The calculated ligand-field splittings ∆E LFS are shown in Figure ). In the following, we first discuss the best-performing complexes, before we turn to a more general discussion of the design strategies. As can be seen, four complexes represented by green circles show larger ∆E LFS than the reference complex VCl 3 (ddpd)for which ∆E LFS is shown as the red line. These complexes comprise species 4, 11, 12, and 18. Complex 4 is an anionic complex featuring an organic ligand comprised of two peripheral pyridine units directly linked by a central phenyl anion; it will be referred to as [VCl 3 (py-ph-py)] -in the following discussion. Complexes 11 and 18 are the neutral complexes VCl 3 (im-im-im) and VCl 3 (bi-bi-bi) with organic ligands comprised by three imidazolylidene or benzimidazolylidene groups, respectively, that are bridged by methylene units. Finally, complex 12 is the anionic complex [VCl 3 (im-ph-im)] -with two peripheral imidazolylidene groups connected via carbonyl units to a central phenyl-anion moiety. The ligand-field splitting ∆E LFS of VCl 3 (ddpd) calculated at the TDDFT level of theory amounts to 1.98 eV. In comparison, ∆E LFS of the four complexes is larger by ca. 0.1 eV.