Theoretical Study on the Geometry, Aromaticity, and Electronic Properties of Benzo[3,4]cyclobutathiophenes and Their Homologues.

The geometry, aromaticity, and electronic properties of benzo[3,4]cyclobutathiophenes (BCTs) and their homologues have been examined theoretically using density functional theory calculations. The harmonic oscillator measure of aromaticity and nucleus-independent chemical shift analyses revealed the aromaticity characteristics of the two regioisomers benzo[3,4]cyclobuta[1,2-b]thiophene and benzo[3,4]cyclobuta[1,2-c]thiophene. When the aromaticity of one of the six-π-electron rings increases, it concomitantly decreases in the other ring. The anti-aromaticity of the four-membered ring varies depending on the π-electron density of the shared bond with the thiophene ring. This leads to a large difference of the highest occupied molecular orbital-lowest unoccupied molecular orbital gap between the isomers. Linear BCT homologues show medium diradical characters and the smallest EGap values. In the angular and branched homologues, the π-electrons of central benzene rings are localized avoiding the shared bonds, which results in a nonaromatic character. These data were compared to those of the parent hydrocarbons. Because of the diene character of the thiophene ring, the number and position of annulated thiophenocyclobutadieno moieties significantly influence the aromaticity and EGap values of BCT homologues. The present study does not only provide insight into the aromaticity and the properties of organic compounds containing four-membered rings but also affords helpful design guidelines of novel organic semiconductors.