Electron delocalisation in a trinuclear copper(II) complex: high-field EPR characterization and magnetic properties of Na3[Cu3(mal)3(H2O)] x 8H2O

The complex Na3Cu3(mal)3(H2O)] x 8H2O was obtained from evaporation of an aqueous solution containing Cu(OAc)2, malic acid (HO2CCH2CHOHCO2H) and NaOH and was characterised by X-ray diffraction on single crystal, X-band and high-field EPR spectroscopy (HF-EPR) and magnetic susceptibility measurements. The trinuclear complex Cu3(mal)3(H2O)]3- is trapped in a three-dimensional network with sodium cations. The three copper atoms are connected by alkoxo bridges and form an almost isosceles triangle with Cu...Cu distances of 3.076(1), 3.504(1) and 3.513(1) A. Two of the copper ions are also bridged by an extra aquo ligand. EPR spectroscopy combined with magnetic susceptibility measurements provide a powerful tool to resolve the electronic structure of the complex. The overall magnetic behaviour corresponds to an antiferromagnetically coupled triangular system. The 285 GHz-EPR spectrum (g = 2; 10.18 T) is characteristic of a spin state S = 1/2, with a rhombic anisotropy of g]. This rhombic pattern allows us to propose that the electronic spin density is delocalised on the three copper ions.