Macrocyclic receptors incorporating two facing π-electron-rich aromatic surfaces, held at a distance of approximately 7 A by polyether spacers, bind bipyridinium-based guests. This recognition motif, which is dictated by π−π stacking and [C−H···O] hydrogen-bonding interactions, has led to the development of efficient template-directed syntheses of mechanically interlocked molecules, such as catenanes and rotaxanes. By employing a supramolecularly assisted synthetic methodology based on these interactions, we have self-assembled two novel [3]catenanes, each incorporating two 1,5-dioxynaphtho-38-crown-10 components and one bipyridinium-based tetracationic cyclophane component. Single-crystal X-ray analyses of these [3]catenanes revealed that they possess internal cavities bounded on two opposite sites by π-electron-rich 1,5-dioxynaphthalene units separated by a distance of approximately 7−8 A. Despite the presence of apparently ideal “binding pockets”, these mechanically interlocked compounds steadfastly re...