Gold Complexes with Difunctional Perfluoroalkyl Chains: Quantifying the Energy of Aurophilic Interactions in Flexible Open‐Chain Complexes

The first binuclear Au^I compounds containing bridging (CF₂)_n chains (n=4, 6, 8) and Au^III metallaperfluorocyclopentanes have been obtained by photoinitiated reactions of LAuMe (L=PPh₃, PMe₃, PCy₃, or IPr) with α,ω‐diiodoperfluorocarbons. Complexes LAu(CF₂)₄AuL present an unusual looped structure stabilized by an aurophilic interaction for L=PMe₃, PPh₃, and PCy₃. The study of their dynamic behaviour has provided new insights about the strength of aurophilic interactions in solution, allowing quantification of the energy of a single Au???Au interaction.