Superatom‐in‐Superatom [RhH@Ag<sub>24</sub>(SPhMe<sub>2</sub>)<sub>18</sub>]<sup>2−</sup> Nanocluster
Hanseok Yi, Sang Myeong Han, Suhwan Song, Min-Seok Kim, Eunji Sim, Dongil Lee
Abstract
Abstract Heterometal doping is a powerful method for tuning the physicochemical properties of metal nanoclusters. While the heterometals doped into such nanoclusters predominantly include transition metals with closed d‐shells, the doping of open d‐shell metals remains largely unexplored. Herein, we report the first synthesis of a [RhHAg 24 (SPhMe 2 ) 18 ] 2− nanocluster, in which a Rh atom with open d‐shells ([Kr]4d 8 5s 1 ) is incorporated into the Ag 24 framework by forming a RhH superatom with closed d‐shells ([Kr]4d 10 ). Combined experimental and theoretical investigations showed that the Ag 24 framework was co‐doped with Rh and hydride and that the RhH dopant was a superatomic construct of a Pd atom. Additional studies demonstrated that the [RhHAg 24 (SPhMe 2 ) 18 ] 2− nanocluster was isoelectronic to the [PdAg 24 (SPhMe 2 ) 18 ] 2− nanocluster with the superatomic 8‐electron configuration (1S 2 1P 6 ). This study demonstrated for the first time that a superatom could be incorporated into a cluster superatom to generate a stable superatom‐in‐superatom nanocluster.