Donor–Acceptor [2]‐ and [3]Catenanes Assembled from Versatile Pre‐Organized CpRh/Ir‐Directed Pseudorotaxane Tectons

A stepwise self‐assembly protocol has been used to synthesize [2]‐ and [3]catenanes. Firstly, binuclear Cp*Rh/Ir‐directed (Cp*=pentamethylcyclopentadienyl) pseudorotaxanes were prepared through self‐assembly, driven by donor–acceptor interactions between electron‐deficient naphthalenediimide (NDI) units and an electron‐rich crown ether. Subsequently, the pre‐organized pseudorotaxanes were applied as tectons for self‐assembly of [2]‐ and [3]catenanes by combination with very simple linkers. The structures of the catenanes were confirmed by NMR spectroscopy, ESI mass spectrometry, single‐crystal X‐ray diffraction analysis, and elemental analysis. Interlocked compounds: Donor–acceptor pseudorotaxanes were prepared through Cp*Rh‐ or Cp*Ir‐directed (Cp*=pentamethylcyclopentadienyl) self‐assembly. The pre‐organized binuclear catenaned complexes were used as versatile tectons for [2]‐ and [3]catenanes.