Molecular complexes of water-soluble porphyrins

Abstract

Water-soluble porphyrins tend to form self-aggregates under certain conditions. The structure of the self-aggregate (H-type dimer, H-type higher aggregate, or J-aggregate) sensitively depends on the structure of the peripheral substituents at the meso-positions of the porphyrin. Water-soluble porphyrins also form relatively stable π-stacked complexes with various aromatics. Polar effects are important in complexation of anionic porphyrins with anthraquinonesulfonates. The results suggest that the main attractive interaction for formation of π-stacked complexes of water-soluble porphyrins is the σ-π interaction as claimed by Hunter and Sanders. Meanwhile, the aryl groups at the meso-positions of the water-soluble porphyrins are included by per-O-methylated β-cyclodextrin through van der Waals interactions to form extremely stable 1:2 complexes (porphyrin:cyclodextrin). Such a character of the water-soluble porphyrins can be applied to convenient preparation of supramolecular hetero-porphyrin arrays.