A series of six new free base porphyrins were synthesized for use as photosensitizers in TiO2 dye-sensitized
photo-electrochemical cells. The porphyrin sensitizers are attached to the TiO2 photoelectrode by phosphonic
or carboxylic acid anchoring groups. These anchoring groups were placed on different substitution positions on
the porphyrin moiety. The new dyes were fully characterized by absorption and emission spectroscopies,
electrochemistry and photo-electrochemical spectroscopy. The photo-electrochemical performances of the
sensitizers are discussed and compared to the known 5,10,15,20-tetra(4-carboxyphenyl)porphyrin sensitizer. In
this study, we show that the nature of the anchoring group (phosphonic or carboxylic acids) has little impact
on the photo-electrochemical performance of the cell. However, the substitution position of the anchoring
group on the porphyrin strongly influences the monochromatic photon-to-electron conversion efficiency of the
resulting cell. The results indicate that the electronic coupling of this type of dye with the d-band of the
semiconductor is one of the key parameters in the design of efficient sensitizers
