基于二苯砜的热激活延迟荧光材料的合成及性能研究

论文总字数：22247字

摘 要

热激活延迟荧光(TADF)材料是当前有机电致发光领域的研究热点。不含贵金属的热激活延迟荧光分子由于存在从最低三线态(T₁)到最低单线态(S₁)的反向隙间窜越，从而具有独特的光电性能。TADF材料通过反向隙间窜越(T₁→S₁)，收获由荧光转变来的三线态激子，有望代替贵金属配合物用于制备低成本的光电器件。

本文设计和合成了系列基于空穴传输基团咔唑、三苯胺和电子传输基团二苯砜的TADF 材料。研究了这些材料的构效关系，包括光物理性质和电化学性质。主要研究内容如下：

(1) 合成了以N-苯基咔唑基团、以间位接两个咔唑的苯环基团作为空穴传输基团，分别通过在苯环的3,5-位和在苯环的另一个间位引入电子传输基团二苯砜基，得到了两种新型TADF材料9-（3,5-二(4-(苯基磺酰基)苯基)苯基)-9H-咔唑(TM1)和9-(3-(4-(苯基磺酰基)苯基)-5-(9H-咔唑基)苯基)-9H-咔唑(TM2)。系统研究了分子结构对这些材料的光物理、电化学和热稳定性的影响。TM1和TM2的△E_ST仅为0.19 eV 和0.27 eV，可作为TADF 材料。

(2) 合成了以N-苯基咔唑基团、以三苯胺基团作为空穴传输基团，分别通过在咔唑环的3-位和在苯环的对位引入电子传输基团二苯砜基，得到了两种新型TADF材料9-苯基-3-(4-(苯基磺酰基)苯基)-9H-咔唑(TM3)和4-(4-(苯基磺酰基)苯基)-N，N-二苯基苯胺(TM4)。系统研究了分子结构对这些材料的光物理、电化学和热稳定性的影响。TM3和TM4的△E_ST为0.99 eV 和0.58 eV，不宜作为TADF 材料。

关键词：热激活延迟荧光;光电材料;有机电致发光

Abstract

The design and characterization of thermally activated delayed fluorescence(TADF) materials for optoelectronic applications represents an active area of recent research in organoelectronics. Noble metal-free TADF molecules offer unique optical and electronic properties arising from the efficient transition and interconversion between the lowest singlet (S₁) and triplet (T₁) excited states. Their ability to harvest triplet excitons for fluorescence through facilitated reverse intersystem crossing (T₁→S₁) could directly impact their properties and performances, which is attractive for a wide variety of low-cost optoelectronic devices. It is very important for us to develop novel TADF materials.

In this thesis, we have designed and synthesized a series of novel materials based on electron

-transporting groups such as diphenyl sulfone,hole-transporting groups such as triphenylamine, carbazole. The structure-property relationships including photophysical, electrochemical and electroluminescent properties have been systematically investigated. The main contents are described as follows:

（1）A series of bipolar TADF materials named 9- (3,5-bis (4- (phenylsulfonyl) phenyl) phenyl) -9H- carbazole (TM1) based on N-phenyl carbazole group as a hole-transport group and introducing electron transport group diphenyl sulfone on 3,5-position of the benzene ring have been synthesized. A series of bipolar TADF materials named 9- (3- (4- (phenylsulfonyl) phenyl) -5- (9H- carbazol-9-yl) phenyl) -9H- carbazole (TM2) based on meta position of the phenyl ring by two carbazole group as a hole transport group and introducing electron transport group diphenyl sulfone on the meta position of the benzene ring have been synthesized. We studied the influence of molecular structure on the photophysics of these materials, electrochemical and thermal stability. TM1 and TM2 of △EST only 0.19 eV and 0.27 eV, as TADF material.

（2）A series of bipolar TADF materials named 9-phenyl-3- (4- (phenylsulfonyl) phenyl) -9H- carbazole (TM3) based on N-phenyl carbazole group as a hole-transport group and ntroducing electron transport group diphenyl sulfone on Carbazole ring have been synthesized. A series of bipolar TADF materials named 4- (4- (phenylsulfonyl) phenyl) -N, N- diphenyl aniline (TM4) based on Triphenylamine group as a hole-transport group and introducing electron transport group diphenyl sulfone on the benzene ring of position have been synthesized. We studied the influence of molecular structure on the photophysics of these materials, electrochemical and thermal stability. TM3 and TM4 of △E_ST to 0.99 eV and 0.58 eV, not as TADF material.

Keywords: thermally activated delayed fluorescence; Optoelectronic Materials; organic light emitting diodes

目 录

摘 要 I

Abstract II

第一章 引 言 1

第二章 实验部分 3

2.1药品与试剂、设备与仪器 3

2.2 目标化合物的设计与合成 3

2.2.1 设计方案 3

2.2.2 中间体的制备 4

2.2.3 目标化合物的合成 7

2.3 小结 10

第三章 性能研究 11

3.1 设备与仪器 11

3.2 紫外-可见吸收光谱的测定 11

3.3 荧光发射光谱的测定 12

3.4 延迟荧光性能测试 13

3.5 电化学测试 13

3.6 理论计算 15

第四章 结论 16

致谢 17

参考文献 18

附录 20

第一章 引 言

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