Core Size Conversion: Route for Exclusive Synthesis of Au38 or Au40 Nanomolecules

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• 作者：Praneeth Reddy Nimmala ; Vijay Reddy Jupally ; Amala Dass
• 刊名：Langmuir
• 出版年：2014
• 出版时间：March 11, 2014
• 年：2014
• 卷：30
• 期：9
• 页码：2490-2497
• 全文大小：389K
• 年卷期：v.30,no.9(March 11, 2014)
• ISSN：1520-5827

文摘

Gold nanomolecules with a precise number of gold atoms and ligands have promise for catalytic, optical, and biomedical applications. For practical applications, it is essential to develop synthetic protocols to prepare monodisperse gold nanomolecules. A typical synthesis yields a number of nanomolecules with discrete numbers of core atoms. Thermochemical treatment in the presence of excess thiol, etching, is known to narrow down the number of discrete nanomolecules, by selective degradation of sizes with lower stability. Au₃₈(SR)₂₄ and Au₄₀(SR)₂₄ are abundantly formed in these etching reactions due to their extraordinary stability to chemical etching. These nanomolecules are of high interest due in part to its stability, X-ray crystallographic structure availability (Au₃₈), and intrinsic chirality arising from the arrangement of the Au-SR interface. However, the synthetic routes typically yield a mixture of Au₃₈ and Au₄₀, demanding extensive separation protocols. Here, we present a synthetic route to prepare either Au₃₈ or Au₄₀ exclusively in the product of etching. This was made possible by conducting a comprehensive mechanistic study starting from single-sized reactant. Au₆₇ on etching yields Au₄₀ exclusively. Au_103鈥?05(SR)_45鈥?6 on etching also yields Au₄₀ exclusively. Clusters of various sizes smaller than Au₆₇ on etching yield Au₃₈ exclusively. This is the first direct evidence for the exclusive formation of Au₃₈ and Au₄₀ nanomolecules by core size conversion. Mass spectrometry was used to study the core size conversion reactions to understand the mechanism. Au₃₈ and Au₄₀ nanomolecules form via different intermediates, as observed in the mass spectrometry data.