While following our hypothesis resulted in a success in the screening, the detailed analysis of the relaxation mechanisms of VCl 3 (ddpd) and the four designed complexes revealed a complex picture. Despite nominally featuring electronic states of similar character, each complex displayed a unique reaction network in its photodynamics. This suggested that the success in the screening did not originate by following the assumption of our hypothesis, but rather resulted from some other, more individual electronic-structure features. In conclusion, the excited-state decay pathways of open-shell vanadium(III) complexes are complicated due to the large number of participating electronic states. Consequently, the effect of changing the ligand on their mechanisms are both difficult to predict and not obvious just from static electronic calculations. Instead, insights from more vanadium(III) complexes are needed for which a continued screening of nonadiabatic dynamics using the surface hopping/linear vibronic coupling combination is an efficient supplier.