Two three-dimensional polyanionic clusters [M(P4Mo6)2] (M = Co, Zn) exhibiting excellent photocatalytic CO2 reduction performance

Two captivating {P4Mo6}-based compounds, formulated as (H(2)bbi)(2){[Co-2(bbi)][Co-2.33(H2O)(4)][H9.33CoP8Mo12O62]}center dot 4H(2)O (1) and (H(2)bbi){[Zn(Hbbi)](2)[Zn-0.75(bbi)][K2Zn(H2O)(4)][H8.5ZnP8Mo12O62]} (2) [bbi = 1,1'-(1,4-butanediyl)bis(imidazole)], were successfully synthesized under hydrothermal conditions. Structural analysis demonstrates that compounds 1 and 2 are constructed from hourglass-shaped structures [M(P4Mo6O31)(2)](n-) (M = Co, Zn), which are all made up of molybdophosphates and one transition metal ion as the central connecting node. Compounds 1 and 2 feature three-dimensional (3D) frameworks, which are all connected to form a 3D structure by metal ions and bbi ligands. More interestingly, compound 1 exhibits higher catalytic activity than 2 in CO2 photoreduction due to the suitable energy band structure of Co species in {P4Mo6} clusters. The CO yield was 3261 mu mol g(-1) with high selectivity in 8 h for compound 1 in photocatalytic CO2 reduction, which is highly promising in the photocatalytic field. Additionally, the photoluminescence properties of 2 were investigated.