Weak Coordinating Character of Organosulfonates in Oriented Silica Films: An Efficient Approach for Immobilizing Cationic Metal-Transition Complexes.

Iron (II) tris(2,2'-bipyridine) complexes, [Fe(bpy)], have been synthesized and immobilized in organosulfonate-functionalized nanostructured silica thin films taking advantage of the stabilization of [Fe(HO)] species by hydrogen bonds to the anionic sulfonate moieties grafted to the silica nanopores. In a first step, thiol-based silica films have been electrochemically generated on indium tin oxide (ITO) substrates by co-condensation of 3-mercaptopropyltrimethoxysilane (MPTMS) and tetraethoxysilane (TEOS). Secondly, the thiol function has been modified to sulfonate by chemical oxidation using hydrogen peroxide in acidic medium as an oxidizing agent. The immobilization of [Fe(bpy)] complexes has been performed in situ in two consecutive steps: (i) impregnation of the sulfonate functionalized silica films in an aqueous solution of iron (II) sulfate heptahydrate; (ii) dipping of the iron-containing mesostructures in a solution of bipyridine ligands in acetonitrile. The in situ formation of the [Fe(bpy)] complex is evidenced by its characteristic optical absorption spectrum, and elemental composition analysis using X-ray photoelectron spectroscopy. The measured optical and electrochemical properties of immobilized [Fe(bpy)] complexes are not altered by confinement in the nanostructured silica thin film.