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The free anions were obtained as well by co\u2010deposition of IrF<jats:sub>6<\/jats:sub> with laser\u2010ablated metals (Ir or Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two\u2010component quasi\u2010relativistic DFT methods accounting for spin\u2010orbit coupling (SOC) effects as well as multi\u2010reference configuration\u2010interaction (MRCI) approaches with SOC. Inclusion of SOC is crucial in the prediction of spectra and properties of IrF<jats:sub>6<\/jats:sub><jats:sup>\u2212<\/jats:sup> and its alkali\u2010metal ion pairs. The observed IR bands and the computations show that the IrF<jats:sub>6<\/jats:sub><jats:sup>\u2212<\/jats:sup> anion adopts an <jats:italic>O<\/jats:italic><jats:sub>h<\/jats:sub> structure in a nondegenerate ground state stabilized by SOC effects, and not a distorted <jats:italic>D<\/jats:italic><jats:sub>4h<\/jats:sub> structure in a triplet ground state as suggested by scalar\u2010relativistic calculations. The corresponding \u201cclosed\u2010shell\u201d M[IrF<jats:sub>6<\/jats:sub>] ion pairs with <jats:italic>C<\/jats:italic><jats:sub>3v<\/jats:sub> 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 IrF<jats:sub>7<\/jats:sub>, IrF<jats:sub>7<\/jats:sub><jats:sup>\u2212<\/jats:sup> or M[IrF<jats:sub>7<\/jats:sub>] (M=Na, K, Rb, Cs) ion pairs in our experiments.<\/jats:p>","DOI":"10.1002\/chem.202401015","type":"journal-article","created":{"date-parts":[[2024,4,15]],"date-time":"2024-04-15T05:14:33Z","timestamp":1713158073000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Investigation of Isolated IrF<sub>5<\/sub><sup>\u2212<\/sup>, IrF<sub>6<\/sub><sup>\u2212<\/sup> Anions and M[IrF<sub>6<\/sub>] (M=Na, K, Rb, Cs) Ion Pairs by Matrix\u2010Isolation Spectroscopy and Relativistic Quantum\u2010Chemical Calculations"],"prefix":"10.1002","volume":"30","author":[{"given":"Yan","family":"Lu","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Chemie und Biochemie-Anorganische Chemie Freie Universit\u00e4t Berlin  Fabeckstrasse 34\/36 14195 Berlin Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Artur","family":"Wody\u0144ski","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Theoretische Chemie\/Quantenchemie Technische Universit\u00e4t Berlin  Sekr. 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