DT-TTF was synthesised according to previously described procedures. This six-step synthetic route provides a higher yield than those previously reported (see ESI †). Arylated DT-TTF derivatives were obtained by optimising a previously reported synthetic procedure based on the palladium-catalysed direct C-H arylation of aromatic compounds with aryl halides. In this study, the aryl bromides used in the reaction were functionalised with electron-withdrawing -NO 2 (2) or electron-donating -NMe 2 (3) groups to evaluate their influence on the DT-TTF electronic properties (HOMO and LUMO energy levels). The reaction of DT-TTF (1) (1 equiv.) with aryl bromides (1 equiv.) in the presence of cesium carbonate, tri-tert-butylphosphonium tetrafluoroborate and palladium acetate (5 mol%) in THF under reflux yielded the monoarylated derivatives 2 and 3 in 13% and 85% yields, respectively (Scheme 3 and ESI † for experimental details). The lower yield in the case of using electron-withdrawing aryl bromides such as Br-Ar-NO 2 has also been observed in other direct C-H arylation reactions under similar conditions. 33