Ferromagnetic Exchange and Slow Magnetic Relaxation in Cobalt Bis(1,2-dithiolene)-Bridged Dilanthanide Complexes
Abstract
The construction of multinuclear lanthanide-based molecules with significant magnetic exchange interactions represents a key challenge in the realization of single-molecule magnets with high operating temperatures. Here, we report the synthesis and magnetic characterization of two series of heterobimetallic compounds, (Cp*2Ln)2(μ-Co(pdt)2) (Ln = Y3+, Gd3+, Dy3+; pdt2- = 1,2-diphenylethylenedithiolate) and [K(18-crown-6)][(Cp*2Ln)2(μ-Co(pdt)2)] (Ln = Y3+, Gd3+), featuring two lanthanide centers bridged by a cobalt bis(1,2-dithiolene) complex. Dc magnetic susceptibility data collected for the Gd congeners indicate significant Gd-Co ferromagnetic exchange interactions with fits affording J = +11.5 and +7.33 cm-1, respectively. Magnetization decay and ac magnetic susceptibility measurements carried out on the single-molecule magnet (Cp*2Dy)2(μ-Co(pdt)2) reveal full suppression of quantum tunneling and open-loop hysteresis persisting up to 3.5 K. These results, along with those of high-field EPR spectroscopy, suggest that transition metalloligands can enforce strong exchange interactions with adjacent lanthanide centers while maintaining a geometry that preserves molecular anisotropy. Furthermore, the magnetic properties of [K(18-crown-6)][(Cp*2Gd)2(μ-Co(pdt)2)] show that increasing the spin of the ground state of the bridging complex may be a viable alternative to increasing J in obtaining well-isolated, strongly coupled magnetic ground states.
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