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.