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Rhenium chalcohalide cluster compounds are a photoluminescent family of mixed-anion chalcohalide cluster materials. Here we report the new material Rb6Re6S8I8, which crystallizes in the cubic space group Fm m and contains isolated [Re6S8I6]4− clusters. Rb6Re6S8I8 has a band gap of 2.06(5) eV and an ionization energy of 5.51(3) eV, and exhibits broad photoluminescence (PL) ranging from 1.01 eV to 2.12 eV. The room-temperature PL exhibits a PL quantum yield of 42.7% and a PL lifetime of 77 μs (99 μs at 77 K). Rb6Re6S8I8 is found to be soluble in multiple polar solvents including N,N-dimethylformamide, which enables solution processing of the material into films with thickness under 150 nm. Light-emitting diodes based on films of Rb6Re6S8I8 were fabricated, demonstrating the potential for this family of materials in optoelectronic devices. 

Abstract Despite large theoretical energy densities, metal‐sulfide electrodes for energy storage systems face several limitations that impact the practical realization. Here, we present the solution‐processable, room temperature (RT) synthesis, local structures, and application of a sulfur‐rich Mo₃S₁₃chalcogel as a conversion‐based electrode for lithium‐sulfide batteries (LiSBs). The structure of the amorphous Mo₃S₁₃chalcogel is derived throughoperandoRaman spectroscopy, synchrotron X‐ray pair distribution function (PDF), X‐ray absorption near edge structure (XANES), and extended X‐ray absorption fine structure (EXAFS) analysis, along with ab initio molecular dynamics (AIMD) simulations. A key feature of the three‐dimensional (3D) network is the connection of Mo₃S₁₃units through S−S bonds. Li/Mo₃S₁₃half‐cells deliver initial capacity of 1013 mAh g⁻¹during the first discharge. After the activation cycles, the capacity stabilizes and maintains 312 mAh g⁻¹at a C/3 rate after 140 cycles, demonstrating sustained performance over subsequent cycling. Such high‐capacity and stability are attributed to the high density of (poly)sulfide bonds and the stable Mo−S coordination in Mo₃S₁₃chalcogel. These findings showcase the potential of Mo₃S₁₃chalcogels as metal‐sulfide electrode materials for LiSBs. 

The dioxomolybdenum( vi ) complex MoO 2 Cl 2 (dmf) 2 reacts with Pb(DOPO Q ) 2 (DOPO = 2,4,6,8-tetra- tert -butyl-1,9-dioxophenoxazinate) to give MoO 2 (DOPO Q ) 2 , which has an eight-coordinate structure with normal molybdenum-oxo bond distances and angles but elongated distances to the dioxophenoxazine ligand. The dioxo complex is deoxygenated by phosphines to produce octahedral Mo(DOPO Cat ) 2 , in which reduction has taken place at the ancillary ligands. This compound in turn reacts with trimethylamine- N -oxide to regenerate MoO 2 (DOPO Q ) 2 , allowing a catalytic cycle for phosphine oxidation. This represents an example of four-electron nonclassical oxygen atom transfer in which both the oxidized and reduced forms of the metal complexes can be observed.