Metal-organic frameworks (MOFs) have many possible applications including gas storage and catalysis that require the presence of coordinatively unsaturated metal ions. Methods for generating open metal sites in MOFs need to be developed. Our approach uses organic linkers featuring two distinct metal-binding sites, such as tetra(4-carboxyphenyl)porphyrin (TCPP), to generate tunable heterobimetallic frameworks. For TCPP, a �structural� metal ion binds to the carboxylate groups defining the framework and a �functional� metal ion binds at the porphyrin ring. When ions such as Cd(II),  Pb(II) and In(III) are used as the structural metal, it is possible to synthesize several families of two- and three-dimensional MOFs containing a wide range of functional metal ions, including Mn(III), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Pd(II). The reactivity of these solids and their thermal stability will be discussed. The results of reactions using Pb(II) and In(III) as structural metal ions will be presented.

Heterobimetallic metal-organic frameworks with tunable open-metal sites

243rd National Meeting (2012)

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