Luminescent twelve-nuclear rhenium clusters

The first luminescent twelve-nuclear rhenium cluster complexes were obtained. Three new clusters, namely, [Re12CS14(μ-Cl)3Cl6]5-, [Re12CS14(μ-Br)3Cl6]5- and [Re12CS14(μ-Br)3Br6]5-, were synthesized using the non-isovalent substitution of μ-O ligands within the {Re12CS14(μ-O)3}0 cluster core by halide anions. The geometry of the new clusters was investigated by X-ray structural analysis, and the electronic structures were evaluated by the use of DFT calculations. It was found that compounds based on these anions showed red luminescence in both the solid state and solution that was never observed before for previously studied twelve-nuclear rhenium clusters.