Antiaromaticity of Planar Bisdehydro[12]- and Tetrakisdehydro[16]annulenes Fused with Dithieno[3,4-b:3′,4′-d]thiophenes

Thermally stable bisdehydro[12]- and tetrakisdehydro[16]-annulenes with planar structures were successfully synthesized by fusion with two dithieno[3,4-b:3',4'-d]thiophene units. The planarized [4n]annulene cores induced substantial antiaromaticity. However, the HOMO-LUMO gap slightly increased as the pi-core expanded from the planar cyclooctatetraene. This phenomenon, in contrast to that of typical pi-conjugated systems, was attributed to the decrease in antiaromaticity of the [4n]annulene cores. Both TD-HF and GIAO-HF calculations supported this conclusion.