Manganese(II1) porphyrins were successfully incorporated into Nafion, wherein they are located in the ionic pockets of the polymer. The results of UV-visible spectroscopy indicate that at least one solvent molecule and the anion accompany the macrocycle into the membrane. The anion is only loosely associated with the porphyrin, but strongly coordinating solvents such as pyridine remain in the axial coordination sites. Dramatic changes which were observed in the electronic and resonance Raman spectra when THF and dioxane were used as incorporation solvents indicate that the geometry of the macrocycle also changes when in Nafion. Puckering of the porphyrin ring apparently occurs as it interacts with the restrictive environment in Nafion.CCC 0377 0486/9.5/110981 09 199.5 by John Wiley & Sons, Ltd spectra" that are sensitive to changes in the metal environment. There has been much recent work on axial ligation16-19 and the spectral consequences of weak axial binding in manganese(II1) porphyrins are well characterized.' 3-'5 Resonance Raman (RR) spectroscopy is another useful tool for studying manganese porphyrins. The highly structured low-wavenumber includes axial ligand-dependent modes20*22 that give information about the immediate metal environment. The in-plane skeletal modes, occurring at higher wavenumbers, are sensitive to changes in core size and doming or ruffling in metallo-p~r p h y r i n s '~,~~~~~ Hence it is believed that a combined RR and UV-visible study would be beneficial to probe the immediate environment of the metal and the influence that Nafion exerts as a host material.Manganese porphyrins with the structure
X YOMe, H, CN CI -H CI-, Br
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