An atomically resolved gold nanocluster Au 99 (CCC 6 H 3 -2,4-F 2 ) 40 (Au 99 ) with an unusual 59 valence electrons has been synthesized. Single-crystal X-ray diffraction reveals that its Au 79 kernel is a Au 49 Marks decahedron capped by two Au 15 units. The surface structure of Au 99 consists of 20 linear Au(CCR) 2 staples. Intercluster interactions are observed between these D 5 symmetric clusters. The existence of an unpaired electron is verified by magnetic measurement. Interestingly, this open-shell gold cluster Au 99 stays intact in toluene solution at 80 °C for more than a week, and it has good charging−discharging capability under electrochemical conditions. The compact ligand shell protection around the symmetric core accounts for the high stability. This work suggests that geometric factors may play a crucial role in determining the stability of a metal nanocluster, even though the cluster has an open-shell electronic structure.

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For the first time site-specified doping of silver into a spherical Au25 nanocluster has been achieved in [Au19Ag6(MeOPhS)17(PPh3)6] (BF4)2 (Au19Ag6) through a dual-ligand coordination strategy. Single crystal X-ray structural analysis...