By implementing very subtle changes in the structures of two regioisomeric, quadrupolar, centrosymmetric, π-expanded diketopyrrolopyrroles, it is possible to completely alter their emissive properties. Moving nitro groups from distant position to the sp2 carbon atom close to C=O bond decreases the fluorescence intensity by a factor of 10. Contrarily, placing the nitro group at a distant position leads to super strong emitter with optical brightness ≈ 110,000 at 635 nm. TD-DFT computations for dyes 7 and 8, indicate, that upon excitation, these molecule reach a bright S1 state characterized by ππ* nature, with the energy of the dark S2 state being only slightly higher than that of the S1 (Fig. ). Unlike dye 7, EDPP 8, once in the bright S1 state, undergoes rapid internal conversion to the dark S2 state through thermal activation. Photophysical studies in frozen glass provide convincing evidence that the rate constant knr for the non-emissive EDPP reaches values comparable to those of the emissive DPP below 120 K. Broadband pump-probe suggest that thermally activated internal conversion through CT S2 state is mediated by intramolecular structural relaxation. The fundamental difference between dyes 7 and 8 arises from the fact that the presence of the nitro group at the ortho position relative to the bridge with the DPP core, is sufficient to induce non-planarity in both the ground state and excited state conformations of dye 8. In this context, the presence of the nitro group plays a decisive role, as the Coulombic repulsion between the negative charges (with the second being the oxygen of the C=O group) results in a nonplanar conformation. Their excellent properties, such as record-breaking optical brightness opens the door for future applications in optoelectronics. Given the recent renaissance of interest in nitroaromatics this work should inspire the future design of strongly emitting fluorophores bearing NO2 groups, with distinctive π-expanded architectures.