Heterobismetal Complexes of [26]Hexaphyrin(1.1.1.1.1.1)

Au^IIICu^III and Au^IIIRh^I heterobismetal complexes of meso-aryl-substituted [26]hexaphyrin were rationally prepared from a monometal Au^III complex. The Au^IIICu^III complex is an aromatic molecule with a rectangular shape, while Au^IIIRh^I complexes are out-of-plane macrocycles, being either aromatic or antiaromatic depending upon the number of conjugated π electrons. The 26π Au^IIIRh^I complex was converted into an aromatic and planar 26π Au^IIIRh^III complex via double C−H bond activation upon refluxing in pyridine.