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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
dc.contributor.author | Wei, Jianyu | |
dc.contributor.author | Rodríguez-Kessler, P. L. | |
dc.contributor.author | Halet, Jean François | |
dc.contributor.author | Kahlal, Samia | |
dc.contributor.author | Saillard, Jean Yves | |
dc.contributor.author | Muñoz-Castro, Alvaro | |
dc.date.accessioned | 2021-06-22T16:18:03Z | |
dc.date.available | 2021-06-22T16:18:03Z | |
dc.date.issued | 2021 | |
dc.identifier | 10.1021/acs.inorgchem.1c00799 | |
dc.identifier.issn | 00201669 | |
dc.identifier.uri | https://hdl.handle.net/20.500.12728/8941 | |
dc.description.abstract | 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. | es_ES |
dc.language.iso | en | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.title | 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 | es_ES |
dc.type | Article | es_ES |