Abstract
Manganese K-edge EXAFS of [Mn(III)(TPP)X] (X = Cl −, Br −, I −) were recorded in the solid state and when incorporated into the perfluorinated ion-exchange polymer Nation. Refinement of the solid sample data produced interatomic distances typical of Mn(III) porphyrins and Mn-X bond lengths which increase with the size of the axial anion. On incorporation into Nation, the porphyrins become planar with Mn-N av < 2 Å, and six-coordinate with oxygen groups occupying the axial sites. The anion does not appear to accompany the macrocycle into Nafion. However, the solvent used to incorporate the porphyrins into Nafion occupies at least one of the axial coordination sites.
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