Theoretical Investigation of Single-Molecule-Magnet Behavior in Mononuclear Dysprosium and Californium Complexes

Early-actinide-based (U, Np, and Pu) single molecule magnets (SMMs) have yet to show magnetic properties similar to those of highly anisotropic lanthanide-based ones. However, there are not many studies exploring the late-actinides (more than half-filled f shells) as potential candidates for SMM applications. We computationally explored the electronic structure and magnetic properties of a hypothetical Cf(III) complex isostructural to the experimentally synthesized Dy(dbm)3(bpy) complex (bpy = 2,2 '-bipyridine; dbm = dibenzoylmethanoate) via multireference methods and compared them to those of the Dy(III) analogue. This study shows that the Cf(III) complex can behave as a SMM and has a greater magnetic susceptibility compared to other experimentally and computationally studied early-actinide-based (U, Np, and Pu) magnetic complexes. However, Cf spontaneously undergoes alpha-decay and converts to Cm. Thus, we also explored the isostructural Cm(III)-based complex. The computed magnetic susceptibility and g-tensor values show that the Cm(III) complex has poor SMM behavior in comparison to both the Dy(III) and Cf(III) complexes, suggesting that the performance of Cf(III)-based magnets may be affected by alpha-decay and can explain the poor performance of experimentally studied Cf(III)-based molecular magnets in the literature. Further, this study suggests that the ligand field is dominant in Cf(III), which helps to increase the magnetization blocking barrier by nearly 3 times that of its 4f congener.

Automated summary

By computationally exploring the electronic structure and magnetic properties of a hypothetical Cf(III) complex, we found that it can behave as a single molecule magnet (SMM) with higher magnetic susceptibility compared to other early-actinide-based magnetic complexes. However, due to alpha-decay, Cf can convert to Cm and affect its SMM behavior. Additionally, the study suggests that the ligand field is dominant in Cf(III), which significantly increases its magnetization blocking barrier compared to its 4f congener.