Slow magnetic relaxation in a europium(II) complex.

Errulat, Dylan; Harriman, Katie L M; Gálico, Diogo A; Salerno, Elvin V; van Tol, Johan; Mansikkamäki, Akseli; Rouzières, Mathieu; Hill, Stephen et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Single-ion anisotropy is vital for the observation of Single-Molecule Magnet (SMM) properties (i.e., a slow dynamics of the magnetization) in lanthanide-based systems. In the case of europium, the occurrence of this phenomenon has been inhibited by the spin and orbital quantum numbers that give way to J = 0 in the trivalent state and the half-filled population of the 4f orbitals in the divalent state. Herein, by optimizing the local crystal field of a quasi-linear bis(silylamido) Eu<sup>II</sup> complex, the [Eu<sup>II</sup>(N{SiMePh<sub>2</sub>}<sub>2</sub>)<sub>2</sub>] SMM is described, providing an example of a europium complex exhibiting slow relaxation of its magnetization. This behavior is dominated by a thermally activated (Orbach-like) mechanism, with an effective energy barrier of approximately 8 K, determined by bulk magnetometry and electron paramagnetic resonance. Ab initio calculations confirm second-order spin-orbit coupling effects lead to non-negligible axial magnetic anisotropy, splitting the ground state multiplet into four Kramers doublets, thereby allowing for the observation of an Orbach-like relaxation at low temperatures.