Ferrocenyl Functionalized Silver-Chalcogenide Nanoclusters

详细信息    查看全文

• 作者：Daniel G. MacDonald ; Christian Ku虉bel ; John F. Corrigan
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：April 18, 2011
• 年：2011
• 卷：50
• 期：8
• 页码：3252-3261
• 全文大小：1096K
• 年卷期：v.50,no.8(April 18, 2011)
• ISSN：1520-510X

文摘

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}OCH₂CH₂ESiMe₃ (E = S, Se) and (Ph₃P)₂路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^{鈭?/sup>/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鈭?/sup>. 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.}