Abstract: | Porphyrin–AuIII complexes, which were partially or totally modified with C6F5 at the meso positions, were synthesized. The highly electron‐withdrawing substituents induced electron‐deficient states and Lewis acid properties. Single‐crystal X‐ray analysis of the ion pairs revealed ion‐pairing assemblies with characteristics dependent on the number and substitution pattern of the C6F5 units and the geometries of the anions. |