Binding CO2 by a Cr8 Metallacrown

The {Cr₈} metallacrown CrF(O₂C^tBu)₂]₈, containing a F‐lined internal cavity, shows high selectivity for CO₂ over N₂. DFT calculations and absorption studies support the multiple binding of F‐groups to the C‐center of CO₂ (C⋅⋅⋅F 3.190(9)–3.389(9) Å), as confirmed by single‐crystal X‐ray diffraction.