Chang‐Hee Lee

A π‐extended, diaza‐triphenylene embedded, mono‐anionic corrole analogue and its Ni II complex were synthesized from a diaza‐triphenylene precursor, which was obtained from a double one‐carbon insertion into a naphthobipyrrole diester. Following conversion to the corresponding activated diol and acid‐catalyzed condensation with pyrrole, subsequent reaction with pentafluorobenzaldehyde afforded mono‐anionic, π‐extended bipyricorrole‐like macrocycle. Attempted Ni II insertion with Ni(OAc) 2 ⋅ 4H 2 O resulted an ESR active, Ni II bipyricorrole radical complex, which was converted to a stable cationic Ni II complex upon treatment with [(Et 3 O) + (SbCl 6 ) − ]. Both complexes were characterized by 1 H and 13 C NMR, UV/Vis spectroscopy and single crystal X‐ray diffraction analysis. The Ni II bipyricorrole radical complex is converted to a cationic Ni II complex by single‐electron reduction using cobaltocene. Both the cationic Ni II complex and the radical Ni II complex exhibited ligand‐centered redox behavior, whereas the Ni II remains in the +2 oxidation state.