Redox-Switchable Allosteric Effects in Molecular Clusters.

We demonstrate that allosteric effects and redox state changes can be harnessed to create a switch that selectively and reversibly regulates the coordination chemistry of a single site on the surface of a molecular cluster. This redox-switchable allostery is employed as a guiding force to assemble the molecular clusters Zn3Co6Se8L'6 (L' = Ph2PN(H)Tol, Ph = phenyl, Tol = 4-tolyl) into materials of predetermined dimensionality (1- or 2-D) and to encode them with emissive properties. This work paves the path to program the assembly and function of inorganic clusters into stimuli-responsive, atomically precise materials.