Traditional applications of metal-organic frameworks (MOFs) are focused on gas storage and separation, which take advantage of the inherent porosity and high surface area of these materials. However, a virtually untapped area of MOF chemistry is related to their potential to mediate redox reactivity. We show that MOFs can be thought of as unique weak-field ligands that give rise to unusual molecular coordination environments where small molecule species can be isolated in a matrix-like environment, akin to the metal binding pockets of metalloproteins. By employing a mild cation-exchange synthetic method and a suite of spectroscopic techniques, we have undertaken forays into the redox chemistry of the MOFs' metal nodes, an exciting new area for the room temperature isolation of highly reactive, biologically-relevant metal-oxygen and nitrogen species, and for small molecule activation.

Metal-organic frameworks as small molecules: Redox chemistry and small molecule activation at MOF secondary building units

248th National Meeting (2014)

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