Ferrocenyl Functionalized Silver-Chalcogenide Nanoclusters

New (chalcogenoethyl)ferrocenylcarboxalate functionalized silver chalcogenide nanoclusters were synthesized using a combination of silylated chalcogen reagents at low temperatures. The addition of E(SiMe3)(2) to reaction mixtures of FcC{O}OCH2 CH2ESiMe3 (E = S, Se) and (Ph3P)(2)center dot AgOAc affords nanoclusters with approximate molecular formulas [Ag36S9(SCH2CH2O{O} CFc)(18)(PPh3)(3)] (1), [Ag100Se17(SeCH2CH2O{O}CFc)(66)(PPh3)(10)] (2), and [Ag180Se54(SeCH2CH2O{O}CFc)(72)(PPh3)(14)] (3) as noncrystalline solids. Compositions were formulated on the basis of elemental analysis, high resolution transmission electron microscopy, and dynamic light scattering experiments. Solutions of these polyferrocenyl assemblies display a single quasi-reversible redox wave with some adsorption to the electrode surface as studied by cyclic voltammetry. With the smaller clusters 1, the addition of [Bu4N][HSO4] results in a shift of the reduction wave to less positive potentials than those of the complex in the absence of these oxoanions. No further shift is observed after the addition of approximately 1 equivalent of HSO4-/ferrocene branch. Cyclic voltammograms of the larger clusters 2 and 3 show the appearance of a new, irreversible wave at less positive potentials than the initial wave upon the addition of HSO4-. The appearance of this new wave together with the disappearance of the reduction wave indicates a stronger interaction between the nanoclusters and the hydrogen sulfate anion.