The mechanism of the excited-state dynamics of VCl 3 (ddpd) has been discussed in Section 2.1. In short, intersystem crossing from the 3 T 1 ' states (dark blue line) populates singlet states (violet line) which reach a maximum population of 43% at ca. 4 ps. Afterwards, the singlet population falls again due to intersystem crossing to the 3 T 2 states (green line) from where the population relaxes to the 3 T 1 ground states (red line). Not all population leaves the singlet states, however, as we find a singlet population of ca. 9% after 100 ps that can be available for phosphorescence. Similar to VCl 3 (ddpd), we find pronounced intersystem crossing that populates the singlet states in all four newly designed complexes. During the simulations each singlet population reaches at least 41%, the largest one being 54% in the case of [VCl 3 (im-ph-im)] -, see Figure . All singlet population maxima are found within the first 5 ps simulation times. At later simulation times all singlet populations drop to lower values, however, leading to two different outcomes among the four complexes.