Atomically Precise Metal Nanoclusters: Novel Building Blocks for Hierarchical Structures

Atomically precise ligand‐protected nanoclusters (NCs) constitute an important class of compounds that exhibit well‐defined structures and, when sufficiently small, evident molecular properties. NCs provide versatile building blocks to fabricate hierarchical superstructures. The assembly of NCs indeed offers opportunities to devise new materials with given structures and able to carry out specific functions. In this Concept article, we highlight the possibilities offered by NCs in which the physicochemical properties are controlled by the introduction of foreign metal atoms and/or modification of the composition of the capping monolayer with functional ligands. Different approaches to assemble NCs into dimers and higher hierarchy structures and the corresponding changes in physicochemical properties are also described. Metal nanocluster‐based structures: Ultrasmall ligand‐protected nanoclusters (NCs) can be prepared with atomic precision and exhibit well‐defined structures and properties, and therefore, provide versatile building blocks to fabricate hierarchical superstructures. Here, some of the possibilities offered by NCs suitably tailored to self‐assemble are highlighted, and changes observed in the physicochemical properties of the ensuing systems are described.