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

ABSTRACT: The structures and magnetic properties of the arsenic- and selenium-ligated dysprosium single-molecule magnets (SMMs) [Cp'3Dy(AsH2Mes)] (3-Dy), [(?5-Cp'2Dy){?-As(H)Mes}]3 (4-Dy), [Li(thf)4]2[(?5-Cp'2Dy)3(?3-AsMes)3Li] ([Li(thf)4]2[5-Dy]), and [(?5-Cp'2Dy){?-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.

SUBMITTER: Pugh T 

PROVIDER: S-EPMC5968533 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature