Dithieno[a,e]pentalenes: Highly Antiaromatic Yet Stable π-Electron Systems without Bulky Substituents

Dithieno[a,e]penalenes (DTPs) with various substituents were synthesized as a class of antiaromatic compounds. Annulation of thiophene rings imparts the pentalene moiety with high thermal stability even without bulky substituents, while retaining antiaromaticity. The higher magnitude of antiaromaticity in DTPs, in addition to the differences in the electronic structures of the fused aromatic rings, resulted in a narrower HOMO-LUMO gap than that of the corresponding dibenzo[a,e]pentalene analog, giving rise to red-shifted electronic absorption that reaches the near-infrared region. Moreover, systematic investigations on the solid-state packing structure revealed that DTPs prefer offset face-to-face packing motifs rather than face-centered π-π stacking. In particular, the thienyl-substituted DTP bearing hydrophilic side chains exhibited thermochromic behavior in polar solvents, which was ascribed to the formation of aggregates.