Highly Selective Synthesis of Iridium(III) Metalla[2]catenanes through Component Pre‐Orientation by π⋅⋅⋅π Stacking

Abstract A series of molecular metalla[2]catenanes featuring Cp*Ir vertices have been prepared by the template‐free, coordination‐driven self‐assembly of dinuclear iridium acceptors and 1,5‐bis[2‐(4‐pyridyl)ethynyl]anthracene donors. The metalla[2]catenanes were formed by using a strategically selected linker type that is capable of participating in sandwich‐type π–π stacking interactions. In the solid state, the [2]catenanes adopt two different configurations depending on the halogen atoms at the dinuclear metal complex bridge. Altering the solvent or the concentration, as well as the addition of guest molecules, enabled controlled transformations between metalla[2]catenanes and tetranuclear metallarectangles.