Abstract
AbstractThe spin density distributions in the cation radicals of various covalently linked porphyrin dimers have been studied by liquid phase ESR and ENDOR methods to find out whether these systems show intramolecular electron delocalization. Such a delocalization is known to occur in the bacteriochlorophyll dimer (“special pair”) in the photosynthetic reaction center. The dimers that were studied in this work were derived from zinc mesotetratolylporphyrin (ZnTTP) and linked at the ortho or para positions of one phenyl ring with varying bridge lengths. 1H and I4N hyperfine coupling constants could be measured for the dimer cation radicals and compared with those of monomeric ZnTTP as well as ZnTTP derivatives that carry alkoxy or hydroxy substituents to mimic the bridges of the dimers. By comparing the hyperfine data of the monomer and dimer cation radicals it is concluded that in the present dimers the unpaired electron is localized on one porphyrin unit.
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