Bis-Copper(II)/π-Radical Multi-Heterospin System with Non-innocent Doubly N-Confused Dioxohexaphyrin(1.1.1.1.1.0) Ligand.

A contracted doubly N-confused dioxohexaphyrin(1.1.1.1.1.0) complex consisting of two paramagnetic copper metals and open-shell π-radical ligand was synthesized as a new multi-heterospin motif. X-ray spectroscopy supported the divalent character of the inner copper centers, and electron paramagnetic resonance and magnetometric studies suggested the presence of unpaired d electrons strongly antiferromagnetically coupled with π-radicals delocalized on the macrocycle. The 25 π non-innocent dioxohexaphyrin ligand allowed the facile interconversion between antiaromatic 24 π and aromatic 26 π species, respectively, upon redox reactions.