【作者】 张亮；

【导师】 陈传峰；

【作者基本信息】 中国矿业大学 ， 应用化学， 2020， 博士

【摘要】 本论文主要介绍了基于酰亚胺超长室温磷光（RTP）材料的光物理性质及其功能化应用,制备了一系列具有热激活延迟荧光（TADF）和超长RTP性质的材料并且介绍了它们在高级防伪加密领域的应用;此外还合成了一类新型TADF材料,并且对该材料进行了光物理性质的表征以及有机发光二极管（OLED）器件的应用。具体内容如下:第一,通过改变邻苯二甲酰亚胺上的卤素取代基团,设计合成了三种新型的有机发光材料Br-Al-Cz、Cl-Al-Cz和F-AI-Cz。它们不仅具有非常明显的聚集诱导发光（AIE）效应,还表现出显著的TADF以及晶态诱导的RTP性质。其中,化合物Br-Al-Cz表现出肉眼可见的长余辉室温磷光现象,因此在数据加密等领域具有潜在用途。第二,通过改变咔唑基团的位置,制备了一系列基于酰亚胺的新型发光材料o-AI-Cz、m-AI-Cz和p-AI-Cz。这类发光材料在薄膜和结晶态下的单重态-三重态能级差(ΔE_ST)非常都小,因此表现出显著的TADF和RTP性质。其中,o-AI-Cz具有超长RTP性质,其在空气中的磷光寿命为602 ms,因此可以用作高级加密材料中的防伪油墨。此外,o-AI-Cz具有强烈的分子内相互作用,而p-AI-Cz在固态下可以形成直径为13.171?的规则六边形孔,这可能是它们磷光寿命不同的主要原因。第三,基于酰亚胺设计合成了一种新型的室温磷光材料AI-N-Cz。该材料具有高达775 ms的超长磷光寿命,是其异构体AI-Cz（1.9 ms）的磷光寿命的400倍以上。AI-N-Cz的超长RTP可能是由于较小的ΔE_ST和H聚集的结合,这为设计超长有机室温磷光材料提供了一种非常有效的策略。第四,通过改变电子给体的种类,制备了一组基于喹啉受体的新型发光分子Fene、Fens和Yad。这组分子具有非常小的ΔE_ST和扭曲的刚性结构,这使它们表现出显著的TADF和AIE性质。而且,它们还显示出聚集诱导延迟荧光（AIDF）性质和良好的光致发光（PL）特性。此外,采用Fene、Fens和YAD作为发光层制备非掺杂OLED器件,分别获得14.9%,13.1%和17.4%的最大外部量子效率(EQE_max)。这些器件都表现出较低的开启电压（3 V至3.2 V）,这可能是由于其扭曲的构型和AIDF性质所致。该结果表明基于喹啉的发光体在非掺杂的OLED中具有非常广阔的应用前景。该论文有106幅图、10个表和147篇参考文献。更多还原

【Abstract】 In this dissertation,we have studied the photophysical properties and functionalization of imide-based ultralong room-temperature phosphorescent（RTP）materials and prepared a series of materials with thermally activated delayed fluorescence（TADF）and ultralong RTP properties.In addition,we also synthesized a new type of TADF materials and characterized the photophysical properties of the material and the application of organic light emitting diode（OLED）devices.The details were showed as follows:In the first,three new types of organic light-emitting materials Br-Al-Cz,Cl-Al-Cz and F-AI-Cz were designed and synthesized by changing the halogen substitution groups on phthalimide.They not only showed strong aggregation-induced emission（AIE）effect,but also exhibited thermally activated delayed fluorescence（TADF）in films and crystallization-induced room-temperature phosphorescence（RTP）properties.Especially,RTP with marked afterglow for Br-AI-Cz was observed by naked eye,which could be used as the promising smart materials for the encryption application.In the second,a series of new imide-based luminescent materials o-AI-Cz,m-AI-Cz and p-AI-Cz were prepared by changing the position of the carbazole group.They showed TADF and RTP properties due to their smallΔE_ST in both film and crystalline states.o-AI-Cz exhibited an ultralong RTP with a lifetime of 602 ms in air and remarkable afterglow,which could allow it to be used as a security ink for application in anti-counterfeiting materials.Moreover,o-AI-Cz showed intense intramolecular interaction between the donor and the acceptor subunits,while p-AI-Cz could form regular hexagonal pores with a diameter of13.171?in the solid state,which might result in their different RTP properties.In the third,compound AI-N-Cz was conveniently synthesized,and it exhibited ultralong room-temperature phosphorescence（RTP）with the lifetime of 775 ms,which was more than400 times of the RTP lifetime of its isomer AI-Cz（1.9 ms）.The ultralong RTP of AI-N-Cz might be due to the combination of small singlet-triplet splitting energy(ΔE_ST)and H-aggregation,and it could be an efficient strategy for the further design of ultralong organic room temperature materials.In the fourth,three new emitters,namely Fene,Fens and Yad,featuring quinoline as a new electron acceptor have been designed and conveniently synthesized by changing the type of electron donor.These emitters possessed small singlet-triplet splitting energy(ΔE_ST)and twisted structures,which not only endow them show thermally activated delayed fluorescence（TADF）property but also afford a remarkable aggregation-induced emission（AIE）feature.Moreover,they also showed aggregation-induced delayed fluorescence（AIDF）property and good photoluminescence（PL）property,which are the ideal emitters for non-doped OLEDs.Furthermore,High-performance non-doped organic light-emitting diodes（OLEDs）are achieved with neat film of Fene,Fens and YAD achieved excellent maximum external quantum efficiencies(EQE_max)of 14.9,13.1%and 17.4%,respectively.It was also found that the devices all exhibited relatively low turn-on voltages ranging from 3 V to 3.2 V probably due to their twisted conformation and the AIDF properties.These results demonstrate that the quinoline-based emitters have a promising application in non-doped OLEDs.This dissertation contains 106 Figures,10 Tables,and 147 references.更多还原