Synergy of Magnetic Anisotropy and Ferromagnetic Interaction Triggering a Dimeric Cr(II) Zero-Field Single-Molecule Magnet

A novel Cr^II-dimeric complex, [Cr^IIN(SiⁱPr₃)₂(μ-Cl)(THF)]₂ (1), has been successfully constructed using a bulky silyl-amide ligand. Single-crystal structure analysis reveals that complex 1 exhibits a binuclear motif, with a Cr₂Cl₂ rhombus core, where two equivalent tetra-coordinate Cr^II centers in the centrosymmetric unit display quasi-square planar geometry. The crystal structure has been well simulated and explored by density functional theory calculations. The axial zero-field splitting parameter (D < 0) with a small rhombic (E) value is unambiguously determined by systematic investigations of magnetic measurements, high-frequency electron paramagnetic resonance spectroscopy, and ab initio calculations. Remarkably, ac magnetic susceptibility data unveil that 1 features slow dynamic magnetic relaxation typical of single-molecule magnet behavior with U_eff = 22 K in the absence of a dc field. This increases up to 35 K under a corresponding static field. Moreover, magnetic studies and theoretical calculations point out that a non-negligible ferromagnetic coupling (FMC) exists in the dimeric Cr-Cr units of 1. The coexistence of magnetic anisotropy and FMC contributes to the first case of Cr^II-based single-molecule magnets (SMMs) under zero dc field.