A New Entry to Doubly N‐Confused [26]Hexaphyrins(1.1.1.1.1.1) from Normal [26]Hexaphyrins(1.1.1.1.1.1) through an Unprecedented Double Pyrrolic Rearrangement

Treatment of hexakis(pentafluorophenyl)‐substituted [26]hexaphyrin(1.1.1.1.1.1) ( 1 ) with CuCl in the presence of pyridine and molecular oxygen led to formation of doubly N‐confused [26]hexaphyrin(1.1.1.1.1.1) 2 in a moderate yield through an unprecedented double pyrrolic rearrangement. Macrocycle 2 has been shown to serve as an effective bis‐metal‐coordinating ligand and exhibits attractive optical properties such as a sharp Soret‐like band at 566 nm and low‐energy fluorescence at 1058 nm.