Fluorine-Rich Fluorides: New Insights into the Chemistry of Polyfluoride Anions

Polyfluoride anions have been investigated by matrix‐isolation spectroscopy and quantum‐chemical methods. For the first time the higher polyfluoride anion [F5]− has been observed under cryogenic conditions in neon matrices at 850 cm−1. In addition, a new band for the Cs+[F3]− complex in neon is reported. Give me F,F,F,F,F, five: The polyfluoride anions [F5]− and Cs+[F3]− have been identified by matrix‐isolation spectroscopy and quantum‐chemical methods. The V‐shaped [F5]− ion gives rise to a band found in many IR laser ablation experiments that, up to now, could not be assigned.