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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 Ag 14 (SPhF 2 ) 12 (PPh 3 ) 8 ( 1 ). The metal frameworks of Ag 38 (SPhF 2 ) 26 (PR′ 3 ) 8 (2 2 ) and Ag 63 (SPhF 2 ) 36 (PR′ 3 ) 8 + ( 2 3 ), where HSPhF 2 = 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 Ag 172 (SR) 72 (PR′ 3 ) 8 ] ( 3 3 ), in the evolution of growth of this cluster sequence.
Yang et al. (Mon,) studied this question.