Slow Magnetic Relaxation in a High-Spin Iron(II) Complex

TLDR

Applying a 1500 Oe dc field induces slow magnetic relaxation in [(tpaMes)Fe]−, following a thermally activated tunneling mechanism at high temperatures (Ueff = 42 cm⁻¹) and a temperature‑independent tunneling process at low temperatures. The high‑spin iron(II) complex [(tpaMes)Fe]− shows slow magnetic relaxation only under a 1500 Oe field, with a maximum relaxation time at that field, strong uniaxial anisotropy (D = −39.6 cm⁻¹), and no slow relaxation at zero field due to quantum tunneling.

Abstract

Slow magnetic relaxation is observed for [(tpaMes)Fe]−, a trigonal pyramidal complex of high-spin iron(II), providing the first example of a mononuclear transition metal complex that behaves as a single-molecule magnet. Dc magnetic susceptibility and magnetization measurements reveal a strong uniaxial magnetic anisotropy (D = −39.6 cm−1) acting on the S = 2 ground state of the molecule. Ac magnetic susceptibility measurements indicate the absence of slow relaxation under zero applied dc field as a result of quantum tunneling of the magnetization. Application of a 1500 Oe dc field initiates slow magnetic relaxation, which follows a thermally activated tunneling mechanism at high temperature to give an effective spin-reversal barrier of Ueff = 42 cm−1 and follows a temperature-independent tunneling mechanism at low temperature. In addition, the magnetic relaxation time shows a pronounced dc-field dependence, with a maximum occurring at ∼1500 Oe.