Investigation of Molecular Iridium Fluorides IrF n ( n =1–6): A Combined Matrix‐Isolation and Quantum‐Chemical Study

The photo‐initiated defluorination of iridium hexafluoride (IrF 6 ) was investigated in neon and argon matrices at 6 K, and their photoproducts are characterized by IR and UV‐vis spectroscopies as well as quantum‐chemical calculations. The primary photoproducts obtained after irradiation with λ =365 nm are iridium pentafluoride (IrF 5 ) and iridium trifluoride (IrF 3 ), while longer irradiation of the same matrix with λ =278 nm produced iridium tetrafluoride (IrF 4 ) and iridium difluoride (IrF 2 ) by Ir−F bond cleavage or F 2 elimination. In addition, IrF 5 can be reversed to IrF 6 by adding a F atom when exposed to blue‐light ( λ =470 nm) irradiation. Laser irradiation ( λ =266 nm) of IrF 4 also generated IrF 6 , IrF 5 , IrF 3 and IrF 2 . Alternatively, molecular binary iridium fluorides IrF n ( n =1–6) were produced by co‐deposition of laser‐ablated iridium atoms with elemental fluorine in excess neon and argon matrices under cryogenic conditions. Computational studies up to scalar relativistic CCSD(T)/triple‐ ζ level and two‐component quasirelativistic DFT computations including spin‐orbit coupling effects supported the formation of these products and provided detailed insights into their molecular structures by their characteristic Ir−F stretching bands. Compared to the Jahn‐Teller effect, the influence of spin‐orbit coupling dominates in IrF 5 , leading to a triplet ground state with C 4v symmetry, which was spectroscopically detected in solid argon and neon matrices.