Description:
<jats:title>Abstract</jats:title><jats:p>The Cs<jats:sup>+</jats:sup>[F<jats:sub>3</jats:sub>]<jats:sup>‐</jats:sup> ion pair as well as a so far unknown higher polyfluoride anion, [F<jats:sub>5</jats:sub>]<jats:sup>‐</jats:sup> are matrix‐isolated by reaction of laser‐ablated Cs atoms with F<jats:sub>2</jats:sub> in excess neon at 4 K, and characterized by IR spectroscopy and coupled‐cluster molecular structure calculations.</jats:p>