Journal
NATURE COMMUNICATIONS
Volume 9, Issue -, Pages -Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/s41467-018-05584-9
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Funding
- National Key R&D Program of China [2017YFA0207302]
- National Natural Science Foundation of China [21731005, 21420102001, 21333008, 21721001]
- iChEM, Xiamen University
- China's National Innovation and Intelligence Introduction Base visitor program
- Academy of Finland [266492, 294217]
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This paper reports co-crystallization of two atomically precise, different-size ligand-stabilized nanoclusters, a spherical (AuAg)(267)(SR)(80) and a smaller trigonal-prismatic (AuAg)(45)(SR)(27)(PPh3)(6) in 1:1 ratio, characterized fully by X-ray crystallographic analysis (SR = 2,4-SPhMe2). The larger cluster has a four concentric-shell icosahedral structure of Ag@M-12@M-42@M-92@Ag-120(SR)(80) (M = Au or Ag) with the inner-core M-147 icosahedron observed here for metal nanoparticles. The cluster has an open electron shell of 187 delocalized electrons, fully metallic, plasmonic behavior, and a zero HOMO-LUMO energy gap. The smaller cluster has an 18-electron shell closing, a notable HOMO-LUMO energy gap and a molecule-like optical spectrum. This is the first direct demonstration of the simultaneous presence of competing effects (closing of atom vs. electron shells) in nanocluster synthesis and growth, working together to form a co-crystal of different-sized clusters. This observation suggests a strategy that may be helpful in the design of other nanocluster systems via co-crystallization.
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