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High-nuclearity silver(Ⅰ)clusters have attracted considerable attention not only owing to their structural diversity,but also due to their potential properties reflected in the field of fluorescence,magnetic,electrochemical,gas sensing and separation.Here,phosphonate ligands as structure-directing components have been employed to construct four new high-nuclearity silver(Ⅰ)sulfide-ethynide-thiolate clusters,in which silver(Ⅰ)aggregates tBuC≡C(>)Ag3,tBuC≡C(>)Ag4 and 2tBuC≡C(>)Ag7 are bridged by tBuS-ligands to engender respective silver(Ⅰ)ethynide-thiolate clusters functioning as integral shell components,which are supported by phosphonate ligands.In each silver(Ⅰ)sulfide-ethynide-thiolate cluster,a different encapsulated silver sulfide cluster serves as a core template.