Synthesis of A 2 B 6 ‐Type [36]Octaphyrins: Copper(II)‐Metalation‐Induced Fragmentation Reactions to Porphyrins and N ‐Fusion Reactions of meso ‐(3‐Thienyl) Substituents

5,10,15‐Tris(pentafluorophenyl)tetrapyrromethane was efficiently prepared through a route involving stepwise diaroylation of 5‐pentafluorophenyldipyrromethane. A 2 B 6 ‐type [36]octaphyrins were prepared by the cross condensation of the tetrapyrromethane with aryl aldehydes in moderate yields. A 2 B 6 ‐type [36]octaphyrins bearing 2,4,6‐trifluorophenyl, 2,6‐dichlorophenyl, and phenyl substituents underwent Cu II ‐metalation‐induced fragmentation to give two molecules of AB 3 ‐type Cu II porphyrins. A 2 B 6 ‐type [36]octaphyrin bearing 3‐thienyl substituents underwent thermal N ‐thienyl fusion reactions to provide a modestly aromatic [38]octaphyrin, which, upon treatment with MnO 2 , underwent further N ‐thienyl fusion and subsequent oxidation to give a nonaromatic doubly N ‐thienyl fused [36]octaphyrin.