Air-/Heat-Stable Crystalline Carbon-Centered Radicals Derived from an Annelated N-Heterocyclic Carbene

Organic radicals are open-shell species and have been extensively applied to functional materials due to their unique physicochemical properties with unpaired electrons; however, most of them are highly reactive and short-lived. Herein, a series of stable radicals were readily accessed in two steps from a bis(imino)acenaphthene-supported N-heterocyclic carbene (IPr(BIAN)) through enhancing the delocalization of spin density. The IPr(BIAN)-based radicals 3a–c, obtained by reduction of the corresponding iminium salts 2a–c with KC8, have been spectroscopically and crystallographically (3a,c) characterized. DFT calculations indicate that increasing the electron-withdrawing properties of the para substituent on the carbene carbon atom results in the spin density evolving from the acenaphthene ring to the phenyl ring. The IPr(BIAN)-based radicals 3a–c show excellent stability: they have half-lives of 1 week in well-aerated solutions and feature a high thermal decomposition temperature up to 200 °C.