It is worth to note, however, the ππ * transition to S 5 at about 5.0 eV. While in PPMet-1 this transition is localized at PrdPyr and posses some oscillator strength, it reveals pure CT character in the case of PPMet-6 and PPMet-4, in which it corresponds to an electron transfer from MeOH to PrdPyr. The important difference between S 5 and lower-lying dark states is its ππ * character, involving the oxygen lone electron pair coupled to the C-H bonding orbitals, interacting with the π density at the PrdPyr moiety (Fig. and Figs. S1-S3 in the ESI). This transition, in contrast to nπ * excitations, exhibits character observed previously in systems undergoing efficient EDPT transformations. Finally, one may have a look at overlapped absorption spectra calculated for the Wigner distribution of vibrationally distorted molecular structures, shown in Figure . For each system, 150 points were included, with Lorentzian peak broadening of 0.05 eV at at the half maximum. In general, for all three systems, the low-energy absorption is dominated by a strong peak centered around 4.4 eV which can be primarily assigned to the S 0 → S 2 transition, with gradually growing contributions from the S 0 → S 3 and higher transitions at increasing excitation energy. The low-energy shoulder visible around 3.2 -3.7 eV originates from the very weak S 0 → S 1 absorption.