On Heteronuclear Isoelectronic Alternatives to [Au₁₃(dppe)₅Cl₂]³⁺: Electronic and Optical Properties of the 18-Electron Os@[Au₁₂(dppe)₅Cl₂] Cluster from Relativistic Density Functional Theory Computations

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 their properties. Here, we explore means density functional theory calculations possibility central gold atom in classical [Au13(dppe)5Cl2]3+cluster (1) Os. Although both [Au13(dppe)5Cl2]3+ and [Os@Au12(dppe)5Cl2] have same total number electrons, show they are not isoelectronic within formalism superatom model, being respectively an 8- 18-electron species. It results exhibit similar structures but present significantly different optical behaviors (ultraviolet/visible circular dichroism). Similar obtained for Ru Fe relatives. Emission properties indicate some redshift T1?S1 decay with respect [Au13(dppe)5Cl2]3+, involving equatorial distortion Au12Cl2 core T1 state, rather than axial afforded 1. sizable highest occupied molecular orbital–lowest unoccupied orbital gaps found three doped species suggest further experimental exploration stable derived from ligand-protected should be encouraged.