The exceedingly strong single-ion anisotropy of lanthanide single-molecule-magnets (SMMs) has garnered an increased interest in their slow relaxation behavior. Stabilization of the high-moment ground states of lanthanide SMMs have strict crystal field requirements, however, that have restricted growth within the field due to coordinatively saturated single-ions or unfavorable interactions in synthetically tunable units. Furthermore, the high anisotropy of lanthanide SMMs along with the relative scarcity of coupling between them has hampered efforts to build suitable models to describe exchange and dipolar interactions within lanthanide SMMs. The cyclooctatetraenide dianion can stabilize the highly anisotropic MJ = 15/2 ground state of Er3+ to yield a synthetically tunable half-sandwich molecular magnetic unit, [ErCOT]+, with robust slow relaxation properties and axial anisotropy along the vector between Er3+ and the COT centroid. This unit has allowed the deliberate design of several dinuclear SMMs displaying ferromagnetic coupling. By varying the angle between ErCOT units with identical crystal fields or the electronic properties of the bridge within structurally analogous complexes, we have begun to probe the operant coupling pathways so as to better inform conscious ligand design.

ErCOT: An anisotropic metal-ligand pair for targeted molecular magnet design

2019 Fall National Meeting

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