Embryonic Growth of Face-Center-Cubic Silver Nanoclusters Shaped in Nearly Perfect Half-Cubes and Cubes

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• 作者：Huayan Yang ; Juanzhu Yan ; Yu Wang ; Haifeng Su ; Lars Gell ; Xiaojing Zhao ; Chaofa Xu ; Boon K. Teo ; Hannu HäkkinenNanfeng Zheng
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：January 11, 2017
• 年：2017
• 卷：139
• 期：1
• 页码：31-34
• 全文大小：416K
• ISSN：1520-5126

文摘

Demonstrated herein are the preparation and crystallographic characterization of the family of fcc silver nanoclusters from Nichol’s cube to Rubik’s cube and beyond via ligand-control (thiolates and phosphines in this case). The basic building block is our previously reported fcc cluster [Ag₁₄(SPhF₂)₁₂(PPh₃)₈] (1). The metal frameworks of [Ag₃₈(SPhF₂)₂₆(PR′₃)₈] (2²) and [Ag₆₃(SPhF₂)₃₆(PR′₃)₈]⁺ (2³), where HSPhF₂ = 3,4-difluorothiophenol and R′ = alkyl/aryl, are composed of 2 × 2 = 4 and 2 × 2 × 2 = 8 metal cubes of 1, respectively. All serial clusters share similar surface structural features. The thiolate ligands cap the six faces and the 12 edges of the cube (or half cube) while the phosphine ligands are terminally bonded to its eight corners. On the basis of the analysis of the crystal structures of 1, 2², and 2³, we predict the next “cube of cubes” to be Ag₁₇₂(SR)₇₂(PR′₃)₈] (3³), in the evolution of growth of this cluster sequence.