Octahedral Hexanuclear Rhenium Cluster Dimers Bridged by Pyrazine or 4,4'-Bipyridine with 23- and 24-Electron Configurations.

Abstract

New pyrazine (pz)- and 4,4'-bipyridine (4,4'-bpy)-bridged octahedral hexanuclear rhenium(III) cluster dimers, [{Re6(μ3-S)8Cl5}2(μ-L)]6- (L = pz, [1]6-; L = 4,4'-bpy, [2]6-), with 2 × 24 d-electrons {Re6(24e)}2 were obtained in a single-step reaction via photoirradiation of [Re6(μ3-S)8Cl6]4- with L in a 2:1 ratio at room temperature. The {Re6(23e)}2 dimers, [{Re6(μ3-S)8Cl5}2(μ-L)]4- (L = pz, [1']4-; L = 4,4'-bpy, [2']4-), were synthesized through two-electron oxidation of [1]6- and [2]6-, respectively. The single-crystal X-ray structures of [1]6- and [1']4- were determined, revealing structural distortion of the Re6 core of [1']4- due to the Jahn-Teller effect. The cyclic voltammograms of [1]6- and [2]6- showed two steps of one-electron redox processes attributable to Re6(23e)Re6(24e)/{Re6(24e)}2 and {Re6(23e)}2/Re6(23e)Re6(24e), respectively. The separation between the two redox potentials is small (0.056 V for [1]6- and 0.039 V for [2]6-). The magnetic susceptibilities of [1']4- and [2']4- were almost temperature-independent, with values of 2.98 and 2.85 μB, respectively, indicating paramagnetism. These results suggest weak electronic interaction between two cluster units bridged by pz or 4,4'-bpy in the intercluster mixed valence state. The compounds [1]6- and [2]6- show photoluminescence in the near-infrared region at 296 K in the solid state.