The two points standing out in Figure with their short O-H distance at the moment of deactivation demonstrate strong O-N-interaction and can be associated with the indirect relaxation path mechanism discussed above. Indeed, in these two cases the O-N distance at the moment of hopping was found to be as low as 2.00 Å. Interestingly, while the points originate from two different dynamics (i.e., PPMet-6 and PPMet-4), both structures adopt the HB pattern characteristic for PPMet-4 (for molecular structures visualization, see Fig. in the ESI). Although this is only a single event, it stays in line with the preference for the photo-relaxation through the PPMet-4 channel. At the same time it should be noted that, in other cases, the final relaxation to the ground electronic state follows almost exclusively the original system configuration; for more details on this aspect, please refer to Fig. in the ESI.