For a long time nitro-aromatics were considered non-emissive. The scattered examples of fluorescent nitroaromatics were regarded as a curiosity and hardly influenced the main stream of functional dyes' chemistry. The discovery of strongly emissive nitro-aromatics during the last decade enabled a partial change of this paradigm. Several quadrupolar, centrosymmetric nitro-aromatics were discovered and investigated. This in turn led to attempts to formulate some general rules governing their strong emission. π-Expanded diketopyrropyrroles were thought to present an ideal synthetic platform for modular access to centrosymmetric nitroaromatics. We recently reported the synthesis of a new type of π-expanded diketopyrrolopyrroles (EDPPs), which exhibit strong fluorescence in various solvents despite the presence of NO2 groups in their structure. The target molecules were synthesized in a two-step process which involved the N-arylation of DPPs followed by an intramolecular direct arylation of the aromatic rings that are present in these building blocks. This established synthetic pathway prompted us to synthesize other pigments, especially those in which the NO2 group is in a different position. Earlier observations indicated that the position of the nitro group in relation to the π-system core, has a profound influence on fluorescence. Here we report how competing excited state processes decide about the fate of centrosym-metric nitro-aromatics in the excited state, through determining their emissivity. To achieve this, we first designed a suitable DPP core containing alkylated fluorene, which ensured photophysical properties in the near-infrared region and provided appropriate solubility of the final dyes.