Cocrystallization‐driven Formation of fcc‐based Ag110 Nanocluster with Chinese Triple Luban Lock Shape

Abstract Luban locks with mortise and tenon structure have structural diversity and architectural stability, and it is extremely challenging to synthesize Luban lock‐like structures at the molecular level. In this work, we report the cocrystallization of two structurally related atom‐precise fcc silver nanoclusters Ag 110 (SPhF) 48 (PPh 3 ) 12 ( Ag 110 ) and Ag 14 ( μ 6 ‐S)(SPhF) 12 (PPh 3 ) 8 ( Ag 14 ). It is worth noting that the Ag 110 cluster is the first compound to simulate the complex Luban lock structure at the molecular level. Meanwhile, Ag 110 is the largest known fcc‐based silver nanocluster, so far, there is no precedent for fcc silver nanocluster with more than 100 silver atoms. DFT calculations show that Ag 110 is a 58‐electron superatom with an electronically closed shell1S 2 1P 6 1D 10 2S 2 1F 14 2P 6 1G 18 . Ag 110 ⋅Ag 14 can rapidly catalyze the reduction of 4‐nitrophenol within 4 minutes. In addition, Ag 110 presents clear structural evidence to reveal the critical size and mechanism of the transformation of metal core from fcc stacking to quasi‐spherical superatom. This research work provides an important structural model for studying the nucleation mechanism and structural assembly of silver nanoclusters.