For [VCl 3 (py-ph-py)] -, the singlet states become almost completely depopulated after 20 ps. Finally, for [VCl 3 (im-ph-im)] -, despite the presence of the Sing --→ 3 T 2 channel, we find the largest long-lived singlet population of ca. 16%. While fortuitous, this discovery must rather be ascribed to serendipity, as it larger long-lived singlet population did not follow from our hypothesis II. Indeed, comparing the full mechanisms across all five simulated complexes in Figure (d) reveals a unique reaction network for each single complex. This individuality is likely ascribed to the many electronic states of similar electronic character that take part in the relaxation mechanisms. Changing the nature of the ligand modifies the electronic structure of the complex in subtle ways that are difficult to predict. This difficulty in predicting excited-state decay pathways translates directly to the rational design of open-shell 3d-luminophores, which instead of single available examples rather must draw from a wide array of tested candidate complexes, which makes efforts such as this screening study all the more needed.