Fluoranthene-Modified Tetraphenylethene Derivatives: Synthesis, Aggregation-Enhanced Emission Characteristic and Their Highly Sensitive Detection of Picric Acid

由於聚集體和固態發光量子效率高等優點，因此聚集誘導發光（AIE）材料成為光電功能材料研究領域的熱點，拓展AIE分子體系始終是這一領域中的關鍵和基礎的科學問題.通過Suzuki-Miyaura偶聯這一條件較為溫和的反應，將AIE生色團四苯基乙烯（TPE）與熒蒽直接共軛鍵接，製備得到單熒蒽和雙熒蒽修飾的TPE衍生物TPE-FA與TPE -DFA，它們具有聚集增強熒光（AEE）行為，聚集體發射峰值波長分別在477和494 nm，固體薄膜的絕對熒光量子產率高達74.1%和40.4%.它們可以高靈敏地檢測苦味酸，熒光猝滅常數大，檢出限低於1 μg·g-1.這兩種AEE分子可望用於其它多硝基取代的芳香類吸電子分子的檢測. © 2016 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences. Aggregation-induced emission (AIE) active compounds and materials have become one of the hottest research topics worldwide, due to their unprecedented merits such as ultra-high fluorescence quantum efficiencies as aggregates or in solid state. Up to now, it is still extremely crucial and fundamental to expand the AIE-genic molecular systems for this research area. Here, we prepared two fluoranthene-modified tetraphenylethene (TPE) derivatives, TPE-FA and TPE-DFA, through the Suzuki-Miyaura coupling between boronate-bearing TPE and bromo-bearing fluoranthene under mild reaction condition. The conjugation between fluoranthene and TPE moieties assures that the as-prepared TPE-FA and TPE-DFA both possess aggrega-tion-enhanced emission (AEE) characteristics. The emission maximum of TPE-FA and TPE-DFA as aggregates in THF/water mixtures is at 477 nm and 494 nm, and the absolute quantum yields of the two compounds in solid films are as high as 74.1% and 40.4%, respectively. They can be utilized as fluorescent probes for picric acid with high sensitivity. Their quenching coef-ficients can be as high as 4×104 L·mol-1, while their detection limits can be lower than 1 μg·g-1. These AEE-active molecules are promising to act as fluorescent probes in the detection of other nitro-substituted electron-deficient molecules. © 2016 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.