For four complexes exhibiting larger ligand-field splitting than VCl lations were performed using the OpenMolcas program package version 21.20. For each complex, 15 singlet and 16 triplet states were calculated using the state-averaged completeactive space self-consistent field (CASSCF) method and the ANO-RCC-VDZP basis sets. Different active spaces of (n, m) = (5,2), (7,4), (9,6), (11,8) and (13,10) were tested distributing m electrons in n orbitals. All active spaces included the five vanadium 3d orbitals and differ in the number of pairs of ligand π and π * orbitals (0-4 pairs). Solvent effects of MeCN were described using the C-PCM model. SOCs between all states were calculated using the atomic mean field (AMFI) approximation in the restricted active space state interaction (RASSI) program in OpenMolcas. Following the CASSCF calculations, energy corrections were calculated using multi-state complete active space second-perturbation theory (MS-CASPT2) where an imaginary level shift of 0.1 a.u. and IPEA shift values of 0.0 a.u. and 0.25 a.u. were compleyed. Similar calculations for VCl 3 (ddpd)were performed in Ref. 1.