作者:Jasper J. Michels、Michael J. O'Connell、Peter N. Taylor、Joanne S. Wilson、Franco Cacialli、Harry L. Anderson
DOI:10.1002/chem.200305245
日期:2003.12.15
of the conjugated polymer pi-systems. Both the solution and the solid-state photoluminescence quantum yields are enhanced upon threading of the conjugated polyaromatic cores through alpha- or beta-cyclodextrins, and the emission spectra of the polyrotaxanes are blue-shifted compared to the corresponding unthreaded polymers. The greater weight of the 0-0 transition in the emission spectra, as well as
一系列的共轭聚轮烷绝缘分子丝是通过水性Suzuki聚合反应合成的,利用疏水键合促进环糊精单元的穿线。这些聚轮烷具有基于聚(对亚苯基),聚芴和聚(二亚苯基-亚乙烯基)的共轭聚合物核,每个重复单元穿过0.9-1.6个环糊精。庞大的3,6-萘二甲酸萘端基可防止大环从共轭聚合物链上滑落。透析实验表明,仅当使用较小的塞子时,环糊精才会脱螺纹。MALDI TOF质谱可检测多达十个螺纹环糊精的低聚物,并揭示某些缺陷的存在,这些缺陷会导致硼酸的氧化均偶联。重均分子量通过分析超离心法测定,证明了逐步增长聚合的效率足以达到高达约20个重复单元(84个对亚苯基)的聚合度。这些聚轮烷的荧光光谱表明,带螺纹的环糊精大环的存在降低了共轭聚合物π-系统的柔韧性。当共轭聚芳族核穿过α-或β-环糊精时,溶液和固态光致发光量子产率都得到提高,与相应的无螺纹聚合物相比,聚轮烷的发射光谱发生了蓝移。发射光谱中0-0跃迁的权重越大