Two-Dimensional Nanosheets from Redox-Active Superatoms.

We describe a new approach to synthesize two-dimensional (2D) nanosheets from the bottom-up. We functionalize redox-active superatoms with groups that can direct their assembly into multidimensional solids. We synthesized Co6Se8[PEt2(4-C6H4COOH)]6 and found that it forms a crystalline assembly. The solid-state structure is a three-dimensional (3D) network in which the carboxylic acids form intercluster hydrogen bonds. We modify the self-assembly by replacing the reversible hydrogen bonds that hold the superatoms together with zinc carboxylate bonds via the solvothermal reaction of Co6Se8[PEt2(4-C6H4COOH)]6 with Zn(NO3)2. We obtain two types of crystalline materials using this approach: one is a 3D solid and the other consists of stacked layers of 2D sheets. The dimensionality is controlled by subtle changes in reaction conditions. These 2D sheets can be chemically exfoliated, and the exfoliated, ultrathin 2D layers are soluble. After they are deposited on a substrate, they can be imaged. We cast them onto an electrode surface and show that they retain the redox activity of the superatom building blocks due to the porosity in the sheets.