dc.contributor.author
Lu, Yan
dc.contributor.author
Wodyński, Artur
dc.contributor.author
Reimann, Marc
dc.contributor.author
Medel, Robert
dc.contributor.author
Kaupp, Martin
dc.contributor.author
Hasenstab-Riedel, Sebastian
dc.date.accessioned
2024-06-26T09:40:03Z
dc.date.available
2024-06-26T09:40:03Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/43483
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-43200
dc.description.abstract
The molecular IrF5−, IrF6− anions and M[IrF6] (M = Na-Cs) ion pairs were prepared by co-deposition of laser-ablated MF with IrF6 and isolated in solid Ne or Ar matrices. The free anions were obtained by co-deposition of IrF6 with laser-ablated metals (Ir, Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two-component quasi-relativistic DFT methods accounting for scalar-relativistic and spin-orbit coupling effects as well as multi-reference configuration-interaction approaches with SOC. Inclusion of SOC is crucial in the prediction of spectra and properties of IrF6− and its alkali-metal ion pairs. The observed IR bands and the computations show that the IrF6− anion adopts an Oh structure in a nondegenerate ground state stabilized by SOC effects, and not a distorted D4h structure in a triplet ground state as suggested by scalar-relativistic calculations. The corresponding “closed-shell” M[IrF6] ion pairs with C3v symmetry are stabilized by coordination of an alkali metal ion to three F atoms, and their structural change in the series from M = Na to Cs was proven spectroscopically. There is no evidence for the formation of IrF7, IrF7− or M[IrF7] (M = Na-Cs) ion pairs in our experiments.
en
dc.format.extent
8 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by/4.0/
dc.subject
IR spectroscopy
en
dc.subject
matrix isolation
en
dc.subject
d4 transition-metal
en
dc.subject
spin-orbit coupling
en
dc.subject
quantum chemistry
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften
dc.title
Investigation of Isolated IrF5−, IrF6− Anions and M[IrF6] (M = Na, K, Rb, Cs) Ion Pairs by Matrix-Isolation Spectroscopy and Relativistic Quantum-Chemical Calculations
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.articlenumber
e202401015
dcterms.bibliographicCitation.doi
10.1002/chem.202401015
dcterms.bibliographicCitation.journaltitle
Chemistry – A European Journal
dcterms.bibliographicCitation.number
34
dcterms.bibliographicCitation.volume
30
dcterms.bibliographicCitation.url
https://doi.org/10.1002/chem.202401015
refubium.affiliation
Biologie, Chemie, Pharmazie
refubium.affiliation.other
Institut für Chemie und Biochemie
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refubium.funding
DEAL Wiley
refubium.note.author
Die Publikation wurde aus Open Access Publikationsgeldern der Freien Universität Berlin gefördert.
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.eissn
1521-3765