Tandem Silver Cluster Isomerism and Mixed Linkers to Modulate the Photoluminescence of Cluster-Assembled Materials

Silver chalcogenolate cluster assembled materials (SCAMs) are a category of promising light-emitting materials the luminescence of which can be modulated by variation of their building blocks (cluster nodes and organic linkers). The transformation of a singly emissive [Ag-12(SBut)(8)(CF3COO)(4)(bpy)(4)](n) (Ag(12)bpy, bpy=4,4-bipyridine) into a dual-emissive [(Ag-12(SBut)(6)(CF3COO)(6)(bpy)(3))](n) (Ag(12)bpy-2) via cluster-node isomerization, the critical importance of which was highlighted in dictating the photoluminescence properties of SCAMs. Moreover, the newly obtained Ag(12)bpy-2 served to construct visual thermochromic Ag(12)bpy-2/NH2 by a mixed-linker synthesis, together with dichromatic core-shell Ag(12)bpy-2@Ag(12)bpy-NH2-2 via solvent-assisted linker exchange. This work provides insight into the significance of metal arrangement on physical properties of nanoclusters.