Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores

Two-dimensional (2D) structures have been shown to possess interesting and potentially useful properties. Because of their isotropic structure, however, clusters tend to assemble into 3D architectures. Here we report the assembly of polyoxometalate clusters into layered structures that feature uniform hexagonal pores and in-plane electron delocalization properties. Because these structures are 2D and visually reminiscent of graphene, they are referred to as 'clusterphenes'. A series of multilayer and monolayer clusterphenes have been constructed with 13 types of polyoxometalate cluster. The resulting clusterphenes were shown to exhibit substantially improved stability and catalytic efficiency towards olefin epoxidation reactions, with a turnover frequency of 4.16 h-1, which is 76.5 times that of the unassembled clusters. The catalytic activity of the clusterphenes derives from the electron delocalization between identical clusters within the 2D layer, which efficiently reduces the activation energy of the catalytic reaction.