Magneto-structural correlations in arsenic- and selenium-ligated dysprosium single-molecule magnets

The structures and magnetic properties of the arsenic- and selenium-ligated dysprosium single-molecule magnets (SMMs) [Cp'₃Dy(AsH₂Mes)] (3-Dy), [(η⁵-Cp'₂Dy){μ-As(H)Mes}]₃ (4-Dy), [Li(thf)₄]₂[(η⁵-Cp'₂Dy)₃(μ₃-AsMes)₃Li] ([Li(thf)₄]₂[5-Dy]), and [(η⁵-Cp'₂Dy){μ-SeMes}]₃ (6-Dy) are described. The arsenic-ligated complexes 4-Dy and 5-Dy are the first SMMs to feature ligands with metalloid elements as the donor atoms. The arsenide-ligated complex 4-Dy and the selenolate-ligated complex 6-Dy show large anisotropy barriers in the region of 250 cm^-1 in zero d.c. field, increasing to 300 cm^-1 upon 5% magnetic dilution. Theoretical studies reveal that thermal relaxation in these SMMs occurs via the second-excited Kramers' doublet. In contrast, the arsinidene-ligated SMM 5-Dy gives a much smaller barrier of 23 cm^-1, increasing to 35 cm^-1 upon dilution. The field-dependence of the magnetization for 4-Dy and 5-Dy at 1.8 K show unusual plateaus around 10 kOe, which is due to the dominance of arsenic-mediated exchange over the dipolar exchange. The effects of the exchange interactions are more pronounced in 5-Dy, which is a consequence of a small but significant increase in the covalent contribution to the predominantly ionic dysprosium-arsenic bonds. Whereas the magnetically non-dilute dysprosium SMMs show only very narrow magnetization versus field hysteresis loops at 1.8 K, the impact of magnetic dilution is dramatic, with butterfly-shaped loops being observed up to 5.4 K in the case of 4-Dy. Our findings suggest that ligands with heavier p-block element donor atoms have considerable potential to be developed more widely for applications in molecular magnetism.