Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

Atomically precise gold/silver clusters protected by organic ligands L, [(Au/Ag) x L y ] z , have gained increasing interest as building units of functional materials because of their novel photophysical and physicochemical properties. The properties of [(Au/Ag) x L y ] z are intimately associated with the quantized electronic structures of the metallic cores, which can be viewed as superatoms from the analogy of naked Au/Ag clusters. Thus, establishment of the correlation between the geometric and electronic structures of the superatomic cores is crucial for rational design and improvement of the properties of [(Au/Ag) x L y ] z . This review article aims to provide a qualitative understanding on how the electronic structures of [(Au/Ag) x L y ] z are affected by geometric structures of the superatomic cores with a focus on three factors: size, shape, and composition, on the basis of single‐crystal X‐ray diffraction data. The knowledge accumulated here will constitute a basis for the development of ligand‐protected Au/Ag clusters as new artificial elements on a nanometer scale.