Coordination-Driven Synthesis, Characterization, and Computational Study of a Rhodium-Based [2]Catenane

We report the efficient single-step synthesis of [2]catenane Rh-1, achieved through the self-assembly of 1,4-naphthalenediamine-derived bidentate ligands and binuclear half-sandwich rhodium(III) clips. Single-crystal X-ray diffraction confirms the interlocked structure of Rh-1 . Density functional theory calculations reveal that π–π stacking and hydrogen bonding interactions play crucial roles in the formation and stabilization of Rh-1 . In addition, the effects of ligand modification and metal ion substitution on the self-assembly process were also theoretically investigated from the perspective of thermodynamics. This work provides valuable insights for the rational design and synthesis of functional [2]catenanes and higher-order interlocked architectures.