We then tested our hypothesis in two steps. First, we designed 18 complexes based on design principles established for other 3dmetal complexes with large ligand-field splitting. Thereby we found that strategies of including ligands that are strong σ -donors or both σ and π donors are particularly successful. Among the 18 candidates complexes, we identified four complexes with ligandfield splitting larger than VCl 3 (ddpd). In the second step, we then performed long-time nonadiabatic dynamics simulations. For the four complexes, we could observe similar or larger transfer of electronic population via intersystem crossing from the triplet to the singlet states when compared to VCl 3 (ddpd). For two of the complexes, [VCl 3 (py-ph-py)] -and VCl 3 (im-im-im), reverse intersystem crossing subsequently depopulated the singlet states on a 20 ps time scale making them non-promising candidates for near-infra emission despite their large ligand-field splitting. For the other two complexes, however, we found long-lived singlet population that remains constant even after 100 ps simulation time. For VCl 3 (bi-bi-bi), this population of ca. 7% is of the same size as that for the reference VCl 3 (ddpd) complex (9%). For [VCl 3 (im-ph-im)] -, in turn, the long-lived singlet population is almost doubled to 16%, i.e., making it a promising candidate for efficient 3d-metal based near-infrared emitters.