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 (SBu ^t ) ₈ (CF ₃ COO) ₄ (bpy) ₄ ] _n (Ag ₁₂ bpy, bpy=4,4'-bipyridine) into a dual-emissive [(Ag ₁₂ (SBu ^t ) ₆ (CF ₃ COO) 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/NH ₂ by a mixed-linker synthesis, together with dichromatic core-shell Ag ₁₂ bpy-2@Ag ₁₂ bpy-NH ₂ -2 via solvent-assisted linker exchange. This work provides insight into the significance of metal arrangement on physical properties of nanoclusters.
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