RESUMO
While Ln2O2S oxysulphides have increasingly gained attention due to their structural and optoelectronic properties, an expansive compositional space lies beyond as the sulphur-to-oxygen ratio increases. In these oxysulphides, the compounded effect of the 4f states is manifold in the lanthanoid ions and the changing bonding and environment symmetry enables the tuning of their electronic structure and photophysical properties. Their challenging syntheses have made these materials largely unexplored, but recent efforts have been made to bridge the knowledge gap. In this article we present some of the structural characteristics and photophysical properties of the lanthanoid oxysulphide spectrum LnxOySz.
RESUMO
The electronic structure and local coordination of binary (Mo6T8) and ternary Chevrel Phases (MxMo6T8) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the Mo L3-edge and K-edge X-ray absorption near edge structure across the suite of chalcogenides MxMo6T8 (M = Cu, Ni, x = 1-2, T = S, Se, Te), quantifying the effect of compositional and structural modification on electronic structure. Furthermore, we highlight the expansion, contraction, and anisotropy of Mo6 clusters within these Chevrel Phase frameworks through extended X-ray absorption fine structure analysis. Our results show that metal-to-cluster charge transfer upon intercalation is dominated by the chalcogen acceptors, evidenced by significant changes in their respective X-ray absorption spectra in comparison to relatively unaffected Mo cations. These results explain the effects of metal intercalation on the electronic and local structure of Chevrel Phases across various chalcogen compositions, and aid in rationalizing electron distribution within the structure.
