In order to investigate the excited-state dynamics of the candidate complexes, we must first determine their suitability given by the size of their ligand-field splitting. Due to the open-shell electronic structure of these metal-complexes, a correct description of the electronic structure of these complexes requires a multi-reference quantum chemical ansatz. As such calculations are computationally expensive and cannot be performed in a black-box manner, we opted to pre-screen the size of the ligand-field splitting using density functional theory (DFT). Thus, geometry optimization and frequency calculations were performed using DFT at the B3LYP/ZORA-def2-SVP level of theory. At the optimized geometries, excited states were calculated using time-dependent DFT (TDDFT) at the CAM-B3LYP/ZORA-def2-SVP level of theory. The strength of the ligand-field splitting was then calculated as the average difference between the energies of three components of the 3 T 1 ground-state term and the two components of the first excited 3 T 2 term, i.e., ∆E LFS = E( 3 T 2 ) -E( 3 T 1 ). We note that TDDFT is only capable of describing two of the three components of the 3 T 2 term as it includes only single excitations. This limitation is extended to a range of other low-lying states in vanadium(III) complexes and it is one of the reasons why a complete description of the excited-state properties can only be achieved using multi-reference methods including higher-order excitations such as CASSCF/CASPT2. Nevertheless, to obtain a measure of the ligand-field splitting, calculating the electronic states with DFT/TDDFT is sufficient as demonstrated below.