Impact of Heterocycle Annulation on NIR Absorbance in Quinoid Thioacene Derivatives

The synthesis and characterisation of a homologous series of quinoid sulfur‐containing imidazolyl‐substituted heteroacenes is described. The optoelectronic and magnetic properties were investigated by UV/vis, fluorescence and EPR spectroscopy as well as quantum‐chemical calculations, and were compared to those of the corresponding benzo congener. The room‐temperature and atmospherically stable quinoids display strong absorption in the NIR region between 678 and 819 nm. The dithieno[3,2‐b:2′,3′‐d]thiophene and the thieno[2′,3′:4,5]thieno[3,2‐b]thieno[2,3‐d]thiophene derivatives were EPR active at room temperature. For the latter, variable‐temperature EPR spectroscopy revealed the presence of a thermally accessible triplet state, with a singlet‐triplet separation of 14.1 kJ mol(−1).