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.

Automated summary

Atomically-precise noble metal nanoclusters with distinct structural, optical, and electronic properties have been widely studied for various applications. Thiolate-protected silver nanoclusters (Ag NCs) have shown great potential in sensing, bioimaging, and photovoltaics, but are limited by their susceptibility to oxidation. Reticular chemistry has provided a solution through the formation of silver cluster-assembled materials (SCAMs) that combine Ag NCs with organic linkers, resulting in enhanced catalytic activity and structural stability. This review discusses recent developments in the synthesis of Ag(I)-thiolate NCs, size control, stability, optical properties, and the synergistic interactions between Ag NCs and organic linkers in SCAMs, as well as the challenges and opportunities in functional devices and applications.