show a strong positive solvatochromism akin to that observed for DMAC-TRZ (Figure and Ref. 20) The large positive PL solvatochromism observed for both compounds suggests that the emissive excited state has a large permanent dipole moment, thus confirming the CT character of this state in both compounds. The progressive broadening of the emission band in the solvatochromism study is a result of polarityinduced inhomogeneous broadening. The well-resolved vibronic structure of the emission band in non-polar solvents is often considered an indication of a local nature of the relevant excitation. Therefore, to prove the CT nature of the lowest transition in DMAC-py-TRZ in all solvent, including non-polar ones, Figure shows spectra collected for the two molecular fragments, DMAC and py-TRZ. For py-TRZ, only absorption spectra are shown since the species is not emissive. The spectroscopic features of both molecular fragments are located at higher energies than the lowest energy feature seen in DMAC-py-TRZ, confirming that this specific feature is related to a CT state. An important and unusual result is recognized in the large Stokes shift observed for DMAC-py-TRZ in non-polar solvents (Table ): in methylcyclohexane, the absorption band is located at 370 nm, while the emission is seen at 472 nm, amounting to a Stokes shift of ~0.7 eV. This large Stokes shift can only be explained in terms of a very large molecular relaxation upon photoexcitation, well in line with the TD-DFT results that predict the relaxation of the S1 state from the bent to the orthogonal geometry.