Orthogonal Dynamic Metal-Templated Synthesis of Fully π-Conjugated [2]Catenane with Switchable Mechanical Chirality

Orthogonality in intermolecular interactions, exemplified by the highly selective hydrogen bonding in DNA base pairing, underpins the precision of dynamic self-assembly in biological systems. Dynamic coordination bonds offer significant potential for the construction of molecular architectures with complexity surpassing that of biological systems. Herein, we report a novel strategy utilizing an orthogonal combination of classical Cu(I)-sp² nitrogen coordination bonds and Au(I)–C dynamic σ-bonds, both of which are reversible dynamic bonds. This strategy enables the efficient synthesis of a nitrogen-doped [2]catenane, composed of two mechanically-interlocked [12]cycloparaphenylene (CPP)-based frameworks through the dynamic metal-templated reorganization of triangular macrocyclic gold complexes mediated by Cu(I) ions, followed by reductive elimination. Computational and experimental analyses highlight the key role of Cu(I)-mediated bond exchange in directing the selective formation of interlocked intermediate metal complexes. The resulting [2]catenane encapsulates chiral guest molecules in solution, enabling control over its mechanical chirality. This work introduces a new paradigm for orthogonal self-assembly, paving the way for advanced supramolecular architectures with applications in circularly polarized luminescence, enantioselective catalysis, and beyond.