Dimensional Control of Assembling Metal Chalcogenide Clusters

Abstract

The ability to synthesize novel functional materials at the nanoscale relies on the design and synthesis of versatile, tunable, atomically precise building blocks. Clusters of atoms exhibit physical properties beyond those of their constituent atoms, and new phenomena (e.g. electronic, magnetic) can emerge in such materials. This minireview describes a method to create site‐differentiated clusters and presents various synthetic approaches toward creating materials from these building blocks. The cobalt selenide clusters fundamental to this study are members of a larger class of clusters with the [M6E8] stoichiometry (M = metal, E = chalcogen). There are two ways to prepare suitably reactive [M6E8] monomeric clusters for bonded assemblies: (1) incorporating a secondary functionality on the capping ligand, and (2) introducing removable, reactive ligands on the cluster surface. Rationally designed chemical transformations give us precise control over the extent and dimensionality of the resulting materials. The new bottom‐up approaches towards extended solids presented in this minireview reveal how to build from 0‐dimensional building blocks into 1‐, 2‐, and 3‐dimensional systems that comprise clusters.