Structural rearrangement of Ag₆₀ nanocluster endowing different luminescence performances

It is well known that structure determines property, but obtaining a pair of silver nanoclusters with comparable structures to understand the structure–property relationship is a very challenging task. A new 60-nuclei silver nanocluster (SD/Ag60a) protected by a mixed-ligand shell of ^tBuS⁻ and o-CH₃OPhCOO⁻ was obtained and characterized. Single crystal x-ray diffraction reveals that SD/Ag60a has an identical metal nuclearity and core–shell structural type to SD/Ag1 previously reported by our group, whereas the compositions of the core and shell have undergone a rearrangement from an Ag₁₂ cuboctahedron core and an Ag₄₈ rhombicuboctahedron shell in SD/Ag1 to an Ag₁₄ rhombic dodecahedron core and an oval Ag₄₆ shell in SD/Ag60a. The core enlargement from Ag₁₂ to Ag₁₄ originates from the replacement of two S²⁻ in Ag₁₂S₁₅ by two Ag⁺, which gives a new Ag₁₄S₁₃ core. This result indicates that the metal frameworks of silver nanoclusters have some extent flexibility despite the same nuclearity, which can be influenced by ligands, solvents, anion templates, and others in the embryonic stage of the assembly. Interestingly, different core–shell architectures of Ag₆₀ nanoclusters also significantly endow the different optical absorption bands, photocurrent-generating properties, and luminesecent behaviors. This work not only realizes the regulation of the core–shell structure of silver nanoclusters with the same nuclearity but also provides a comparable model for investigating the relationship of structure–photoelectric properties.