Synthesis of Polycyclic Arenes Composed of Four-, Five-, Six-, and Eight-Membered Rings via an Unexpected Four-Membered Ring Formation Reaction.

The synthesis of polycyclic arenes composed of four-, five-, six-, and eight-membered rings via an unexpected four-membered ring formation reaction is reported. The carbonylation of an octalithiated tetraphenylene yielded a tricarbonylated arene containing a four-membered ring or a tetracarbonylated one, depending on the carbonyl reagents. The structures were determined by X-ray crystallography, and their electronic properties were examined by using absorption spectroscopy and cyclic voltammetry. The antiaromaticity of the four-, five-, and eight-membered rings of these compounds was studied by theoretical calculations.