Strategy (i) of including strong σ -donors such as N-heterocyclic carbenes appears successful, since three of the four complexes with larger ∆E LFS than VCl 3 (ddpd) contain at 2-3 carbene units, i.e., [VCl 3 (im-ph-im)] -(4), VCl 3 (im-im-im) (11), and VCl 3 (bi-bi-bi) (18). However, some of the complexes featuring one or multiple carbene units, e.g., 7 or 14, possess smaller ∆E LFS than VCl 3 (ddpd) or the similar complexes 2 and 3. Thus, it seems to be important with which other units the carbene ligands are combined in order to achieve large ligand-field splitting. In strategy (ii), large ligand-field splitting should be realized by achieving a coordination geometry that is as close as possible to an ideal octahedral one. In order to quantify this coordination feature, we show ∆E LFS in Figure (b) as a function of the average of the angles between the trans-coordinated atoms in the vanadium(III) complexes. As can be seen, while complexes with the smallest ∆E LFS such as 1 and 6 also show rather small average trans angles, such small angles do not necessarily lead to small ∆E LFS , as exemplified by complexes 5, 9, 15, and [VCl 3 (im-ph-im)] -(4). Strategy (iii) of using strong π-acceptors such as pyridine units sets the baseline for large ligand-field splitting as is realized in VCl 3 (ddpd). However, this strategy appears to be less promising, as complexes designed in this manner are among the ones with the smallest ∆E LFS , e.g., 1, 6, and 10.