Shi Tan-Hao, Tong Shuo, Wang Mei-Xiang
MOE Key Laboratory of Bioorganic Phosphorous and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Angew Chem Int Ed Engl. 2020 May 11;59(20):7700-7705. doi: 10.1002/anie.202002827.
Linearly fused hydrocarbon nanobelts are a unique type of double-stranded macrocycles that would serve as not only the powerful hosts in supramolecular science but also the templates to grow zig-zag carbon nanotubes with defined diameters. Fully conjugated hydrocarbon nanobelts such as belt[n]arenes would also possess unique physical and chemical properties. Despite the importance, both fully conjugated and (partially) saturated hydrocarbon nanobelts remain largely unexplored because of the lack of cyclization methods. Reported here is the construction of nanometer sized H -belt[12]arenes based on the strategy to close up all fjords of resorcin[6]arene by means of six-fold intramolecular alkylation reactions of resorcin[6]arene derivatives. All resulting H -belt[12]arenes produce a very similar nanobelt core structure with six benzene rings and six boat 1,4-cyclohexadiene rings being alternately linear-fused to give a nearly equilateral hexagonal cylinder. The average long diagonal is around 1 nm and the height of the cylinder is about 0.3 nm. The acquired H -belt[12]arenes would be the potential precursors to various hydrocarbon nanobelts including fully conjugated belt[12]arenes.
线性稠合的碳氢纳米带是一种独特的双链大环化合物,它不仅可作为超分子科学中强大的主体,还能作为生长具有特定直径的锯齿形碳纳米管的模板。完全共轭的碳氢纳米带,如带状[n]芳烃,也具有独特的物理和化学性质。尽管其很重要,但由于缺乏环化方法,完全共轭和(部分)饱和的碳氢纳米带在很大程度上仍未得到充分研究。本文报道了基于间苯二酚[6]芳烃衍生物的六重分子内烷基化反应封闭间苯二酚[6]芳烃所有峡口的策略构建纳米尺寸的H -带状[12]芳烃。所有生成的H -带状[12]芳烃都产生了非常相似的纳米带核心结构,六个苯环和六个船式1,4 -环己二烯环交替线性稠合,形成一个近乎等边的六边形圆柱体。平均长对角线约为1 nm,圆柱体高度约为0.3 nm。所获得的H -带状[12]芳烃可能是包括完全共轭的带状[12]芳烃在内的各种碳氢纳米带的潜在前体。