Directed Assembly of Transition-Metal-Coordinated Molecular Loops and Squares from Salen-Type Components. Examples of Metalation-Controlled Structural Conversion

A series of transition-metal-containing molecular “loops” and “squares” has been prepared via
a directed-assembly approach and characterized. The molecular loops were prepared from the reaction of
cis-(PEt3)2Pt(OTf)2 with bis(4-pyridyl)-functionalized free-base salen-type ligands. Zn(II)-metalation of the
salen-type ligands in the molecular loops converts the loops to molecular squares. Alternatively, the squares
can be obtained by the directed assembly of cis-(PEt3)2Pt(OTf)2 and bis(4-pyridyl)-functionalized Zn(II)−salen-type ligands. A concentration-dependent dynamic equilibrium between cyclic species was observed
when bis(3-pyridyl)-functionalized free-base salen-type ligand was employed in the reaction. Zn(II) or Cr(III)
metalation of the free-base ligand shifted the equilibrium to the single dimeric species. The incorporation
of multiple reactive metal sites into a single, cavity-containing supramolecular structure points toward catalytic
applications for these new assemblies.