Description:
<jats:title>Abstract</jats:title><jats:p>Molecular alkali tetrafluorido aurate ion pairs M[AuF<jats:sub>4</jats:sub>] (M=K, Rb, Cs) are produced by co‐deposition of IR laser‐ablated AuF<jats:sub>3</jats:sub> and MF in solid neon under cryogenic conditions. This method also yields molecular AuF<jats:sub>3</jats:sub> and its dimer Au<jats:sub>2</jats:sub>F<jats:sub>6</jats:sub>. The products are characterized by their Au–F stretching bands and high‐level quantum‐chemical calculations at the CCSD(T)/triple‐ζ level of theory. Structural changes in AuF<jats:sub>4</jats:sub><jats:sup>−</jats:sup> associated with the coordination of the anion to different alkali cations are proven spectroscopically and discussed.</jats:p>