Our strategy to find near-infrared emitting vanadium(III) complexes with larger photoluminescence yields, is to design complexes with larger ligand-field splitting than VCl 3 (ddpd). The problem of achieving larger ligand-field splitting in first-row transition metal complexes is a common one in current efforts to find replacements using Earth-abundant 3d metals for efficient heavymetal-based chromophores. 40,45-47 Thus, we can base our design on some of the principles that have already been established to achieve very large ligand-field splitting in first-row transitionmetal complexes. In particular, we have employed the five design principles depicted in Figure (ii) high coordination symmetry close to the ideal octahedral one to maximize the overlap/repulsion between metal and ligand orbitals , (iii) strong π-acceptor ligands to stabilize the t 2g orbitals , (iv) combining strong σ -and π-donating properties in cyclometalating ligands , and (v) using stronger σ -donors instead of the Cl -ligands following the spectrochemical series.