Host-guest complexes of anionic porphyrin sensitizers with cyclodextrins

The photodynamic sensitizers zinc(II)- and palladium(II)-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrins and 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin form 1:1 and/or 1:2 supramolecular complexes with native cyclodextrins (CD) and 2-hydroxypropyl cyclodextrins (hpCD) in aqueous neutral solutions. The formation of these assemblies causes a bathochromic shift of the porphyrin Soret band in the UV-vis spectra and a red shift of the fluorescence emission bands. The binding constants span over three orders of magnitude, from 8.1 × 102 M −1 to 5.4 × 105 M −1 (or 1.1 × 106 M −2) depending on the size of the CD cavity and on the functionalization by adding 2-hydroxypropyl groups. The highest binding constants were obtained for hpβCD and hpγCD. The Nuclear Overhauser spectroscopy signals (ROESY) revealed three binding modes: i) inclusion of the porphyrin 4-sulfonatophenyl or 4-carboxyphenyl groups via the secondary face of βCD and hpβCD with sulfonic or carboxylic groups oriented towards the primary hydroxyl groups. ii) inclusion of the porphyrin groups via the primary face of γCD and hpγCD. iii) non-specific binding of the porphyrin monomers or aggregates on the cyclodextrin exterior. The inclusion host-guest complexation via i) or ii) does not influence the inherent photophysical properties of the monomeric porphyrins such as the quantum yields of fluorescence, the triplet states, and the singlet oxygen formation. Due to the deaggregation effect of cyclodextrins, the inclusion complexes remain efficient supramolecular sensitizers of singlet oxygen even under conditions of extensive aggregation in aqueous solutions.