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Antimony pentafluoride is a strong Lewis acid and fluoride‐ion acceptor that has not previously demonstrated any discreet fluoride‐ion donor properties. The first donor‐stabilised [SbF4]+ cations were prepared from the autoionisation of SbF5 in the presence of bidentate N‐donor ligands 2,2’‐bipyridine (bipy) and 1,10‐phenanthroline (phen) as their [SbF6]− salts. The [SbF4(N−N)][Sb2F11] (N−N=bipy,...