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

Abstract

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.