Kekulé versus Lewis: when aromaticity prevents electron pairing and imposes polyradical character

Some conjugated alternant hydrocarbons, of singlet ground state according to Ovchinnikov's rule, may exhibit strong polyradical character, despite admitting complete pairing of electrons in bond orbitals between adjacent atoms. Typical organizations of this kind are encountered in polycyclic frames supporting two or more extracyclic methylene groups. Lewis bond pairing would require quinonization of six-membered rings, whereas safeguarding aromaticity proves sufficient to impose ground-state open-shell character, that is, the existence of unpaired electrons, providing the number of benzene rings to be quinonized is larger than two. Several examples built as variations around para-polyphenylene frames are examined through unrestricted DFT (UDFT) calculations, using various methods for spin decontamination of wavefunctions, geometries, and singlet-triplet energy gaps. They all illustrate how it is possible to conceive architectures that can be written with a closed-shell bond pairing, although they exhibit a large number of unpaired electrons. The same analyses also apply to systems in which quinonization would not kill but only reduce the number of unpaired electrons.