Unexpected Self‐Assembly of a Homochiral Metallosupramolecular M₄L₄ Catenane

Abstract Two enantiomerically pure 9,9′‐spirobifluorene‐based bis(pyridine) ligands 1 and 2 were prepared to study their self‐assembly behavior upon coordination to cis ‐protected palladium(II) ions. Whereas the sterically more demanding ligand, 2 , gave rise to the expected dinuclear metallosupramolecular M 2 L 2 rhombi, the sterically less demanding ligand, 1 , acts as a template to give rise to a homochiral metallosupramolecular M 4 L 4 catenane.