On Heteronuclear Isoelectronic Alternatives to [Au(13)(dppe)(5)Cl(2)](3+): Electronic and Optical Properties of the 18-Electron Os@[Au(12)(dppe)(5)Cl(2)] Cluster from Relativistic Density Functional Theory Computations - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2021

On Heteronuclear Isoelectronic Alternatives to [Au(13)(dppe)(5)Cl(2)](3+): Electronic and Optical Properties of the 18-Electron Os@[Au(12)(dppe)(5)Cl(2)] Cluster from Relativistic Density Functional Theory Computations

Résumé

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 [Au(13)(dppe)(5)Cl(2)](3+)cluster (1) by Os. Although both [Au(13)(dppe)(5)Cl(2)](3+) and [Os@Au(12)(dppe)(5)Cl(2)] 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 T(1)→S(1) decay with respect to [Au(13)(dppe)(5)Cl(2)](3+), involving an equatorial distortion of the Au(12)Cl(2) core in the T(1) 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 Au(12)Cl(2) core should be encouraged.

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Dates et versions

hal-03247541 , version 2 (21-06-2021)
hal-03247541 , version 1 (11-05-2023)

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Jianyu Wei, Peter L Rodríguez-Kessler, Jean-François Halet, Samia Kahlal, Jean-Yves Saillard, et al.. On Heteronuclear Isoelectronic Alternatives to [Au(13)(dppe)(5)Cl(2)](3+): Electronic and Optical Properties of the 18-Electron Os@[Au(12)(dppe)(5)Cl(2)] Cluster from Relativistic Density Functional Theory Computations. Inorganic Chemistry, 2021, 60 (11), pp.8173-8180. ⟨10.1021/acs.inorgchem.1c00799⟩. ⟨hal-03247541v2⟩
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