Sun Zhe, Mio Tatsuru, Ikemoto Koki, Sato Sota, Isobe Hiroyuki
Department of Chemistry , The University of Tokyo , Hongo 7-3-1, Bunkyo-ku , Tokyo , 113-0033 , Japan.
Isobe Degenerate π-Integration Project , JST, ERATO , Hongo 7-3-1, Bunkyo-ku , Tokyo , 113-0033 , Japan.
J Org Chem. 2019 Mar 15;84(6):3500-3507. doi: 10.1021/acs.joc.9b00085. Epub 2019 Feb 21.
A series of macrocycles were designed by rendering geodesic phenine frameworks in isoreticular networks of [ n]cyclo- para-phenylenes. Large, nanometer-sized molecules exceeding molecular weights of 2000 Da were synthesized by five-step transformations including macrocyclization of [6]cyclo- meta-phenylene panels. The dependence of both the molecular structures and the fundamental properties on the panel numbers was delineated by a combination of spectroscopic and crystallographic analyses with the aid of theoretical calculations. Interestingly, flexibility of the molecules via panel rotations depends on the hoop size, which has not been disclosed with the small isoreticular [ n]cylco- para-phenylenes. One of the macrocycles served as a host for C, and its association behaviors and crystal structures were revealed.
通过在[ n]环对亚苯基的等规网络中构建测地线菲骨架，设计了一系列大环化合物。通过包括[6]环间亚苯基面板大环化在内的五步转化反应，合成了分子量超过2000 Da的大型纳米级分子。借助理论计算，结合光谱和晶体学分析，描绘了分子结构和基本性质对面板数目的依赖性。有趣的是，分子通过面板旋转的柔韧性取决于环的大小，这在小型等规[ n]环对亚苯基中尚未被揭示。其中一个大环作为C的主体，揭示了其缔合行为和晶体结构。
