Electron localization in nonplanar conjugated macrocycles: Failure of electron buffers to delocalize electrons

► Radical generated by homolysis of the axial metal-ligand bond in a macrocycle. ► Electron delocalization through the conjugated ring contributes to the stability. ► Descriptors about the distribution of the unpaired electron in the radical. ► Competition of electron doping sites: metal-centered versus macrocycle-centered. ► Redox chemistry and electron transfer are affected by planarity.