| Abstract
| - Nanostructured molecular film containing the (μ-hydroxo)bis(μ-carboxylato) diruthenium(III) units, [RuIII2(μ-OH)(μ-CH3COO)2(HBpz3)2]+ ({RuIII2(μ-OH)}), was prepared by an in situ conversion of its μ-oxo precursor, [RuIII2(μ-O)(μ-CH3COO)2(HBpz3)2] ({RuIII2(μ-O)}), in a Nafion membrane matrix, where HBpz3 is hydrotris(1-pyrazolyl)borate.The conversion procedure results in fine nanoparticle aggregates of the {RuIII2(μ-OH)} units in the Nafion membrane(Nf-{RuIII2(μ-OH)}), where an average particle size (4.1 ± 2.3 nm) is close to the Nafion's cluster dimension of∼4 nm. Chemically modified electrodes by using the Nafion molecular membrane films (Nf-{RuIII2(μ-OH)}-MMFEs)were further developed on ITO/glass and glassy carbon electrode (GCE) surfaces, and a selective reduction of nitrosoniumion (NO+), presumably through reaction of a {RuIIRuIII(μ-OH)} mixed-valence state with HNO2, was demonstratedwithout interference by molecular oxygen in an acidic aqueous solution. The Nf-{RuIII2(μ-OH)}-MMFEs are stableeven in a physiological condition (pH 7), where the naked {RuIII2(μ-OH)} complex is readily transformed into itsdeprotonated {RuIII2(μ-O)} form, demonstrating an unusual stabilizing effects for the {RuIII2(μ-OH)} unit by theNafion cluster environment.
|
