subtly tuned via chemical modifications on the dominant crystal-field (CF) interaction. For the complexes with L1 analogue under eight coordination, complexes 1 and 2 (D4d symmetry) with non-coordinated halides showed better magnetic properties as compared to complex 3 (C2v symmetry) due to the presence of strongly coordinated nitrate anion that leads to a change in the structural arrangement. However, complex 4 (C4v symmetry) with nine coordination was found structurally unfavorable comparatively due to the coordination of an additional third ligand (L2) that leads to a higher coordination number as a result of substituent change. Therefore, the presented compounds exhibit ligands substituent as well as counter ions dependent magnetic properties variations. Relatively a higher effective energy barrier (Ueff) was obtained for the compounds having the halide counter anions as compared with the neutral complexes. Moreover, ab initio calculations revealed that the transition magnetic moment probabilities for these compounds present very small or even vanishing quantum tunneling of the magnetization (QTM) between the ground-state Kramers doublets (KDs), and indicate that the slow relaxation might proceed through higher excited states. Finally, the described new compounds are expected to advance the aryloxide single-molecule magnets (SMMs).