Journal article

Tetrachelate Porphyrin Chromophores for Metal Oxide Semiconductor Sensitization: Effect of the Spacer Length and Anchoring Group Position

Four Zn(II)-tetra(carboxyphenyl)porphyrins in soln. and bound to metal oxide (TiO2, ZnO, and ZrO2) nanoparticle films were studied to det. the effect of the spacer length and anchoring group position (para or meta) on their binding geometry and photoelectrochem. and photophys. properties. The properties of three types of anchoring groups (COOH and COONHEt3) for four Zn(II)-porphyrins (Zn(II)-5,10,15,20-tetra(4-carboxyphenyl)porphyrin (p-ZnTCPP), Zn(II)-5,10,15,20-tetra(3-carboxyphenyl)porphyrin (m-ZnTCPP), Zn(II)-5,10,15,20-tetra(3-(4-carboxyphenyl)phenyl)porphyrin (m-ZnTCP2P), and Zn(II)-5,10,15,20-tetra(3-ethynyl(4-carboxyphenyl)phenyl)porphyrin (m-ZnTC(PEP)P)) were compared. In m-ZnTCPP, m-ZnTCP2P, and m-ZnTC(PEP)P the four anchoring groups are in the meta position on the meso-Ph rings of the porphyrin macrocycle, thus favoring a planar binding mode to the metal oxide surfaces. The three meta-substituted porphyrin salts have rigid spacer units of increasing length (Ph (P), biphenyl (P2), and diphenylethynyl (PEP)) between the porphyrin ring and the carboxy anchoring groups, thus raising the macrocycle from the metal oxide surface. All porphyrins studied here, when bound to TiO2 and ZnO, exhibited quenching of the fluorescence emission, consistent with electron injection into the conduction band of the semiconductor. Steady-state UV-vis and fluorescence studies of p-ZnTCPP on insulating ZrO2 showed evidence of aggregation and exciton coupling. This was not obsd. in any of the meta-substituted porphyrins. The photoelectrochem. properties (IPCE, Voc, and Isc) of the porphyrins bound to TiO2 films in solar cells have been measured and rationalized with respect to the sensitizer binding geometry and distance from the surface.


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