Abstract

Sequential adsorption of polyanions and polycations was used to make a five-component energy/electron-transfer cascade, which mimics some of the functions of natural photosynthetic assemblies. The photon antenna part of the system consists of coumarin- and fluorescein-derivatized poly(allylamine hydrochloride) (Coum-PAH and Fl-PAH), palladium(II)tetrakis(4-N,N,N-trimethylanilinium) porphyrin (PdTAPP4+) or palladium(II)tetrakis(4-sulfonatophenyl) porphyrin (PdTSPP4-) layers, interleaved with anionic Zr(HPO4)2·H2O (α-ZrP) sheets. α-ZrP or HTiNbO5 sheets separate the porphyrin electron donor from a polyviologen electron acceptor layer. Layer-by-layer growth of these thin film assemblies was characterized by atomic force microscopy (AFM) and ellipsometry on planar supports, and by elemental analysis, surface area measurements, and transmission electron microscopy high on surface area silica supports. UV−vis absorption and steady-state emission spectroscopies showed that the overall energy/electron-transfer re...

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