On the Influence of the Bridge on Triplet State Delocalization in Linear Porphyrin Oligomers.

The extent of triplet state delocalization is investigated in rigid linear zinc porphyrin oligomers as a function of interporphyrin bonding characteristics, specifically in meso-meso singly linked and β,meso,β fused structures, using electron paramagnetic resonance techniques. The results are compared with those of earlier measurements on porphyrin oligomers with alkyne linkers exhibiting different preferred conformations. It is shown that dihedral angles near 90° between the porphyrin planes in directly meso-to-meso linked porphyrin oligomers lead to localization of the photoexcited triplet state on a single porphyrin unit, whereas previous work demonstrated even delocalization over two units in meso-to-meso ethyne or butadiyne-bridged oligomers, where the preferred dihedral angles amount to roughly 30° and 0°, respectively. The triplet states of fused porphyrin oligomers (i.e., porphyrin tapes) exhibit extended conjugation and even delocalization over more than two porphyrin macrocycles, in contrast to meso-to-meso ethyne or butadiyne-bridged oligomers, where the spin density distribution in molecules composed of more than two porphyrin units is not evenly spread across the oligomer chain.