Intramolecular coupling of bis(2-ethylthio-1,3-thiazolium) salts upon electrochemical reduction leads to dithiadiazafulvalenes (DTDAF). These novel pi-electron donor molecules show extremely high donating properties compared to their sulfur analogues, tetrathiafulvalenes (TTF). In addition we report that a DTDAF precursor substituted by a dithiafulvenyl group undergoes dimerization upon oxidation to afford vinylogous TTF. Cathodic coupling of the corresponding tetra(2-ethylthio-1,3-thiazolium) salt leads to a new donor including two different donor families: DTDAF and vinylogous TTF.