A new self-assembled inorganic–organic hybrid layered compound containing hexarhenium cluster: [MV][{Mn(CH3OH)2}{Re6Se8(CN)6}]

A new layered compound, [MV][{Mn(CH3OH)2}{Re6Se8(CN)6}] (1) consists of a layer alternately knitted by hexarhenium cluster and Mn complex, and MV2+ cations (methyl viologen dication=1,1′-dimethyl-4,4′-bipyridilium dication) reside between the layers. The title compound 1 is the first layered framework containing cyano-hexarhenium clusters with photoactive guest molecules, MV2+. The MV2+ can be partly exchanged by H2TMB2+ (N,N,N′,N′-tetramethylbenzidine dication) to form a compound [H2TMB2+]x[MV2+]1−x [{Mn(CH3OH)2}{Re6Se8(CN)6}] (2) showing an electronic interaction between the layered framework and [H2TMB]2+ cation.