Antiaromatic Dicyclopenta[]/[]naphthalene Isomers Showing an Open-Shell Singlet Ground State with Tunable Diradical Character.

Since the first isolation of 1,3,5,7-tetra--butyl--indacene in 1986, core-expanded - and -indacenes have attracted intensive interest. However, there is no reported synthesis of such type of molecules due to their high reactivity for over 30 years. Herein, we report the successful synthesis of two relatively stable, core-expanded indacene isomers, dicyclopenta[]-naphthalene () and dicyclopenta[]naphthalene (). X-ray crystallographic analyses reveal that the backbone of adopts a bond-delocalized structure, while that of exhibits a bond-localized character. Variable-temperature H NMR/ESR measurements, electronic absorption spectra, and theoretical calculations confirm that both molecules are globally antiaromatic and have an open-shell singlet ground state. However, shows stronger antiaromaticity, a larger diradical character ( = 48%), and a smaller singlet-triplet energy gap (Δ = -0.99 kcal mol) compared to ( = 30%, Δ = -6.88 kcal mol), which can be explained by their different quinoidal structures.