、R8与R9能够以共价键方式相连成环，Y3、Y4与Y5能够以共价键方式相连成环。
在一些实施方式中，所述热激活延迟荧光材料为以下结构中的一种：
Figure BDA0002496538050000052
Figure BDA0002496538050000061
Figure BDA0002496538050000071
Figure BDA0002496538050000081
Figure BDA0002496538050000091
Figure BDA0002496538050000101
但不限于此。
在一些实施方式中，还提供一种电致发光器件，包括发光层，所述发光层包括上述任一所述的热激活延迟荧光材料。
在一些实施方式中，还提供一种电致发光器件，所述发光层包括0.01％-100％的上述热激活延迟荧光材料和0-99.9％的有机功能材料。
在一些实施方式中，所述有机电致发光器件包括功能层，所述功能层包括分别设置在所述发光层上下两端的电子功能层和空穴功能层；所述电子功能层包括电子注入层、电子传输层和空穴阻隔层；所述空穴功能层包括空穴注入层、空穴传输层和电子阻隔层。
下面通过具体的实施例对本发明进行详细说明。
实施例1
化合物11的制备方法包括以下步骤：
1)、中间体11-1的制备反应式如下：
Figure BDA0002496538050000111
准备一个25mL干燥的圆底烧瓶，0℃温度下加入4-溴二苯基亚砜(1.12g,4.0mmol)、叠氮化钠(0.31g,4.8mmol)和8mL三氯甲烷，逐滴加入1.60mL浓硫酸，混合物45℃加热，搅拌12h。4-溴二苯基亚砜完全反应完后，冷却至室温，水淬灭反应，三氯甲烷萃取有机层，盐洗，有机层用无水硫酸钠干燥后过滤，浓缩，粗产物通过柱层析色谱柱进一步纯化，得到无色固体，即中间体11-1(0.83g,2.8mmol)，HPLC纯度99.3％，产率70％。MS(MALDI-TOF):m/z 294.9[M+]；
2)、中间体11-2的制备反应式如下：
Figure BDA0002496538050000112
在20mL舒伦克封管中加入中间体11-1(29mg,0.1mmol)，二苯二硫醚(33mg,0.15mmol)，碘化亚铜(3.8mg,0.02mmol)，醋酸钠(24.6mg,0.3mmol)和DMSO(2mL)，混合物60℃搅拌15h，反应完全后粗产物通过柱层析色谱柱纯化，得到中间体11-2(28mg,0.07mmol)，HPLC纯度99.5％，产率70％。MS(MALDI-TOF):m/z 402.9[M+]。
3)、化合物11的制备反应式如下：
Figure BDA0002496538050000113
在20mL舒伦克封管中加入中间体11-1(29mg,0.1mmol)，二苯二硫醚(33mg,0.15mmol)，碘化亚铜(3.8mg,0.02mmol)，醋酸钠(24.6mg,0.3mmol)和DMSO(2mL)，混合物60℃搅拌15h，反应完全后粗产物通过柱层析色谱柱纯化，得到中间体11-2(28mg,0.07mmol)，HPLC纯度99.5％，产率70％。MS(MALDI-TOF):m/z 402.9[M+]。
实施例2
化合物15的制备方法包括以下步骤：
1)、中间体15-1的制备反应式如下：
Figure BDA0002496538050000121
在50mL圆底烧瓶中加入4-溴二苯基亚砜(1.13g,4.0mmol,1.0equiv.)，PhI(OAc)2(3.87g,12.0mmol,3.0equiv.)，氨基甲酸铵(1.25g,16.0mmol,4.0equiv.)和甲醇(8.0mL)，室温敞口搅拌30min后旋转蒸发除去溶剂，粗产物通过柱色谱法纯化，真空干燥，得到无色固体，即中间体15-1(0.83g,2.80mmol)，HPLC纯度99.2％，产率70％。MS(MALDI-TOF):m/z294.9[M+]。
2)、中间体15-2的制备反应式如下：
Figure BDA0002496538050000122
在150mL单口圆底烧瓶中加入中间体15-1(0.75g,3.0mmol)、三乙胺(0.68mL,0.83g,5.2mmol)和50mL二氯甲烷，溶解，冰浴冷却，逐滴加入苯甲酰氯(0.55mL,0.6g,6.0mmol)。混合物逐渐升至室温，搅拌12h。水洗(2x 100mL)、盐洗(100mL)，有机层用无水硫酸镁干燥后过滤，浓缩，粗产物通过柱层析色谱柱进一步纯化，得到白色固体，即中间体15-2(1.02g,2.55mmol)，HPLC纯度99.7％，产率85％。MS(MALDI-TOF):m/z400.3[M+]。
3)、化合物15的制备反应式如下：
Figure BDA0002496538050000131
将中间体15-2(1.0g,2.50mmol,1.0equiv.)，9,10-二氢-9,9-二甲基吖啶(DMAC，1.2equiv.)，醋酸钯(0.1equiv.)，三叔丁基膦四氟硼酸盐(0.2equiv.)，碳酸铯(2.5equiv.)加入连有冷凝管的两口瓶中，除气并通入氮气，反复三次。加入干燥甲苯(10mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到淡黄色固体，即化合物15(1.19g,2.25mmol)，HPLC纯度99.2％，产率：90％。MS(MALDI-TOF):m/z 528.2[M+]。元素分析结果(％)：C 77.25；H 5.34；N 5.30；O 6.05；S6.06。
实施例3
化合物45的制备方法包括以下步骤：
1)、中间体45-1的制备反应式如下：
Figure BDA0002496538050000132
在250mL单口圆底烧瓶中依次加入2-溴二苯并噻吩(2.62g,10.0mmol)，碘苯二乙酸(16.10g,50.0mmol,5equiv.)，碳酸铵(2.88g,30.0mmol,3equiv.)和80mL甲醇，将上述混合物室温搅拌48小时。旋转蒸发除去溶剂后柱层析纯化，真空干燥得到无色固体2.40g(8.20mmol)，HPLC纯度99.5％，产率82％。MS(MALDI-TOF):m/z 293.0[M+]。
2)、中间体45-2的制备反应式如下：
Figure BDA0002496538050000141
在150mL单口圆底烧瓶中依次加入中间体45-1(0.75g,2.6mmol)溶解在50mL二氯甲烷中，二苯基次磷酰氯(1.21g,0.98mL,5.2mmol)和吡啶(0.41mL,0.41g,5.2mmol)。反应混合物回流24h。待反应液冷却至室温，溶液水洗(2x 100mL)、盐洗(100mL)，无水硫酸镁干燥后过滤，浓缩，粗产物通过柱层析色谱柱进一步纯化，得到白色固体，即中间体45-2(0.70g,1.7mmol)，HPLC纯度99.7％，产率65％。MS(MALDI-TOF):m/z493.0[M+]。
3)、化合物45的制备反应式如下：
Figure BDA0002496538050000142
将中间体45-2(0.5g,1.01mmol,1.0equiv.)，9,10-二氢-9,9-二甲基吖啶(DMAC，1.2equiv.)，醋酸钯(0.1equiv.)，三叔丁基膦四氟硼酸盐(0.2equiv.)，碳酸铯(2.5equiv.)加入连有冷凝管的两口瓶中，除气并通入氮气，反复三次。加入干燥甲苯(10mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到淡黄色固体，即化合物45(0.57g,0.91mmol)，HPLC纯度99.1％，产率：90％。MS(MALDI-TOF):m/z 622.2[M+]。元素分析结果(％)：C 75.22；H 5.02；N 4.50；O 5.14；P4.97；S 5.15
实施例4
化合物49的制备方法包括以下步骤：
1)、中间体49-2的制备反应式如下：
Figure BDA0002496538050000151
在150mL单口圆底烧瓶中加入中间体45-1(0.75g,2.6mmol)、三乙胺(0.59mL,0.72g,5.2mmol)和50mL二氯甲烷，溶解，冰浴冷却，逐滴加入苯甲酰氯(0.48mL,0.52g,5.2mmol)。混合物逐渐升至室温，搅拌12h。水洗(2x 100mL)、盐洗(100mL)，有机层用无水硫酸镁干燥后过滤，浓缩，粗产物通过柱层析色谱柱进一步纯化，得到白色固体，即中间体49-2(0.84g,2.1mmol)，HPLC纯度99.2％，产率83％。MS(MALDI-TOF):m/z 397.0[M+]。
2)、化合物49的制备反应式如下：
Figure BDA0002496538050000152
将中间体49-2(0.5g,1.26mmol,1.0equiv.)，9,10-二氢-9,9-二甲基吖啶(DMAC，1.2equiv.)，醋酸钯(0.1equiv.)，三叔丁基膦四氟硼酸盐(0.2equiv.)，碳酸铯(2.5equiv.)加入连有冷凝管的两口瓶中，除气并通入氮气，反复三次。加入干燥甲苯(10mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到淡黄色固体，即化合物49(0.58g,1.11mmol)，HPLC纯度99.5％，产率88％。MS(MALDI-TOF):m/z 526.1[M+]。元素分析结果(％)：C 77.54；H 4.98；N 5.32；O 6.08；S6.09。
实施例5
化合物115的制备方法包括以下步骤：
1)、中间体115-1的制备反应式如下：
Figure BDA0002496538050000161
在500mL单口圆底烧瓶中依次加入2-溴噻蒽(2.95g,10.0mmol)，碘苯二乙酸(32.20g,100.0mmol,10equiv.)，碳酸铵(5.76g,60.0mmol,6equiv.)和150mL甲醇，将上述混合物室温搅拌48小时。旋转蒸发除去溶剂后柱层析纯化，真空干燥得到无色固体3.03g(8.50mmol)，HPLC纯度99.2％，产率85％。MS(MALDI-TOF):m/z 355.9[M+]。
2)、中间体115-2的制备反应式如下：
Figure BDA0002496538050000162
在500mL单口圆底烧瓶中依次加入中间体115-1(0.93g,2.6mmol)溶解在100mL二氯甲烷中，二苯基次磷酰氯(2.42g,1.96mL,10.2mmol)和吡啶(0.82mL,0.82g,10.2mmol)。反应混合物回流24h。待反应液冷却至室温，溶液水洗(2x 200mL)、盐洗(200mL)，无水硫酸镁干燥后过滤，浓缩，粗产物通过柱层析色谱柱进一步纯化，得到白色固体，即中间体115-2(1.18g,1.56mmol)，HPLC纯度99.7％，产率60％。MS(MALDI-TOF):m/z756.0[M+]
3)、化合物115的制备反应式如下：
Figure BDA0002496538050000171
将中间体115-2(1.18g,1.56mmol,1.0equiv.)，9,10-二氢-9,9-二甲基吖啶(DMAC，1.2equiv.)，醋酸钯(0.1equiv.)，三叔丁基膦四氟硼酸盐(0.2equiv.)，碳酸铯(2.5equiv.)加入连有冷凝管的两口瓶中，除气并通入氮气，反复三次。加入干燥甲苯(30mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到淡黄色固体，即化合物115(1.17g,1.33mmol)，HPLC纯度99.5％，产率85％。MS(MALDI-TOF):m/z 885.2[M+]。元素分析结果(％)：C 69.14；H 4.66；N4.74；O 7.22；P6.99；S 7.24。
实施例6
化合物150的制备方法包括以下步骤：
1)、中间体150-1的制备反应式如下：
Figure BDA0002496538050000181
在250mL单口圆底烧瓶中依次加入2-溴二苯并噻吩(3.13g,10.0mmol)，碘苯二乙酸(16.10g,50.0mmol,5equiv.)，碳酸铵(2.88g,30.0mmol,3equiv.)和80mL甲醇，将上述混合物室温搅拌24小时。旋转蒸发除去溶剂后柱层析纯化，真空干燥得到无色固体2.93g(8.50mmol)，HPLC纯度99.4％，产率85％。MS(MALDI-TOF):m/z 344.2[M+]。
2)、中间体150-2的制备反应式如下：
Figure BDA0002496538050000182
在20mL舒伦克封管中加入中间体150-1(34mg,0.1mmol)，双(三氟甲基)二硫化物(30mg,0.15mmol)，碘化亚铜(3.8mg,0.02mmol)，醋酸钠(24.6mg,0.3mmol)和DMSO(2mL)，混合物60℃搅拌15h，反应完全后粗产物通过柱层析色谱柱纯化，得到中间体150-2(31mg,0.07mmol)，HPLC纯度99.5％，产率70％。MS(MALDI-TOF):m/z 442.9[M+]。
3)、化合物150的制备反应式如下所示：
Figure BDA0002496538050000183
将中间体150-2(0.75g,1.69mmol,1.0equiv.)，吩噁嗪(1.2equiv.)，醋酸钯(0.1equiv.)，三叔丁基膦四氟硼酸盐(0.2equiv.)，碳酸铯(2.5equiv.)加入连有冷凝管的两口瓶中，除气并通入氮气，反复三次。加入干燥甲苯(10mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到黄色固体，即化合物150(0.79g,1.44mmol)，HPLC纯度99.5％，产率85％。MS(MALDI-TOF):m/z 546.6[M+]。元素分析结果(％)：C 63.73；H 3.14；F 10.43；N 5.13；O 5.85；S 11.73。
实施例7
化合物161的制备方法包括以下步骤：
1)、中间体161-2的制备反应式如下：
Figure BDA0002496538050000191
在150mL单口圆底烧瓶中加入中间体15-1(0.75g,3.0mmol)、4-溴苯甲酰氯(0.55mL,1.32g,6.0mmol)、三乙胺(0.68mL,0.83g,5.2mmol)和50mL二氯甲烷，溶解，冰浴冷却。混合物逐渐升至室温，搅拌12h。水洗(2x 100mL)、盐洗(100mL)，有机层用无水硫酸镁干燥后过滤，浓缩，粗产物通过柱层析色谱柱进一步纯化，得到白色固体，即中间体161-2(1.22g,2.55mmol)，HPLC纯度99.7％，产率85％。MS(MALDI-TOF):m/z479.2[M+]。
4)、化合物161的制备反应式如下：
Figure BDA0002496538050000201
将中间体161-2(1.22g,2.55mmol,1.0equiv.)，吩噻嗪(1.2equiv.)，醋酸钯(0.1equiv.)，三叔丁基膦四氟硼酸盐(0.2equiv.)，碳酸铯(2.5equiv.)加入连有冷凝管的两口瓶中，除气并通入氮气，反复三次。加入干燥甲苯(10mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到淡黄色固体，即化合物161(1.37g,2.30mmol)，HPLC纯度99.2％，产率：90％。MS(MALDI-TOF):m/z 596.0[M+]。元素分析结果(％)：C 62.31；H 3.54；Br 13.37；N 4.69；O 5.35；S 10.73。
实施例8
化合物181的制备方法包括以下步骤：
1)、中间体181-2的制备反应式如下：
Figure BDA0002496538050000202
在50mL圆底烧瓶中加入中间体15-1(0.75g,3.0mmol)，氯硫氰酸(0.1equiv.)，钯催化剂(0.01equiv.)，室温搅拌5min后柱层析纯化，得到中间体181-2(0.80g,2.28mmol)，产率76％。MS(MALDI-TOF):m/z 351.9[M+]。
2)、化合物181的制备反应式如下：
Figure BDA0002496538050000211
将中间体181-2(0.80g,2.28mmol,1.0equiv.)，10,10-二苯基-5,10-二氢二苯并[b,e][1,4]氮杂西林(1.2equiv.)，醋酸钯(0.1equiv.)，三叔丁基膦四氟硼酸盐(0.2equiv.)，碳酸铯(2.5equiv.)加入连有冷凝管的两口瓶中，除气并通入氮气，反复三次。加入干燥甲苯(10mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到淡黄色固体，即化合物181(1.28g,2.05mmol)，HPLC纯度99.2％，产率：90％。MS(MALDI-TOF):m/z 621.9[M+]。元素分析结果(％)：C 71.47；H 4.38；N 6.76；O 2.57；S10.31；Si 4.52。
实施例9
化合物190的制备方法包括以下步骤：
1)、中间体190-1的制备反应式如下：
Figure BDA0002496538050000212
在250mL圆底烧瓶中加入2-溴-10H-吩噻嗪(1.5g,5.39mmol)，2-碘代丙烷(0.92g,5.39mmol)和甘油(70mL)，混合物回流28h后，粗产物通过柱层析色谱柱纯化，得到中间体190-1(1.50g,4.69mmol)，HPLC纯度99.5％，产率87％。MS(MALDI-TOF):m/z 319.0[M+]。
2)、中间体190-2的制备反应式如下：
Figure BDA0002496538050000221
在250mL单口圆底烧瓶中依次加入中间体190-1(3.19g,10.0mmol)，碘苯二乙酸(16.10g,50.0mmol,5equiv.)，碳酸铵(2.88g,30.0mmol,3equiv.)和80mL甲醇，将上述混合物室温搅拌48小时。旋转蒸发除去溶剂后柱层析纯化，真空干燥得到无色固体2.87g(8.20mmol)，HPLC纯度99.4％，产率82％。MS(MALDI-TOF):m/z 350.0[M+]。
3)、化合物190的制备反应式如下：
Figure BDA0002496538050000222
将中间体190-3(1.86g,4.56mmol,1.0equiv.)，3,6-二甲氧基-9H-咔唑(1.2equiv.)，醋酸钯(0.1equiv.)，三叔丁基膦四氟硼酸盐(0.2equiv.)，碳酸铯(2.5equiv.)加入连有冷凝管的两口瓶中，除气并通入氮气，反复三次。加入干燥甲苯(10mL)，在氮气下回流24h。反应液冷却至室温后，旋转蒸发除去溶剂，粗产物通过硅胶色谱柱提纯，得到黄色固体，即化合物190(2.17g,3.92mmol)，HPLC纯度99.1％，产率86％。MS(MALDI-TOF):m/z553.2[M+]。元素分析结果(％)：C 67.25；H 4.92；N 7.59；O 8.67；S 11.58。
本发明的上述热激活延迟材料可适用于OLED器件中的发光层。以下结合附图4的器件结构，通过化合物45、49、58这三个实施例详细说明本发明的热激活延迟材料在OLED器件中作为发光层材料的应用效果。
图1为化合物45、49、58的电化学循环伏安图，图2为化合物45、49、58的差式扫描量热分析图，图3为化合物45、49、58的热重分析图。
本发明提供的电致发光器件，参照附图4所示结构，可包括导电玻璃衬底1(ITO)、空穴注入层2(12-六氮杂苯并菲，HAT-CN)、空穴传输层3(4,4’-环己基二[N,N-二(4-甲基苯基)苯胺]，TAPC)、电子阻挡层4(1,3-双(咔唑-9-基)苯，mCP)、发光层5(本发明具有热激活延迟荧光的化合物掺入主体材料的混合物)、空穴阻挡层6(二[2-((氧代)二苯基膦基)苯基]醚，DPEPO)、电子传输层7(3',1″-三联苯-3,3″-二基二吡啶，TmPyPB)、电子注入层8(8-羟基喹啉-锂，Liq)、阴极层9(Al)。其中HAT-CN、mCP、DPEPO、TmPyPB、Liq、TAPC的结构式分别如下：
Figure BDA0002496538050000231
参照附图4所示结构，制造OLED器件，具体步骤为：将镀有氧化铟锡(ITO)的玻璃基板分别用去离子水、丙酮、异丙醇超声洗涤30分钟，紫外线臭氧处理15分钟后，将玻璃基板传送至真空沉积室中；旋涂、蒸镀各有机层及阴极铝层；将该器件从沉积室传送至手套箱中进行封装。
器件具体结构如下：
实施例2-1：
ITO/HAT-CN(5nm)/TAPC(30nm)/mCP(10nm)/DPEPO:10wt.％化合物45(20nm)/DPEPO(10nm)/TmPyPB(30nm)/Liq(1.5nm)/Al(100nm)。
实施例2-2：
ITO/HAT-CN(5nm)/TAPC(30nm)/mCP(10nm)/DPEPO:10wt.％化合物49(20nm)/DPEPO(10nm)/TmPyPB(30nm)/Liq(1.5nm)/Al(100nm)。
实施例2-3：
ITO/HAT-CN(5nm)/TAPC(30nm)/mCP(10nm)/DPEPO:10wt.％化合物58(20nm)/DPEPO(10nm)/TmPyPB(30nm)/Liq(1.5nm)/Al(100nm)。
器件的亮度、发光效率、EQE(外量子效率)由带有校正过的硅光电二极管的Keithley源测量系统(Keithley 2400Sourcemeter、Keithley 2000Currentmeter)完成，寿命结果LT97(亮度衰减到初始亮度97％时达到的时间)由弗士达的FS-MP96寿命测试系统完成，所有测试均在室温大气中完成，测试结果见表1。而且，R1的芳香环结构中的氢被氘取代后，与取代之前的性能基本相当，在此不再列举。
器件的电流-亮度-电压特性由带有校正过的硅光电二极管的Keithley源测量系统(Keithley 2400 Sourcemeter、Keithley 2000 Currentmeter)测定，所有测试均在室温大气中完成，测试结果见表1。
Figure BDA0002496538050000241
从表1可以看出，本发明上述的实施例体现了如下技术效果：
本发明所述发光材料的分子结构为D-A型分子，其中缺电子受体(Acceptor)含有砜亚胺基团，与含氮杂环电子给体(Donor)相连接，通过形成扭转的分子内电荷转移或空间电荷转移态，扭转角大于80°，前线轨道重叠减小，形成小的单重态-三重态能级差，能够实现TADF性质；由于3CT态与局域激发三重态3LE发生能量简并，促进能量上转换，反向系间窜越速率(RISC)增加，光致发光量子产率(PLQY)增强，非辐射跃迁受到抑制；另外，由于砜亚胺基团分子内/分子间相互作用增强，分子刚性增加，无辐射衰减速率减小，发光效率增加；将这些材料用作掺杂有机电致发光器件发光层中的发光客体时，其最大外量子效率可高于20％，器件外量子效率得到了大幅度提高；通过亲核功能化引入不同的吸电子功能团到缺电子的砜亚胺N取代位，方法简单，成本降低，形式多样，能够达到对TADF材料性能的有效调控。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (10)

1.一种热激活延迟荧光材料，其特征在于，所述热激活延迟荧光材料具有以下结构通式：
Figure FDA0002496538040000011
其中，Ar1、Ar2各自独立地选自取代的C6-C60芳香环基，未取代的C6-C60芳香环基，取代的C3-C60芳香杂环基或未取代的C3-C60芳香杂环基；X1选自不成键、单键、-C(R1R2)-、-N(R1)-、-O-、-S-、-S＝O-、-SO2-、-Si(R1R2)-、-Ge(R1R2)-、-P(R1)-或-P＝O(R1)-中的一种；X2选自-R3、-SR3、-Si(R3R4R5)、-COR3、-SO2R3、-POR3R4、-CN或-SCN中的一种；Y1、Y2、R1、R2、R3、R4和R5各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代的C6-C60的芳香环基、未取代的C6-C60的芳香环基、取代的C3-C60的芳杂环基或未取代的C3-C60的芳杂环基的一种；D1为含有杂原子的给电子基团；D2为含有杂原子的给电子基团或氢。
2.根据权利要求1所述热激活延迟荧光材料，其特征在于，所述Y1与Y2相互以共价键方式相连成环，R1、R2、R3、R4和R5以共价键方式相连成环。
3.根据权利要求1所述热激活延迟荧光材料，其特征在于，所述D1、D2独立地选自以下结构中的一种：
Figure FDA0002496538040000012
其中，X3、X4和X5各自独立地选自-O-、-S-、-S＝O-、-SO2-、-C(R8R9)-、-Si(R8R9)-、-Ge(R8R9)-、-N(R8)-、-P(R8)-、-P＝O(R8)-或不成键中的一种；R6、R7、R8、R9、Y3、Y4和Y5各自独立地选自氢、氘、烯基、炔基、胺基、硝基、羰基、砜基、卤素、氰基、烷基、烷氧基、取代或未取代的C6-C60芳香环基及取代或未取代的C3-C60芳杂环基中的一种。
4.根据权利要求3所述的热激活延迟荧光材料，其特征在于，所述R6、R7、R8与R9能够以共价键方式相连成环，Y3、Y4与Y5能够以共价键方式相连成环。
5.根据权利要求1所述热激活延迟荧光材料，其特征在于，所述热激活延迟荧光材料为以下结构中的一种：
Figure FDA0002496538040000021
Figure FDA0002496538040000031
Figure FDA0002496538040000041
Figure FDA0002496538040000051
Figure FDA0002496538040000061
Figure FDA0002496538040000071
6.一种电致发光器件，包括发光层，其特征在于，所述发光层包括权利要求1-5任一所述的热激活延迟荧光材料。
7.根据权利要求6所述的电致发光器件，其特征在于，所述发光层包括0.01％-100％的热激活延迟荧光材料和0-99.9％的有机功能材料。
8.根据权利要求6所述电致发光器件，其特征在于，所述有机电致发光器件包括功能层，所述功能层包括分别设置在所述发光层上下两端的电子功能层和空穴功能层。
9.根据权利要求7所述的电致发光器件，其特征在于，所述电子功能层包括电子注入层、电子传输层和空穴阻隔层。
10.根据权利要求7所述的电致发光器件，其特征在于，所述空穴功能层包括空穴注入层、空穴传输层和电子阻隔层。
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