Hypothesis II was based on the assumption that increasing the ligand-field splitting, the 3 T 2 states may become less available for depopulation of the singlet states, which could result in an larger long-lived singlet population compared to VCl 3 (ddpd). Considering the mechanisms shown in Figure (d), this mod-ification of the excited-state dynamics has only been achieved for VCl 3 (im-im-im), where the singlet states depopulate directly to the 3 T 1 ground states. However, this modification did not lead to a larger long-lived singlet population, as for VCl 3 (im-im-im) it almost to zero within 20 ps. In the other three designed complexes, the singlet depopulation still proceeds to the 3 T 2 states. For VCl 3 (bi-bi-bi), this leads to forward and backward 3 T 2 --→ ←--Sing reactions that result in long-lived singlet population of ca. 7%, i.e., similar to the 9% of VCl 3 (ddpd).