Synthesis, structure, and properties of compounds containing both octahedral rhenium cluster cations and anions

The compound [{Re6S8}(3,5-Me2pzH)6]2[{Re6S8}Br6]•9H2O•4EtOH containing a cluster cation and a cluster anion in a 2: 1 ratio was synthesized by mixing an ethanol solution of the rhenium cluster complex [{Re6S8}(3,5-Me2pzH)6]Br2•2(3,5-Me2pzH) (pzH is pyrazole) with an aqueous solution of Cs4[{Re6S8}Br6]•2H2O. The resulting compound was characterized by a combination of physicochemical methods. In particular, luminescence properties were studied and compared with those of the parent cluster complexes. A crystal suitable for single-crystal X-ray diffraction was obtained by layering these solutions. According to single-crystal X-ray diffraction analysis, this compound is composed of a cluster cation and a cluster anion (in a ratio of 1: 1) and also of Zundel cations (H5O2 +) and solvate water molecules and is described by the formula (H5O2)2[{Re6S8}(3,5-Me2pzH)6][{Re6S8}Br6]•4H2O.