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Effect of nafion on geometry and axial ligation in manganese (III) tetraphenylporphyrins
Author(s) -
Maclean Angela L.,
Armstrong Robert S.,
Kennedy Brendan J.
Publication year - 1995
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1250261102
Subject(s) - porphyrin , raman spectroscopy , chemistry , pyridine , nafion , ionic bonding , manganese , molecule , solvent , ion , resonance raman spectroscopy , photochemistry , inorganic chemistry , coordination geometry , crystallography , organic chemistry , electrochemistry , hydrogen bond , electrode , physics , optics
Manganese(III) porphyrins were successfully incorporated into Nafion, wherein they are located in the ionic pockets of the polymer. The result 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 macrocyle also changes when in Nafion. Puckering of the porphyrin ring apparently occurs as it interacts with the restrictive environment in Nafion.