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 BuS and o-CHOPhCOO 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 Ag cuboctahedron core and an Ag rhombicuboctahedron shell in SD/Ag1 to an Ag rhombic dodecahedron core and an oval Ag shell in SD/Ag60a. The core enlargement from Ag to Ag originates from the replacement of two S in AgS by two Ag, which gives a new AgS 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 Ag 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.
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http://dx.doi.org/10.1063/5.0070138 | DOI Listing |
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