Inorganic compounds with the AB2X4 spinel structure have been studied for many years, because of their unusual physical properties. The spinel crystallographic structure, first solved by Bragg in 1915, has cations occupying both tetrahedral (A) and octahedral (B) sites. Interesting physics arises when the B-site cations become mixed in valence. Magnetite (Fe3O4) is a classic and still unresolved example, where the tendency to form ordered arrays of Fe2+ and Fe3+ ions competes with the topological frustration of the B-site network. The CuIr2S4 thiospinel is another example, well known for the presence of a metal-insulator transition at 230 K with an abrupt decrease of the electrical conductivity on cooling accompanied by the loss of localized magnetic moments. Here, we report the determination of the crystallographic structure of CuIr2S4 below the metal-insulator transition. Our results indicate that CuIr2S4 undergoes a simultaneous charge-ordering and spin-dimerization transition-a rare phenomenon in three-dimensional compounds. Remarkably, the charge-ordering pattern consists of isomorphic octamers of Ir83+S24 and Ir84+S24 (as isovalent bi-capped hexagonal rings). This extraordinary arrangement leads to an elegant description of the spinel structure, but represents an increase in complexity with respect to all the known charge-ordered structures, which are typically based on stripes, slabs or chequerboard patterns.

We have measured the optical conductivity of single crystal LuMnO3 from 10 to 45000 cm(-1) at temperatures between 4 and 300 K. A symmetry allowed on-site Mn d-d transition near 1.7 eV is observed to blueshift ( approximately 0.1 eV) in the antiferromagnetic state due to Mn-Mn superexchange interactions. Similar anomalies are observed in the temperature dependence of the TO phonon frequencies which arise from spin-phonon interaction. We find that the known anomaly in the temperature dependence of the quasistatic dielectric constant epsilon(0) below T(N) approximately 90 K is overwhelmingly dominated by the phonon contributions.

Spintronics holds great potential for next-generation high-speed and low–power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs2Ag(Bi:Fe)Br6, Fe3+ replaces Bi3+ and forms FeBr6 clusters that homogenously distribute throughout the double perovskite crystals. We observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites.

A new crystalline lithium-ion conducting material, LiSnS with an ortho-composition, was prepared by a mechanochemical technique and subsequent heat treatment. Synchrotron X-ray powder diffraction was used to analyze the crystal structure, revealing a space group of P6/ mmc and cell parameters of a = 4.01254(4) Å and c = 6.39076(8) Å. Analysis of a heat-treated hexagonal LiSnS sample revealed that both lithium and tin occupied either of two adjacent tetrahedral sites, resulting in fractional occupation of the tetrahedral site (Li, 0.375; Sn, 0.125). The heat-treated hexagonal LiSnS had an ionic conductivity of 1.1 × 10 S cm at room temperature and a conduction activation energy of 32 kJ mol. Moreover, the heat-treated LiSnS exhibited a higher chemical stability in air than the LiPS glass-ceramic.