The functionalization of tetrathienoanthracene (TTA) with bromine and 2-hexylthiophene moieties is described, and their influence at both the molecular and solid-state level has been investigated. Comparative optical and electrochemical studies indicate an increase in conjugation for the thiophene derivative compared to the parent TTA. In the solid state, these materials form slipped π-stack structures with a number of close intermolecular contacts. Comparison of the two structures reveals a more steeply inclined slipped π-stack for the thiophene derivative resulting in a closer interplanar separation. This, coupled with the extended molecular framework, leads to an enhanced number of π−π interactions within the stack. The combination of increased conjugation at the molecular level, and π-stacked structures with strong intermolecular communication at the solid-state level, augurs well for the use of TTA materials in optoelectronic applications.

The versatility of fourfold Stille coupling to afford oligothiophene‐functionalized tetrathienoanthracene (TTA) and benzene derivatives is described. The influence of the larger, more rigid TTA core on the electronic and structural properties was investigated. Comparative optical and electrochemical studies demonstrate a diminishing HOMO–LUMO gap as the length of the oligothiophene chain increases, with the rigid TTA compounds exhibiting lower energy gaps than the more flexible benzene analogues. X‐ray crystallography studies reveal that the thiophene‐substituted TTA structure consists of slipped π‐stacks with several close intrastack π–π interactions; no close contacts are observed for the benzene derivative due to twisting of the thiophene ligands out of plane. Consequently, the molecules in the benzene analogue are isolated from their neighbours. The thiophene and bithiophene functionalised TTA compounds were fabricated into OTFT devices in bottom‐contact configuration and exhibited mobilities of ca. 10–4 cm2 V–1 s–1 and on/off ratios of more than four orders of magnitude.