Fourth-order zero-field splitting parameters of [Mn(cyclam)Br2]Br determined by single-crystal W-band EPR

Single-crystal W-band (95 GHz) electron paramagnetic resonance (EPR) studies have been performed at 20 K and at room temperature on a tetragonal Mn(III) compound with potential application as a building block for high-spin clusters. The observed EPR spectra correspond to an anisotropic high-spin S = 2 ground state and have been attributed to equivalent centers related by fourfold symmetry. Accurate values for the spin Hamiltonian parameters were obtained from the analysis of the data at both temperatures. At 20 K the contribution of fourth-order zero-field splitting terms was shown to be significant, with parameter values B-4(0) = 0.0009(3) cm(-1), B2 = 0.0006(2) cm(-1) and 4 4 B-4(4) = 0.0017(3) cm(-1), to be considered together with the second-order parameters D = -1.1677(7) cm(-1) and E = -0.0135(6) cm(-1).