Magnetic Anisotropy of Tetrahedral Co^II Single-Ion Magnets: Solid-State Effects

This study reports the static and dynamic magnetic characterization of two mononuclear tetrahedral Co^II complexes, [Co{ⁱPr₂P(E)NP(E)ⁱPr₂}₂], where E = S (CoS₄) and Se (CoSe₄), which behave as single-ion magnets (SIMs). Low-temperature (15 K) single-crystal X-ray diffraction studies point out that the two complexes exhibit similar structural features in their first coordination sphere, but a disordered peripheral ⁱPr group is observed only in CoS₄. Although the latter complex crystallizes in an axial space group, the observed structural disorder leads to larger transverse magnetic anisotropy for the majority of the molecules compared to CoSe₄, as confirmed by electron paramagnetic resonance spectroscopy. Static magnetic characterization indicates that both CoS₄ and CoSe₄ show easy-axis anisotropy, with comparable D values (∼-30 cm^-1). Moreover, alternating-current susceptibility measurements on these Co^II complexes, magnetically diluted in their isostructural Zn^II analogues, highlight the role of dipolar magnetic coupling in the mechanism of magnetization reversal. In addition, our findings suggest that, despite their similar anisotropic features, CoS₄ and CoSe₄ relax magnetically via different processes. This work provides experimental evidence that solid-state effects may affect the magnetic behavior of SIMs.