Multifunctional �-diketone and pyridyltriazole ligands can be used to assemble cyclic metal-organic molecules that bind and react with guest molecules. �-diketonates are flexible when they bind to metal ions, so the supramolecular structures that result are not always the ones predicted on the basis of metal and ligand geometry. Pyridyltriazoles and related ligands may be less flexible in their binding, and they are also much better at stabilizing multiple metal oxidation states.We have studied two types of supramolecular hosts. 2D and 3D molecules can be assembled from bis- and tris(�-diketones), and they bind guests via s and p interactions. Bis(pyridyltriazoles) react with copper(II) to make dimers with metal coordination numbers of 4, 5, and 6. The copper(II) complex of m-xpt, [Cu2(m-xpt)2Cl2]2+, is readily reduced to copper(I), [Cu2(m-xpt)2]2+, which then reacts with CO2(g) to make the oxalate-bridged dimer [Cu2(m-xpt)2(�-C2O4)]2+. Treatment with H+ removes the bound oxalate as H2C2O4, completing a cycle for CO2 reduction under mild conditions. The properties of systems with related multidentate N donor ligands will also be discussed.

Redox reactions and host-guest chemistry of macrocyclic metal-organic complexes

247th National Meeting (2014)

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