Synthesis of RhH-doped Au-Ag alloy nanoclusters and dopant evolution.

Doping atomically precise metal nanoclusters (NCs) with heterometals is a powerful method for tuning the physicochemical properties of the original NCs at the atomic level. While the heterometals incorporated into metal NCs are limited to group 10-12 metals with closed d-shells, the doping of open d-shell metals remains largely unexplored. Herein, we report the synthesis of Rh-doped Au-Ag alloy NCs by a metal-exchange reaction of [RhHAg(SPhMe)] NCs with an Au-thiolate complex.

Superatom-in-Superatom Nanoclusters: Synthesis, Structure, and Photoluminescence.

We report a new strategy in which a thiolate-protected Ag nanocluster can be doped with open d-shell group 8 (Ru, Os) and 9 (Ir) metals by forming metal hydride (RuH , OsH , IrH) superatoms with a closed d-shell. Structural analyses using various experimental and theoretical methods revealed that the Ag nanoclusters were co-doped with the open d-shell metal and hydride species to produce superatom-in-superatom nanoclusters, establishing a novel superatom doping phenomenon for open d-shell metals. The synthesized superatom-in-superatom nanoclusters exhibited dopant-dependent photoluminescence (PL) properties.

Superatom-in-Superatom [RhH@Ag (SPhMe ) ] Nanocluster.

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 (SPhMe ) ] nanocluster, in which a Rh atom with open d-shells ([Kr]4d 5s ) is incorporated into the Ag framework by forming a RhH superatom with closed d-shells ([Kr]4d ).