Stoichiometrically Controlled Revocable Self‐Assembled “Spiro” versus Quadruple‐Stranded “Double‐Decker” Type Coordination Cages

The simple combination of PdII with the tris‐monodentate ligand bis(pyridin‐3‐ylmethyl) pyridine‐3,5‐dicarboxylate, L, at ratios of 1:2 and 3:4 demonstrated the stoichiometrically controlled exclusive formation of the “spiro‐type” Pd1L2 macrocycle, 1, and the quadruple‐stranded Pd3L4 cage, 2, respectively. The architecture of 2 is elaborated with two compartments that can accommodate two units of fluoride, chloride, or bromide ions, one in each of the enclosures. However, the entry of iodide is altogether restricted. Complexes 1 and 2 are interconvertible under suitable conditions.