Bloch, Witold M.Holstein, Julian J.Dittrich, BirgerHiller, WolfClever, Guido H.2018-04-122018-04-122018-03-22http://hdl.handle.net/2003/3683210.17877/DE290R-18833The self‐assembly of eight PdII cations and sixteen phenanthrene‐derived bridging ligands with 60° bite angles yielded a novel M8L16 metallosupramolecular architecture composed of two interlocked D4h‐symmetric barrel‐shaped containers. Mass spectrometry, NMR spectroscopy, and X‐ray analysis revealed this self‐assembled structure to be a very large “Hopf link” catenane featuring channel‐like cavities, which are occupied by NO3− anions. The importance of the anions as catenation templates became imminent when we observed the nitrate‐triggered structural rearrangement of a mixture of M3L6 and M4L8 assemblies formed in the presence of BF4− anions into the same interlocked molecule. Furthermore, the densely packed structure of the M8L16 catenane was exploited in the preparation of a hexyloxy‐functionalized analogue, which further self‐assembled into vesicle‐like aggregates in a reversible manner.enhttps://creativecommons.org/licenses/by-nc/4.0/CatenanesInterlocked structuresSelf-assemblyStructural transformationsSupramolecular chemistry540article (journal)