设计合成确切结构的异官能基笼型倍半硅氧烷一直是国际性的研究热点问题.用“自下而上”的方法,以半笼型结构倍半硅氧烷为模板,成功地制备出具有Janus结构的四乙烯基四氨基苯基、四乙烯基四苯基异官能基笼型倍半硅氧烷.并且,产物在一些极性溶剂(如四氢呋喃、氯仿及二甲基亚砜)中有较好的溶解性,为其衍生化及应用提供了保证.对所制备的异官能基笼型倍半硅氧烷进行了全面的表征分析,证明其具有Janus异官结构特征及完整的笼型结构.紫外可见及荧光发射光谱证实了倍半硅氧烷笼型结构的电子携带及传输作用,反过来证明其具有完整的笼型结构,同时也为其在有机光电材料中应用提供可能.提供了一类通用合成方法,拓宽了倍半硅氧烷功能单体的种类,并拓展了其应用范围.
Design and synthesis of well-defined hetero-functional cubic silsesquioxane remain as international research fo- cuses and challenges. In this work, we demonstrated in detail the synthesis of two Janus hetero-functional cubic silsesquiox- ane. We applied similar "bottom-up" method to construct the aimed Janus HFCSQ, which was carried out by using cyclic tetrasiloxanes as synthetic platforms and followed by further hydrolysis and cage-closure. The obtained products exhibited good solubility in THF, CHC13 and DMSO, which embodied themselves potential use in further derivations and processing. The precise structure of these obtained Janus HFCSQ were fully characterized by FTIR, 1H NMR, Maldi-tof MS, 29Si NMR, WAXD and TGA. Red-shifts observed from Photoluminescence UV-vis analysis further confirmed extended conjugation of the silsesquioxane cages, which in turn proved the formation of completed cages.This work provided us a versatile novel method to prepare the resulting Janus HFCSQs, which can widely expand the species of silsesquioxane monomers and applications as well.