Abstract: | Crown ether usually plays the role of macrocyclic host in supramolecular chemistry, but here the crown ether is also utilized as the stoppers in rotaxanes. In this work, we designed and synthesized two [3]rotaxanes containing four crown ether components by using an approach of template‐directed clipping reaction, of which, two crown ether components were employed as the macrocyclic hosts to assemble the mechanically interlocked framework while another two crown ether units located on the two ends of ammonium template acting as the stoppering groups of rotaxanes. Their self‐assembling process was monitored by the 1H NMR and one of the single crystal structures of [3]rotaxane was obtained. |