Spin-Electric Coupling in a Cobalt(II)-Based Spin Triangle Revealed by Electric-Field-Modulated Electron Spin Resonance Spectroscopy.

A cobalt(II)-based spin triangle shows a significant spin-electric coupling. [Co3 (pytag)(py)6 Cl3 ]ClO4 ⋅3 py crystallizes in the acentric monoclinic space group P21 . The intra-triangle antiferromagnetic interaction, of the order of ca. -15 cm-1 (H=-JSa Sb ), leads to spin frustration. The two expected energy-degenerate ground doublets are, however, separated by a few wavenumbers, as a consequence of magnetic anisotropy and deviations from threefold symmetry. The Co3  planes of symmetry-related molecules are almost parallel, allowing for the determination of the spin-electric properties of single crystals by EFM-ESR spectroscopy. The spin-electric effect detected when the electric field is applied in the Co3  plane was revealed by a shift in the resonance field. It was quantified as ΔgE /E=0.11×10-9  m V-1 , which in terms of frequency corresponds to approximately 0.3 Hz m V-1 . This value is comparable to what was determined for a Cu3  triangle despite the antiferromagnetic interaction being 20 times larger for the latter.