Aiming to obtain novel functional semiconducting materials for their use in organic electronics, the combination of strong donor moieties with electron-withdrawing units is one of the most useful strategies to obtain ambipolar semiconductors with tunable properties. Nowadays most of the efforts headed to efficient materials are based on small changes in the alkyl pendant chains or by replacing single atoms. However, a precise design of new functional materials is still challenging. For this reason, in this work we present a new synthetic approach for achieving redox amphoteric organic semiconductors by tuning their opto-electrochemical properties via rational chemical modifications. All these materials present low-lying LUMO levels, lower than −4.00 eV with broad absorption up to 800 nm in the UV-Vis-NIR spectra. In addition, they have been characterized by DFT, absorption and Raman vibrational spectroscopies, while their charge stabilization abilities are studied by means of spectroelectrochemical techniques. The results point out to a quite complex electronic scenario that goes beyond the expected cumulative effects of the independent molecular units constituting the final molecular assembly.
