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© The development of well–defined atomically precise heteronuclear nanoclusters passivated by protecting ligands is presently a booming area, owing to the fact that doping well–known homonuclear nanostructures allows fine–tuning of their properties. Here, we explore by means of density functional theory calculations the possibility of doping the central gold atom in the classical [Au13(dppe)5Cl2]3+cluster (1) by Os. Although both [Au13(dppe)5Cl2]3+ and [Os@Au12(dppe)5Cl2] have the same total number of electrons, we show that they are not isoelectronic within the formalism of the superatom model, being respectively an 8– and an 18–electron species. It results that they exhibit similar structures but present significantly different optical behaviors (ultraviolet/visible and circular dichroism). Similar results are obtained for the Ru and Fe relatives. Emission properties indicate some redshift of the T1→S1 decay with respect to [Au13(dppe)5Cl2]3+, involving an equatorial distortion of the Au12Cl2 core in the T1 state, rather than the axial distortion afforded by 1. The sizable highest occupied molecular orbital–lowest unoccupied molecular orbital gaps found for the three doped species suggest that further experimental exploration of different stable doped species derived from the ligand–protected Au12Cl2 core should be encouraged.
