Supramolecular Template-Directed Synthesis of Perfect Phenelenediimino-Bridged Ladderlike Polyphenylsiloxanes
作者:Taoyi Zhang、Kuilin Deng、Pingping Zhang、Ping Xie、Rongben Zhang
DOI:10.1002/chem.200501447
日期:2006.4.24
A template synthesis of the soluble, high molecular weight (Mw), and perfect p-phenylenediimino (p-PDA)-bridged ladderlike polyphenylsiloxane (PLPS) is reported. First, N,N'-bis(phenyldichlorosilyl)-p-PDA monomers were self-assembled into a perfect ladder superstructure (LS) by concerted interaction of aromatic pi-pi stacking and hydrogen bonding. Then the LS underwent a novel stoichiometric hydro
报告了可溶,高分子量(Mw)和完美的对苯二胺(p-PDA)桥联梯状聚苯硅氧烷(PLPS)的模板合成。首先,N,N'-双(苯基二氯甲硅烷基)-p-PDA单体通过芳族pi-pi堆积和氢键的协同作用而自组装成理想的梯形上层结构(LS)。然后,LS进行了新颖的化学计量的水解/脱氯化氢-缩合反应,而不是通常的水解/脱水-缩合反应,从而导致了PLPS。PLPS尤其是不稳定的超分子LS的完美梯形结构已确认如下。1)在固体和/或溶液X射线衍射(XRD)光谱中有两个布拉格峰,分别代表阶梯宽度(w)和阶梯厚度(t);这些峰与分子模拟计算得出的峰一致。2)在29Si NMR光谱中,PLPS和LS都具有非常尖锐的吸收峰,且半峰宽较小(Delta(1/2)<0.3 ppm),这表明PLPS和LS存在完美的梯形结构。3)此外,在FT-IR和29Si NMR光谱中未观察到Si-OH和NH2基团的明显吸收峰,表明[三键]