In analogy to how a single ligand is used to make a diverse set of molecular catalysts, metal-organic frameworks with chelating linkers can be used as platforms to synthesize heterogeneous catalysts for a variety of reactions through post-synthetic metalation. A highly porous and thermally robust zirconium metal-organic framework bearing open bipyridine sites, Zr6O4(OH)4(bpydc)6 (bpydc2-�= 2,2'-bipyridne-5,5'-dicarboxylate) (see Figure 1, left), readily reacts with a variety of metal sources to form the corresponding metalated frameworks. Remarkably, Zr6O4(OH)4(bpydc)6 undergoes a single crystal to single crystal transformation upon metalation that leads to a change in space group from Fm-3m to P213.  This structural transformation facilitates the ordering of the metalated linkers within the framework, allowing structural characterization of the metal complexes formed within the framework (see Figure 1, right). Furthermore, Zr6O4(OH)4(bpydc)6 yields active heterogeneous catalysts for aerobic primary alcohol oxidation to aldehydes when metalated with CuX (X = Cl� or BF4�) and arene C-H borylation when metalated with [Ir(COD)2]BF4 (COD = 1,5-cyclooctadiene).

Structurally well-defined heterogeneous catalysts through the metalation of a zirconium metal-organic framework bearing open 2,2'-bipyridine sites

248th National Meeting (2014)

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