In DMAC-py-TRZ, the T1 state is predicted to exist as a twisted geometry in both the rigid (Figure ) and relaxed scans (Figure ). The full optimization of the excited state geometry, however, yields conflicting results. For S1 the situation is clear: taking either the bent or the orthogonal geometry as starting points for the excited state optimization, the S1 geometry (Figure ) always converges to the orthogonal conformation, supporting the results from the relaxed scan analysis. For T1, instead, two different structures are reached depending on the starting geometry (Figure ), with slightly different ΔE !"#$" values (0.93 eV where the dihedral angle is 30 o and 0.41 eV where the dihedral angle is 60 o ). The energy of the two triplet conformations is similar (Δ𝐸 %" !"°$%"°= 0.07 eV), so that a firm conclusion about the equilibrium geometry for T1 cannot be reached. The CT band of DMAC-py-TRZ at 370 nm is slightly blue-shifted with respect to DMAC-TRZ at 382 nm. The most striking difference is, however, in the much larger intensity of the band measured for DMAC-py-TRZ (e =43,800 M -1 cm -1 ) vs DMAC-TRZ (e = 2100 M -1 cm -1 ). This is a direct consequence of the different conformations adopted by the two compounds in the ground state: the orthogonal conformation of DMAC-TRZ (observed in the crystal structure and predicted by DFT) hinders an effective conjugation and suppresses the intensity of the low-energy CT transition. On the other hand, the bent conformation of DMAC-py-TRZ (observed in the crystal structure and predicted by DFT) promotes an efficient conjugation of the two moieties, perfectly in line with the oscillator strength calculated with TD-DFT (oscillator strengths are reported in Figure , together with NTOs).