The distribution of Cu(II) and the magnetic properties of the synthetic analogue of tetrahedrite Cu12Sb4S13

A wide investigation of the synthetic analogue of tetrahedrite, Cu12Sb4S13, has been performed by a combination of several techniques, magnetisation and differential scanning calorimetric measurements, cw, and pulsed EPR spectroscopy, to obtain complementary information about the presence and the distribution of Cu(II). The high temperature susceptibility of the sample accounts for two Cu(II) per formula unit, in agreement with the charge balance. However, strong antiferromagnetic interactions, observed even at room temperature, are associated with a transition at 83(3) K. At lower temperatures a residual susceptibility is observed. At 4.2 K ESEEM experiments enabled observation of the chemical environment of the residual paramagnetic species. Cu(II) was found randomly distributed in the M(1) site. The statistical presence of nearest neighbouring Cu(II) ions justify the observed antiferromagnetic interactions and transition. Nevertheless, isolated paramagnetic ions have been determined below the Ne´ el temperature: they are mainly located near the surface of the grains. A colour centre, previously observed in natural samples, has been also identified.