Issue 8, 2014

Synthesis and photophysical characterization of porphyrin and porphyrin–Ru(ii) polypyridyl chromophore–catalyst assemblies on mesoporous metal oxides

Abstract

A layer-by-layer procedure has been used to prepare chromophore–catalyst assemblies consisting of phosphonate-derivatized porphyrin chromophores and a phosphonate-derivatized Ru(II) water oxidation catalyst on the surfaces of SnO2 and TiO2 mesoporous, nanoparticle films. In the procedure, initial surface binding of the phosphonate-derivatized porphyrin is followed in sequence by reaction with ZrOCl2 and then with the phosphonate-derivatized water oxidation catalyst [RuII(2,6-bis-(1-methylbenzimidazole-2-yl)pyridine)(2,2′-bipyridine-4,4′-hydroxymethylphosphonate)(H2O)]2+, [RuII(Mebimpy)(4,4′-(PO(OH)2–CH2)2-bpy)(OH2)]2+. Fluorescence from both the free base and Zn(II) porphyrin derivatives on SnO2 is quenched; substantial emission quenching of the Zn(II) porphyrin occurs on TiO2. Transient absorption difference spectra provide direct evidence for appearance of the porphyrin radical cation on SnO2via excited-state electron injection. For the chromophore–catalyst assembly on SnO2, transient absorption difference spectra demonstrate rapid intra-assembly electron transfer oxidation of the catalyst following excitation and injection by the porphyrin chromophore.

Graphical abstract: Synthesis and photophysical characterization of porphyrin and porphyrin–Ru(ii) polypyridyl chromophore–catalyst assemblies on mesoporous metal oxides

Supplementary files

Article information

Article type
Edge Article
Submitted
25 Mar 2014
Accepted
07 May 2014
First published
08 May 2014

Chem. Sci., 2014,5, 3115-3119

Synthesis and photophysical characterization of porphyrin and porphyrin–Ru(II) polypyridyl chromophore–catalyst assemblies on mesoporous metal oxides

A. Nayak, R. R. Knauf, K. Hanson, L. Alibabaei, J. J. Concepcion, D. L. Ashford, J. L. Dempsey and T. J. Meyer, Chem. Sci., 2014, 5, 3115 DOI: 10.1039/C4SC00875H

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