Intercluster Reactions between Au25(SR)18 and Ag44(SR)30

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• 作者：K. R. Krishnadas ; Atanu Ghosh ; Ananya Baksi ; Indranath Chakraborty ; Ganapati Natarajan ; Thalappil Pradeep
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：January 13, 2016
• 年：2016
• 卷：138
• 期：1
• 页码：140-148
• 全文大小：642K
• ISSN：1520-5126

文摘

We present the first example of intercluster reactions between atomically precise, monolayer protected noble metal clusters using Au₂₅(SR)₁₈ and Ag₄₄(SR)₃₀ (RS– = alkyl/aryl thiolate) as model compounds. These clusters undergo spontaneous reaction in solution at ambient conditions. Mass spectrometric measurements both by electrospray ionization and matrix assisted laser desorption ionization show that the reaction occurs through the exchange of metal atoms and protecting ligands of the clusters. Intercluster alloying is demonstrated to be a much more facile method for heteroatom doping into Au₂₅(SR)₁₈, as observed by doping up to 20 Ag atoms. We investigated the thermodynamic feasibility of the reaction using DFT calculations and a tentative mechanism has been presented. Metal core-thiolate interfaces in these clusters play a crucial role in inducing these reactions and also affect rates of these reactions. We hope that our work will help accelerate activities in this area to establish chemistry of monolayer protected clusters.