Due to the extended delocalization of electron density for both dyes 7 and 8, we expected, in analogy with formerly reported quadrupolar molecules 6a , NIR excited state absorptions to take place. Pump-probe measurements in the 800-910 nm spectral range have been performed for both compounds in toluene and chloroform solutions with the US-pp setup described in Supporting Information and the Global analysis results have been reported in Figure . In chloroform, both dyes 7 and 8 showed a broader spectral shape than in toluene as well as a slight time-dependent blue shift of band maximum; which is practically absent in toluene. Dynamical spectral shift and spectral broadening are very common markers for the stabilization of excited states. This is due to polar and slightly polar solvents strongly suggesting that excited state absorption involves a state characterized by a certain degree of charge separation. Global analysis, within a two-component sequential model scheme, revealed one main spectral component relaxing back to the ground state, with the time constant of this process being in very good agreement with that of the ground state bleaching decay. The first picosecond component has been ascribed to intramolecular structural relaxation. Transient infrared spectra (Fig S13) are in good agreement with the UV-Vis pump-probe, showing ground state recovery on the hundred's picosecond timescale for EDPP 8 in THF. 11 Additional evidence that the presence of a CT state plays the key role in determining fluorescence properties of dyes 7 and 8, has been obtained from temperature-dependent fluorescence lifetime measurements in 2Me-THF. The data are reported in Figure , Figure and table TS1. Dye 7 shows no temperature dependence from 298 K to 77 K, while EDPP 8 evidence a clear increase of fluorescence lifetimes upon cooling down the solution. Broadband pumpprobe measurements in the visible spectral range have been also performed in frozen solvent and at romm temperature. Results, reported in Figure and S12 of the Supporting Information, show no spectral shift in the first 200 ps, demonstrating that in a glassy solvent, the structural relaxation is blocked. These results suggest that both thermal activation and structural relaxation play key roles in the radiative and non-radiative decay mechanisms of excited states EDPPs 7 and 8.