Origin of the fast magnetization tunneling in the single-molecule magnet [Ni(hmp)(tBuEtOH)Cl]4
C. Kirman, J. Lawrence, S. Hill, E-C. Yang, D. N. Hendrickson
Abstract
We present high-frequency angle-dependent EPR data for crystals of [NixZn1-x(hmp)(t-BuEtOH)Cl]4 (x = 1 and 0.02). The x = 1 complex behaves as a single-molecule magnet at low temperatures, displaying hysteresis and exceptionally fast magnetization tunneling. We show that this behavior is related to a 4th-order transverse crystal-field interaction, which produces a significant tunnel-splitting (~10 MHz) of the ground state of this S = 4 system. The magnitude of the 4th-order anisotropy, and the dominant axial term (D), can be related to the single-ion interactions (Di and Ei) at the individual NiII sites, as determined for the x = 0.02 crystals.
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