Recent progress in dichalcophosphate coinage metal clusters and superatoms

Abstract

Atomically precise clusters of group 11 metals (Cu, Ag, and Au) attract considerable attention owing to their remarkable structure and fascinating properties. One of the unique subclasses of these clusters is based on dichalcophosphate ligands of [(RO)₂PE₂]⁻ type (E = S or Se, and R = alkyl). These ligands successfully stabilise the most diverse Cu, Ag, and Au clusters and superatoms, spanning from simple ones to amazing assemblies featuring unusual structural and bonding patterns. It is noteworthy that such complicated clusters are assembled directly from cheap and simple reagents, metal(I) salts and dichalcophosphate anions. This reaction, when performed in the presence of a hydride or other anion sources, or foreign metal ions, results in hydrido- or anion-templated homo- or heteronuclear structures. In this feature article, we survey the recent advances in this exciting field, highlighting the powerful synthetic capabilities of the system “a metal(I) salt – [(RO)₂PX₂]⁻ ligands – a templating anion or borohydride” as an inexhaustible platform for the creation of new atomically precise clusters, superatoms, and nanoalloys.