Nonplanar, Noninnocent, and Chiral: A Strongly Saddled Metallocorrole

The first crystal structure of a copper β-octabromo-meso-triarylcorrole exhibits a uniquely saddled corrole macrocycle, where adjacent pyrrole rings are tilted relative to each other by 60−80°. Such strong nonplanarity may be contrasted with the essentially planar macrocycle conformations observed in the vast majority of metallocorrole crystal structures. Density functional theory calculations suggest that two effects, ligand noninnocence and peripheral overcrowding, acting in concert, are responsible for the unique, observed conformation.