Knowledge Management System Of Institute of process engineering,CAS
室温磷光材料以其独特的激发态性质，在生物医学成像、有机光电材料、防伪系统以及化学传感器等领域广泛应用。目前大多数的磷光材料为无机物和贵金属配合物，鉴于这些化合物较为昂贵且具有一定的毒性，亟待开发低成本、低毒且结构可设计的纯有机室温磷光材料。本文选取喹啉类的有机离子盐作为研究对象，分别考察重原子效应和共轭效应对纯有机室温磷光离子盐发光性能的影响。主要进展如下：（1）探究重原子效应对发光性能的影响，合成了Cl-、Br-、I-以及PF6-等不同阴离子的N-烯丙基喹啉卤化物。测试产物的发光性能表明，阴离子为Br-的N-烯丙基喹啉有机离子盐有微弱磷光，阴离子为Cl-和PF6-的N-烯丙基喹啉离子盐由于不含重原子则以荧光为主，尤其以PF6-为阴离子的有机盐具有强荧光，其余几乎不发光。此外，阴离子为Br-的离子盐在外部滴加CHCl3的情况下磷光量子产率Фem由几乎为零提高至2.76%，发光颜色由原来的橘黄色变成绿色。（2）研究共轭效应对材料发光性能的影响，合成了一系列基于异喹啉、酞嗪、1,10-菲罗啉等阳离子不同的室温磷光有机溴化物。测试产物的发光性能表明，合成的有机离子盐都有磷光性质。N-烯丙基异喹啉溴化物中心共轭体系中的氮原子位置改变，造成了其对CHCl3的溶剂刺激响应作用不明显，只是对发光强度有所影响。N-烯丙基酞嗪溴化物对比前者在邻位多了一个氮原子，两者性质类似。对N-烯丙基-1,10-菲罗啉溴化物，共轭体系的延长由于空间位阻等原因，CHCl3难以在分子之间产生明显微扰，对晶体排布的影响较小。综上所述，Br-诱发分子产生室温磷光的效果最好，不含重原子的离子盐则以荧光性质为主，结合产物对CHCl3特殊的外部溶剂刺激响应作用，开拓了N-烯丙基喹啉溴化物在防伪材料方面的应用；在探究共轭效应对有机离子盐磷光影响时，杂原子氮以及烯丙基的位置变化导致中心共轭体系电子云的分布和晶型的改变，使得磷光材料对CHCl3的溶剂刺激效应不明显。;Materials with room-temperature phosphorescence (RTP) have important applications in bioimaging, organic optoelectronic materials, anti-counterfeiting systems and chemical sensors due to their unique excited state properties. At present, most phosphorescent materials are mainly inorganic and coordination complexes that contain noble metals. Considering that these compounds are relatively expensive and toxic, pure organic room-temperature phosphorescent materials with low cost, low toxicity and high designability are in urgent need of development. Herein, quinolinium salts were selected as the main research objects. Heavy atom effect and conjugation effect on the luminescence properties of pure organic room temperature phosphorescent salts were investigated, respectively. The main contents are summarized as follows: (1) To investigate the influence of heavy atom effect on luminescent properties, N-allylquinolium halides with different anions such as Cl-, Br-, I- and PF6- were synthesized to test their luminescent properties. The results showed that the salt with Br- was weakly phosphorescent, and the N-allylquinolium salts with Cl- and PF6- counterparts were mainly fluorescent due to the absence of heavy atoms, and especially the organic salt with PF6- emitted strong fluorescence, while the rest compounds are barely luminescent. In addition, quantum yield (Фem) of salt with Br- is promoted from almost zero to 2.76% after the addition of CHCl3, and the luminescent color is changed from the original orange to green. (2) To investigate the conjugated effect on the luminescent properties of the materials, a series of organic bromides with RTP based on different cations such as N-allylquinolinium, N-allylphthalazinium and N-allyl-1,10-phenanthrolinium were synthesized and studied. The results showed all the compounds were phosphorescent. The position of the nitrogen atom in the conjugated system of N-allylisoquinolinium bromide was changed, leading to that there was barely solvent stimuli response to CHCl3, and the addition of solvent only had an effect on the intensity of the luminescence. Compared with the former, N-allylpyridazinium bromide had one more nitrogen atom in the ortho position and they had similar properties. For N-allyl-1,10-phenanthrolinium bromide, the extension of conjugated system resulted in that it was difficult for CHCl3 to produce significant perturbation between molecules due to the steric hindrance, besides there were no obvious effect on the crystal arrangements. In conclusion, Br- showed the best performance to induce phosphorescence in organic salts while the compounds without heavy atoms were mainly fluorescent; combining the special external solvent stimuli response to CHCl3, the application of N-allylquinoline bromide in anti-counterfeiting materials has been developed; to investigate the effect of conjugation on the phosphorescence of organic salts, the positions of heteroatom nitrogen and allyl group lead to the distribution changes of the central conjugated electron cloud and crystal phase transition, which caused that the compounds did not have an obvious solvent stimuli response to CHCl3.
|熊青霞. 室温磷光有机离子盐的设计合成及表征[D]. 中国科学院大学,2019.|
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