This red ESA feature has a lifetime of 12.2 ns matching very closely to the fluorescence lifetime of 15.5 ns, indicating this band originates from the ICT species (Supplementary Table and 3). We also observe a 10-15 nm relaxation of this state within this lifetime. This dispersion arises from dihedral angle inhomogeneity in a twisted D-A molecule, giving a broad-range of excited state lifetimes. In DCM, the instantaneous 560 nm band was observed to decay very rapidly within 1 ps, with the formation of an initial ICT ESA at 730 nm, that rapidly relaxes to 820 nm within ca. 1.7 ps (Figure and Supplementary Fig. ). This is consistent with the higher polarity and reorganisation of the DCM solvation shell (vide infra). The 820 nm ESA has a lifetime of 1.5 ns that matches the 1.5 ns fluorescence lifetime. Notably, from MCH to DCM a solvent shift of 60 nm is observed in the ICT ESA, which is less than the ca. 100 nm solvatochromic shift observed in fluorescence. The band shape and position of this red ESA is very similar to previous observations of ESA from the 1 (Cz) + species Finally, the fast photo-dynamics of o-ICz-PI has signatures consistent with both the other molecules. In MCH, instantaneous ESA at 570 nm (which we correlate with the 410 nm shoulder observed in the o-ICz-PI fluorescence) proceeds to rapid formation of ESA at 650 nm in 1.7 ps that slowly relaxes to 660 nm within 10 ps (Supplementary Fig. and). This state decays with a lifetime of 14 ns, in line with the fluorescence lifetime (Supplementary Table ). Again, we associate this ESA feature with a localised 1 (Cz) + donor species. Within ca. 1 ps, a long wavelength ESA emerges extending beyond 830 nm. This band decays in ca.