Metal organic frameworks (MOFs) have recently been the target of intense study as materials for gas storage and separation. MOFs with unsaturated metal sites (UMS) are of particular interest because the Lewis acidity of the metals can lead to increased uptake and tighter binding. We note that these UMS can resemble small molecule systems, and when redox-active metals are employed, they might be expected to participate in a wealth of chemistry that is similar to the small molecule analogues.This contribution discribes the incorporation of Mn and Fe in systems with architectures known to have UMS or readily exchangeable X-type ligands. We have explored one-electron chemical reductions and oxidations of such systems with the aim of understanding the scope of the redox transformations in which MOFs with UMS can participate and how this reactivity compares with small molecule analogues.

Stoichiometric redox chemistry at accessible metal sites in porous frameworks

245th National Meeting (2013)

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