Modulating the Coordination Properties of 4-Coordinate Copper(I) Using Catenane Ligands Composed of Differently Sized Macrocycles

Upon coordination to catenane ligands derived from interlocked macrocycles of different size, gradual deviation of the coordination structure of the resulting 4-coordinate copper(I) complexes from the preferred tetrahedral geometry is resulted, and such structural distortion represents a new mechanism for modulating the thermodynamic, kinetic, photophysical and electrochemical properties of the transition metal complexes via ligand mechanical interlocking. Results from this study hence not only first demonstrate that the extend of catenand effect on metal coordination properties can be tuned by a physical attribute characteristic to mechanical interlocking, but also are implicated in the reactivity and potential applications of a distinct, rarely studied class of transition metal complexes supported by mechanically bonded ligands.