Zinc(II) tetraarylporphyrins anchored to TiO2, ZnO, and ZrO2 nanoparticle films through rigid-rod linkers

Langmuir : the ACS Journal of Surfaces and Colloids
Jonathan Rochford, E Galoppini

Abstract

A series of six Zn(II) tetraphenylporphyrins (ZnTPP), with a phenyl (P) or oligophenyleneethynylene (OPE = (PE) n ) rigid-rod bridge varying in length (9-30 A) and terminated with an isophthalic acid (Ipa) anchoring unit, were prepared as model dyes for the study of sensitization processes on metal oxide semiconductor nanoparticle surfaces (MO(n) = TiO(2), ZnO, and insulating ZrO(2)). The dyes were designed such that the electronic properties of the central porphyrin chromophore remained consistent throughout the series, with the rigid-rod anchoring unit allowing each porphyrin unit to be located at a fixed distance from the metal oxide nanoparticle surface. Electronic communication between the porphyrin and the rigid-rod unit was not desired. Rigid-rod porphyrins ZnTPP-Ipa, ZnTPP-P-Ipa, ZnTPP-PE-Ipa, ZnTPP-(PE)(2)-Ipa, ZnTPP-(PE)(3)-Ipa, and ZnTMP-Ipa (with mesityl substituents on the porphyrin ring) were synthesized using combinations of mixed aldehyde condensations and Pd-catalyzed cross-coupling reactions. Their properties, in solution and bound, were compared with that of Zn(II) 5,10,15,20-tetra(4-carboxyphenyl)porphyrin ( p-ZnTCPP) as the reference compound. Solution UV-vis and steady-state fluorescence spectra for all si...Continue Reading

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