Progress and prospects in the design of functional atomically-precise Ag(I)-thiolate nanoclusters and their assembly approaches

Atomically-precise noble metal nanoclusters have raised nanomaterials research to new heights by merit of their distinct structural, optical and electronic properties, which can be leveraged for wide-ranging applications. The photoluminescence characteristics has given greater prominence to thiolate-protected silver nanoclusters (Ag NCs) for sensing, bioimaging and photovoltaics. Notwithstanding high potential, the susceptibility to oxidation has left Ag NCs with limited applicability. Reticular chemistry providing a platform for the transformation of discrete entities to extended structures, Ag NCs could be linked with organic struts via strong coordination bonds to form periodic networks called silver cluster-assembled materials (SCAMs) that revealed abundant catalytically active sites and unprecedented architectural stability. This Review highlights the recent developments in the synthesis of Ag(I)-thiolate NCs with special emphasis on size control, stability and optical properties, besides discussing the synergistic interactions between Ag NCs and organic linkers in coordination-assembled SCAMs facilitating the activity as well as morphology evolution from supramolecular self-assembly of Ag NCs. Finally, we provide an outlook of the challenges and opportunities covering from fundamentals to functional devices and applications.