The Mn and Ni [M(AcPyOx) 3 (BPh)] + complexes in Fig. possess energetically well-isolated orbitally singlet ground states leading to the ground SO manifolds characterized by the real spin of the ions and negligible first-order orbital contributions. The g-shifts and g-anisotropy ∆ g = g ∥g ⊥ in the Mn complex are so small that one can safely ignore the dipolar contributions to the observed paramagnetic chemical shifts. In the Ni complex, the second order SO interaction with the excited states leads to a small ZFS D = 7.5 cm -1 and g-anisotropy with SO-CASPT2 g ∥ = 2.20, g ⊥ = 2.24, observable by EPR. However, the values are too small to introduce significant magnetization anisotropy at room temperature. In comparison to the total paramagnetic chemical shifts, the data in Table show minute dipolar shifts, the most significant of which are for those in close proximity to the paramagnetic center. Even though they are small, the dipolar hyperfine shifts computed for some nuclei using the unrestricted DFT based ZORA-PBE0 and SO-CASSCF hyperfine tensors differ due to the differences in g-shifts. Consequently, NMR chemical shifts in both complexes are predominantly governed by diamagnetic and contact contributions, with dipolar effects being inherently small in the Ni complex due to ZFS anisotropy. The absence of first-order orbital contributions results in the reduction of the paramagnetic susceptibility χ to the spin-only values (χ ≈ χ s ) for the ground manifolds. This equivalence allows for similar estimations of contact shifts, whether derived from the spin Hamiltonian manifold or spanning the entire ab initio energy spectrum, as exemplified by the comparison of paramagnetic chemical shifts in the Ni complex (see Table ).