It is necessary to note that the relationship between overlapping magnetic orbitals and the antiferromagnetic nature of the coupling is revisited in Goodenough-Kanamori's model to understand the magnetic behavior of complexes in solid-state . Thus, the orthogonality and overlapping between magnetic orbitals are essential descriptors for exploring magnetic properties from a chemical point of view. Nonetheless, other structural parameters also act onto the orbital orthogonality and overlapping, such as planarity of the ring, which can affect the magnetic exchange between corroles, as found in the literature for bis-copper corroles . For this reason, the geometrical distortion (gd, Table ) of the CuN4 core was compared to the symmetric square plane structure (point group D4h) as a descriptor of the ligand field influence on the magnetic behavior. Thus, the higher gd value is found for stronger antiferromagnetic coupling in C5, reaching almost the unity. Besides, a statistical study to rationalize the magnetic behavior, structural parameters, and electronic properties demonstrate correlations of magnetic coupling with α, δ, gd, and S 2 , displaying correlation parameters of 0.77, 0.81, 0.95, and 0.99, respectively (Fig. ). Lastly, we highlighted that even the non-innocent character of corroles is strongly dependent on the planarity of corrole, substituent steric effects, and the metal center , corroborating the significant influence of structural and chemical modification on the electronic properties of corroles.