Sing. crease of the ligand-field splitting leads to more population being initially transferred from the triplet to the singlet states. This is apparent in the maximum singlet population in Figure (b), that is larger for VCl 3 (im-im-im), [VCl 3 (im-ph-im)] -, and VCl 3 (bi-bi-bi) compared to VCl 3 (ddpd), and of the same order for [VCl 3 (py-ph-py)] -. However, contradicting hypothesis II, an increase of the ligand-field splitting does not correlate with larger long-lived singlet population. While we find similar or larger long-lived singlet population for VCl 3 (bi-bi-bi) and [VCl 3 (im-ph-im)] -, respectively, compared to VCl 3 (ddpd), the singlet population drops to almost zero for [VCl 3 (py-ph-py)] -and VCl 3 (im-im-im), see Figure . The reason for the partial affirmation and contradiction lies in the mechanisms dictating the excited-state dynamics of each complex. They are depicted in Figure . In this figure, states which are populated at the start of the dynamics simulations are shown at the top with labels above them denoting the initial population in percentage, e.g., 54% for the Hypothesis I was based on the assumption that increasing the ligand-field splitting could destabilize the 3 A 2 states belonging to the e 2 g configuration. This could quench the internal conversion from the 3 T 1 ′ states to the 3 A 2 states, which is the main com-peting pathway to the intersystem crossing populating the singlet states in VCl 3 (ddpd). As can be seen, this assumption is realized in the dynamics of [VCl 3 (py-ph-py)] -, [VCl 3 (im-ph-im)] -, and VCl 3 (bi-bi-bi), where T 1 ′ --→ 3 A 2 internal conversion is either completely quenched ([VCl 3 (py-ph-py)] -) or its importance reduced to a few percentage. In contrast, for VCl 3 (im-im-im), internal conversion to the 3 A 2 states becomes the almost sole deactivation pathway from the 3 T 1 ′ states. Nevertheless, however, more population reaches the singlet states for VCl 3 (im-im-im) (48%) compared to VCl 3 (ddpd) (43%), as the singlet states now receive population from the 3 T 2 states. Furthermore, it is interesting to note that the pathway populating the singlet states in each of the four designed complexes is different from that of VCl 3 (ddpd), where all population entering the singlets is received from the 3 T 1 ′ states. For [VCl 3 (py-ph-py)] -and for [VCl 3 (im-ph-im)] -, the singlet states are populated from the 3 DL states that possess ligandcentered excitation character, while for VCl 3 (bi-bi-bi), the singlet states are populated via the 3 T 2 similar to the other tricarbene-ligand bearing complex VCl 3 (im-im-im). Thus, while our hypothesis I that increasing the ligand-field splitting leads to larger population transfer to the singlet states is confirmed, its cause stems from different modifications in the reaction mechanisms of the different complexes.