Yu Chin-Yang, Lai Yu-Chun
Department of Materials Science and Engineering, National Taiwan University of Science and Technology 43, Section 4, Keelung Road Taipei 10607 Taiwan
RSC Adv. 2018 May 25;8(35):19341-19347. doi: 10.1039/c8ra03025a.
4-Bromo substituted [2.2]paracyclophane-1,9-diene was synthesized from the corresponding dithia[3.3]paracyclophane in three steps through benzyne Steven rearrangement, oxidation, and a thermal elimination reaction. 4-Triphenylvinylphenyl substituted [2.2]paracyclophane-1,9-diene was successfully prepared by the Suzuki-Miyaura cross-coupling reaction of 4-bromo substituted [2.2]paracyclophane-1,9-diene and 4,4,5,5-tetramethyl-2-(4-(1,2,2-triphenylvinyl)phenyl)-1,3,2-dioxaborolane using Pd(OAc) as a catalyst, -Phos as a ligand and KPO as a base. The structures of bromo substituted [2.2] paracyclophane-1,9-diene and triphenylvinylphenyl substituted [2.2]paracyclophane-1,9-diene were fully characterized by H NMR spectroscopy and X-ray crystallography. 4-Triphenylvinylphenyl substituted [2.2]paracyclophane-1,9-diene exhibited aggregation-induced emission characteristics when the water fraction was higher than 80% in the THF/water mixtures. 4-Triphenylvinylphenyl substituted [2.2]paracyclophane-1,9-diene displays much higher fluorescence when the water fraction is 90% compared to that of model compounds due to both through bond and through space conjugation. To the best for our knowledge, we are the first to synthesize triphenylvinylphenyl substituted [2.2]paracyclophane-1,9-diene with aggregation-induced emission characteristics.
4-溴取代的[2.2]对环芳烷-1,9-二烯是由相应的二硫杂[3.3]对环芳烷通过苯炔史蒂文重排、氧化和热消除反应分三步合成的。通过使用醋酸钯作为催化剂、-Phos作为配体和磷酸钾作为碱，使4-溴取代的[2.2]对环芳烷-1,9-二烯与4,4,5,5-四甲基-2-(4-(1,2,2-三苯基乙烯基)phenyl)-1,3,2-二氧杂硼烷发生铃木-宫浦交叉偶联反应，成功制备了4-三苯基乙烯基苯基取代的[2.2]对环芳烷-1,9-二烯。溴取代的[2.2]对环芳烷-1,9-二烯和三苯基乙烯基苯基取代的[2.2]对环芳烷-1,9-二烯的结构通过核磁共振氢谱和X射线晶体学进行了全面表征。当四氢呋喃/水混合物中水的比例高于80%时，4-三苯基乙烯基苯基取代的[2.2]对环芳烷-1,9-二烯表现出聚集诱导发光特性。由于通过键和通过空间共轭，当水的比例为90%时，4-三苯基乙烯基苯基取代的[2.2]对环芳烷-1,9-二烯比模型化合物显示出更高的荧光。据我们所知，我们是第一个合成具有聚集诱导发光特性的三苯基乙烯基苯基取代的[2.2]对环芳烷-1,9-二烯的。
