Heterobismetal Complexes of [26]Hexaphyrin(1.1.1.1.1.1)

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

以单金属三价金（AuIII）配合物为起始原料，可理性制备得到介位芳基取代的[26]六吡咯卟啉的AuIIICuIII与AuIIIRhI异双金属配合物。AuIIICuIII配合物为具有矩形结构的芳香性分子；而AuIIIRhI配合物则为面外大环结构，其芳香性或反芳香性取决于共轭π电子的数目。26π电子构型的AuIIIRhI配合物可通过在吡啶中回流，经双重C-H键活化反应，转化为兼具芳香性与平面结构的26π电子构型AuIIIRhIII配合物。