Tetraoxolene-bridged rare-earth complexes: a radical-bridged dinuclear Dy single-molecule magnet

Two families of neutral tetraoxolene-bridged dinuclear rare earth complexes of general formula [((HBpz₃)₂RE)₂(μ-tetraoxolene)] (RE = Y and Dy; HBpz₃^- = hydrotris(pyrazolyl)borate; tetraoxolene = fluoranilate (fa^2-; 1-RE) or bromanilate (ba^2-; 2-RE)) have been synthesised and characterised. In each case, the bridging tetraoxolene ligand is in the diamagnetic dianionic form and each rare earth metal centre has two HBpz₃^- ligands completing the coordination. Electrochemical studies on the soluble 2-RE family reveal a tetraoxolene-based reversible one-electron reduction. Bulk chemical reduction with cobaltocene affords the cobaltocenium (CoCp⁺) salt of the 1e-reduced analogue: [CoCp][((HBpz₃)₂RE)₂(μ-ba˙)] (3-RE) that incorporates a radical trianionic form of the bromanilate bridging ligand. Alternating current (ac) magnetic susceptibility studies of 2-Dy reveal slow magnetic relaxation only in the presence of an applied magnetic field, but reduction to radical-bridged 3-Dy affords frequency-dependent peaks in the out-of-phase ac susceptibility in zero applied field. Exchange coupling between the Dy(iii) ions and the radical bridging ligand thus reduces zero-field magnetisation quantum tunnelling and confers single-molecule magnet status on the complex. Comprehensive analysis of the magnetic relaxation data indicates that a combination of Orbach, Raman and direct relaxation processes are required to fit the data for both dysprosium bromanilate complexes.