The electrochemical properties of DT-TTF derivatives 1-4 were investigated by cyclic voltammetry (CV) using n-Bu 4 NPF 6 (0.15 M) as electrolyte in CH 2 Cl 2 at room temperature (Fig. ). Cyclic voltammogram of unsubstituted DT-TTF shows two redox processes assigned to the oxidation to the radical cation DT-TTF •+ (E ox1 = +0.29 V vs Fc/Fc + ) and dication DT-TTF 2+ (E ox2 = +0.74 V vs Fc/Fc + ) species. As expected, the first (E ox1 = +0.38 V vs Fc/Fc + ) and second (E ox2 = +0.83 V vs Fc/Fc + ) oxidation potentials increase in 2 in comparison to the unsubstituted DT-TTF 1 due to the incorporation of electronwithdrawing -NO 2 functional group. On the contrary, oxidation potentials of 3 (E ox1 = +0.27 V; E ox2 = +0.73 V vs Fc/Fc + ) slightly decrease when introducing electron-donor groups indicating the increase of the HOMO level. Oxidation potentials of 4 also show positive shifts relative to those of 1 which is consistent with the presence of four ester groups. The HOMO energy levels of 1-4 were estimated from the onset of the first oxidation redox processes (see Table ). CV of 5 using n-Bu 4 NPF 6 (0.15 M) as electrolyte in DMF (Figure , ESI †) shows two weak redox peaks at positive potentials which decrease in intensity after consecutive cycles, possibly due to the irreversible decarboxylation process upon oxidation originated by the Kolbe reaction, as it has been previously reported for similar TTF derivatives bearing carboxylic groups. UV-vis spectra of DT-TTF derivatives 1-4 were measured in CHCl 3 (0.05 mM) at room temperature (Fig. ). Whereas absorption spectra of 1 and 3 remain similar, the absorption bands of 2 and 4 are redshifted due to the electron-withdrawing character of the nitro and ester substituents. The optical gaps for 1-4 were calculated from the onset of the most red-shifted band of the UV-vis spectra and were, in turn, used to estimate the energy of the LUMOs (Table ).