Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg24(SR)18]2鈥?/sup> (M = Pd, Pt) Clusters

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• 作者：Juanzhu Yan ; Haifeng Su ; Huayan Yang ; Sami Malola ; Shuichao Lin ; Hannu H盲kkinen ; Nanfeng Zheng
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：September 23, 2015
• 年：2015
• 卷：137
• 期：37
• 页码：11880-11883
• 全文大小：331K
• ISSN：1520-5126

文摘

With the incorporation of Pd or Pt atoms, thiolated Ag-rich 25-metal-atom nanoclusters were successfully prepared and structurally characterized for the first time. With a composition of [PdAg₂₄(SR)₁₈]^{2鈥?/sup> or [PtAg₂₄(SR)₁₈]2鈥?/sup>, the obtained 25-metal-atom nanoclusters have a metal framework structure similar to that of widely investigated Au₂₅(SR)₁₈. In both clusters, a M@Ag₁₂ (M = Pd, Pt) core is capped by six distorted dimeric -RS-Ag-SR-Ag-SR- units. However, the silver-thiolate overlayer gives rise to a geometric chirality at variance to Au₂₅(SR)₁₈. The effect of doping on the electronic structure was studied through measured optical absorption spectra and ab initio analysis. This work demonstrates that modulating electronic structures by transition-metal doping is expected to provide effective means to manipulate electronic, optical, chemical, and catalytic properties of thiolated noble metal nanoclusters.}