Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

The photochemistry of free-base meso-tetraphenylporphyrin linked to methyl viologen via an alkoxy chain (n = 3) at the ortho, meta or para-position of one meso-phenyl group, in Triton X-100 micellar aqueous solutions is reported. The appended viologen does not quench the porphyrin fluorescence nor its triplet excited state due to the different solubilization of both parts of the molecule in the medium where the porphyrin ring resides in the hydrophobic phase and the alkoxy linker protrudes into the rather diffuse outer phase of detergent oxyethylene units, while the viologen moiety penetrates into the aqueous layer. However, laser flash photolysis measurements show that in the presence of nicotinamide dinucleotide, NADH, the porphyrin ring is reduced to phlorin due to the penetration of NADH into the organic phase. For porphyrin-tetraviologen in which a viologen molecule is linked to each of the porphyrin meso-position via alkoxy chain, fluorescence quenching could be achieved. The values of the quenching efficiency are high (94% in acetonitrile) compared to intramolecular quenching and are dependent upon the solvent viscosity.