All compounds were systematically explored with DFT models at the B3LYP-6-31G(d,p) level revealing that the DT-TTF moiety adopts a boat conformation with a low stabilization energy with respect to its planar counterparts of circa 1 kcal/mol for 1 and 2 kcal/mol for 2 and 3. This low energy matches the fact that 1 is flat in the solid state while in vacuum and in CH 2 Cl 2 continuum the presence of imaginary frequencies indicates this is not a minimum (Fig. ). For 4 and 5, the more extensive functionalization implies a larger energetic penalty, 18 kcal/mol, when compared to planar conformations. This is due to the increased number of functional groups and the larger steric hindrance from the extra methyl groups. The HOMO and LUMO energy levels and optical gap were computed at the B3LYP-6-311+G(2d,p)-CH 2 Cl 2 /B3LYP-6-31G(d,p)-CH 2 Cl 2 and give trends in reasonable agreement with the experimental observations (Table ). DFT results on both conformations of 1 show how the effect on the electronic properties on conformation is far from negligible. In addition, 2, 4, and 5 show a strongly reduced density on the TTF DT-TTF moiety (Fig. ) which accounts for the large stabilization estimated experimentally. The HOMOs densities are more homogenous with 1, 2, 4, and 5 showing very similar densities localized on the DT-TTF moiety and only 3 showing a different density.