Aromaticity, as a classical and fundamental concept in chemistry, can enhance thermodynamic stability. In sharp contrast, a previous study showed that antiaromaticity rather than aromaticity can enhance the radical stability of α-methyl heterocyclic compounds. Here, we demonstrate a similar antiaromaticity-promoted radical stability when the methyl group is replaced by five-membered (alkyl)(amino)cyclics (AACs). More interestingly, when an AAC is fused with an antiaromatic ring, the radical stability could be either reduced or enhanced, depending on the spin population. Specifically, when the spin density is populated on an incoming antiaromatic 1,4-dihydro-1,4-diborinine moiety, the radical stability is enhanced whereas when the spin density is maintained on the original five-membered ring, the radical stability is reduced. Our findings highlight the importance of spin density in tuning the radical stability, inviting experimental chemists’ verification.

https://pubs.rsc.org/en/content/articlelanding/2024/cp/d4cp01031k