期刊
MOLECULES
卷 27, 期 17, 页码 -出版社
MDPI
DOI: 10.3390/molecules27175444
关键词
mesoporous silica films; polypyridyl metal complexes; confinement effects; metal ligand coordination; organic-inorganic hybrids; iron-bipyridine derivatives; modified electrodes
资金
- French PIA project Lorraine Universite d 0Excellence [ANR-15-IDEX-04-LUE]
- CPER (program SusChemProc)
Iron (II) tris(2,2 '-bipyridine) complexes have been synthesized and immobilized in nanostructured silica thin films using organosulfonate moieties. The immobilization process does not affect the optical and electrochemical properties of the complexes.
Iron (II) tris(2,2 '-bipyridine) complexes, [Fe(bpy)(3)](2+), have been synthesized and immobilized in organosulfonate-functionalized nanostructured silica thin films taking advantage of the stabilization of [Fe(H2O)(6)](2+) 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)(3)](2+) 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)(3)](2+) 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)(3)](2+) complexes are not altered by confinement in the nanostructured silica thin film.
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