Shedding light on octathio[8]circulene and some of its plate-like derivatives

Abstract

A quantum chemical investigation is made on the recently synthesized octathio[8]circulene (C₁₆S₈), an exotic molecule, the first fully heterocyclic circulene, from the structural and electronic properties and some charge-transport parameters viewpoints. Since the molecule consists of eight thiophene rings fused together, we have chosen to compare it with the acyclic (octathienoacene) analogue and to some relatives thereof, in which the sulfur atoms are substituted by Se, NH, CH₂ and O. C₁₆S₈, C₁₆Se₈ and C₁₆S₄Se₄ are found to show a low reorganization energy comparable or lower than that for already well known field-effect transistor (FET) materials, a promising property which, combined to some others revealed by this study, makes these compounds potential candidates for FET use. In addition, the twist angle is found to be tightly linked to the peripheral bonds lengths, the least twisted structures showing the most interesting properties for organic FET use.