Spectroscopic demonstration of a large antisymmetric exchange contribution to the spin-frustrated ground state of a D3 symmetric hydroxy-bridged trinuclear Cu(II) complex: ground-to-excited state superexchange pathways

Abstract

The magnetic and electronic properties of a spin-frustrated ground state of an antiferromagnetically coupled 3-fold symmetric trinuclear copper complex (TrisOH) is investigated using a combination of variable-temperature variable-field magnetic circular dichroism (VTVH MCD) and powder/single-crystal EPR. Direct evidence for a low-lying excited S = (1)/(2) state from the zero-field split ground (2)E state is provided by the nonlinear dependence of the MCD intensity on 1/T and the nesting of the VTVH MCD isotherms. A consistent zero-field splitting (Delta) value of approximately 65 cm(-1) is obtained from both approaches. In addition, the strong angular dependence of the single-crystal EPR spectrum, with effective g-values from 2.32 down to an unprecedented 1.2, requires in-state spin-orbit coupling of the (2)E state via antisymmetric exchange. The observable EPR intensities also require lowering of the symmetry of the trimer structure, likely reflecting a magnetic Jahn-Teller effect. Thus, the Delta of the ground (2)E state is shown to be governed by the competing effects of antisymmetric exchange (G = 36.0 +/- 0.8 cm(-1)) and symmetry lowering (delta = 17.5 +/- 5.0 cm(-1)). G and delta have opposite effects on the spin distribution over the three metal sites where the former tends to delocalize and the latter tends to localize the spin of the S(tot) = (1)/(2) ground state on one metal center. The combined effects lead to partial delocalization, reflected by the observed EPR parallel hyperfine splitting of 74 x 10(-4) cm(-1). The origin of the large G value derives from the efficient superexchange pathway available between the ground d(x2-y2) and excited d(xy) orbitals of adjacent Cu sites, via strong sigma-type bonds with the in-plane p-orbitals of the bridging hydroxy ligands. This study provides significant insight into the orbital origin of the spin Hamiltonian parameters of a spin-frustrated ground state of a trigonal copper cluster.