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Yang, Huayan; Yan, Juanzhu; Wang, Yu; Su, Haifeng; Gell, Lars; Zhao, Xiaojing; Xu, Chaofa; Teo, Boon K; Häkkinen, Hannu; Zheng, Nanfeng
Journal of the American Chemical Society, 01/2017, Volume: 139, Issue: 1Journal Article
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 (2 2 ) and Ag63(SPhF2)36(PR′3)8+ (2 3 ), 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, 2 2 , and 2 3 , we predict the next “cube of cubes” to be Ag172(SR)72(PR′3)8 (3 3 ), in the evolution of growth of this cluster sequence.
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