4-: Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au20 Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations

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dc.contributor.authorGam, Franck
dc.contributor.authorArratia-Pérez, Ramiro
dc.contributor.authorKahlal, Samia
dc.contributor.authorSaillard, Jean-Yves
dc.contributor.authorMuñoz-Castro, Álvaro
dc.date.accessioned2022-08-30T17:59:22Z
dc.date.available2022-08-30T17:59:22Z
dc.date.issued2018-03
dc.descriptionIndexación Scopuses
dc.description.abstractCharacterization of the tetrahedral Au20 structure in the gas phase remains a major landmark in gold cluster chemistry, where further efforts to stabilize this bare 20-electron superatom in solution to extend and understand its chemistry have failed so far. Here, we account for the structural, electronic, and bonding properties of [M16Ni24(CO)40]4- (M = Cu, Ag, Au) observed in solution for gold and silver. Our results show a direct electronic relationship with Au20, owing that such species share a common tetrahedral [M16]4- central core with a 1S21P61D102S2 jellium configuration. In the case of Au20, the [Au16]4- core is capped by four Au+ ions, whereas in [M16Ni24(CO)40]4- it is capped by four Ni6(CO)10 units. In both cases, the capping entities are a full part of the superatom entity, where it appears that the free (uncapped) [M16]4- species must be capped for further stabilization. It follows that the Ni6(CO)10 units in [M16Ni24(CO)40]4- should not be considered as external ligands as their bonding with the [M16]4- core is mainly associated with a delocalization of the 20 jellium electrons onto the Ni atoms. Thus, the [M16Ni24(CO)40]4- species can be seen as the solution version of tetrahedral M20 clusters, encouraging experimental efforts to further develop the chemistry of such complexes as M(111) finite surface section structures, with M = Ag and Au and, particularly promising, with M = Cu. Furthermore, optical properties were simulated to assist future experimental characterization. © 2018 American Chemical Society.es
dc.description.urihttps://pubs-acs-org.recursosbiblioteca.unab.cl/doi/10.1021/acs.jpcc.8b00227
dc.identifier.citationJournal of Physical Chemistry C Volume 122, Issue 8, Pages 4723 - 47301 March 2018es
dc.identifier.doi10.1021/acs.jpcc.8b00227
dc.identifier.issn19327447
dc.identifier.urihttps://repositorio.unab.cl/xmlui/handle/ria/23669
dc.language.isoenes
dc.publisherAmerican Chemical Societyes
dc.rights.licenseCC BY-NC-ND 4.0
dc.subjectFluorescencees
dc.subjectMetal Clusterses
dc.subjectIcosahedrones
dc.title4-: Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au20 Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculationses
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