Intuitive Control of Low-Energy Magnetic Excitations via Directed Dipolar Interactions in a Series of Er(III)-Based Complexes

Dipolar coupling is rarely invoked as a driving force for slow relaxation dynamics in lanthanide-based single-molecule magnets, though it is often the strongest mechanism available for mediating inter-ion magnetic interactions in such species. Indeed, for multinuclear lanthanide complexes, the magnitude and anisotropy of the dipolar interaction can be considerable given their ability to form highly directional, high-moment ground states. Herein, we present a mono-, di-, and trinuclear erbium-based single-molecule magnet sequence, ([Er-TiPS2COT](+))(n) (n = 1-3), wherein a drastic reduction in the allowedness of magnetic relaxation pathways is rationalized within the framework of the dipole-dipole interactions between angular momentum quanta. The resulting design principles for multinuclear molecular magnetism arising from intramolecular dipolar coupling interactions between highly anisotropic magnetic states present a nuanced justification of the relaxation dynamics in complex manifolds of individual quantized transitions. Experimental evidence for the validity of this model is provided by coupling the relaxation dynamics to an AC magnetic field across an unprecedented frequency range for molecular magnetism (10(3)-10(-5) Hz). The combination of slow dynamics and multiple, low-energy transitions leads to a number of noteworthy phenomena, including a lanthanide single-molecule magnet with three well-defined relaxation processes observable at a single temperature.