Large Anisotropy Barrier in a Tetranuclear Single-Molecule Magnet Featuring Low-Coordinate Cobalt Centers

The tetranuclear cobalt cluster compound [Co4(μ-NPtBu3)4]­[B­(C6F5)4] (tBu = tert-butyl) was synthesized by chemical oxidation of Co4(NPtBu3)4 with [FeCp2]­[B­(C6F5)4] and magnetically characterized to study the effect of electronic communication between low-coordinate metal centers on slow magnetic relaxation in a transition metal cluster. The dc magnetic susceptibility data reveal that the complex exhibits a well-isolated S = 9/2 ground state, which persists even to 300 K and is attributed to the existence of direct metal–metal orbital overlap. The ac magnetic susceptibility data further reveals that the complex exhibits slow magnetic relaxation in the absence of an applied field, and that the relaxation dynamics can be fit with a combination of Orbach, quantum tunneling, and Raman relaxation processes. The effective spin reversal barrier for this molecule is 87 cm–1, the largest reported to date for a transition metal cluster, and arises due to the presence of a large easy-axis magnetic anisotropy. The complex additionally exhibits waist-restricted magnetic hysteresis and magnetic blocking below 3.6 K. Taken together, these results indicate that coupling of low-coordinate metal centers is a promising strategy to enhance magnetic anisotropy and slow magnetic relaxation in transition metal cluster compounds.