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| - Directed Assembly of Transition-Metal-Coordinated MolecularLoops and Squares from Salen-Type Components. Examplesof Metalation-Controlled Structural Conversion
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| - A series of transition-metal-containing molecular “loops” and “squares” has been prepared viaa directed-assembly approach and characterized. The molecular loops were prepared from the reaction ofcis-(PEt3)2Pt(OTf)2 with bis(4-pyridyl)-functionalized free-base salen-type ligands. Zn(II)-metalation of thesalen-type ligands in the molecular loops converts the loops to molecular squares. Alternatively, the squarescan 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 observedwhen 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 incorporationof multiple reactive metal sites into a single, cavity-containing supramolecular structure points toward catalyticapplications for these new assemblies.
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