Exploring ligand non-innocence of coordinatively-versatile diamidodipyrrinato cobalt complexes.

The non-innocence of diamidodipyrrin is explored in a series of cobaltous complexes with novel binding motifs. By varying the coordination modes, a reversible one-electron reduction is remarkably shifted by nearly 200 mV in a single metal-ligand platform. Our study illustrates a new strategy for modifying the redox activity of porphyrin-like scaffolds.