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 [RhHAg24(SPhMe2)(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 [RhHAg24(SPhMe2)(18)](2-) nanocluster was isoelectronic to the [PdAg24(SPhMe2)(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.
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