Precise control over the shape and size of metal nanoclusters through anion template-driven self-assembly is one of the key scientific goals in the nanocluster community, however, it is still not understood comprehensively. In this work, we report the controllable synthesis and atomically precise structures of silver nanowheels Ag37 and Ag46, using homo (Cl- ions) and heteroanion (Cl- and CrO4 2- ions) template strategies, along with macrocyclic p-phenyl-thiacalix[4]arene and small iPrS- ligands. Structural analyses revealed that in Ag37, Cl- ions serve as both local and global templates, whereas CrO4 2- ions function as local and Cl- ions as global templates in Ag46, resulting in a pentagonal nanowheel (Ag37) and a hexagonal (Ag46) nanowheel. The larger ionic size and more negative charges of CrO4 2- ions than Cl- ions offer more coordination sites for the silver atoms and are believed to be the key factors that drive the nanowheel core to expand significantly. Also, by taking advantage of the deep cavity of thiacalix[4]arene with an extended phenyl group, Ag46 has been used as a host material for dye adsorption depending on the charge and size of organic dyes. The successful use of heteroanions to control the expansion of well-defined silver nanowheels fills the knowledge gap in understanding the directing role of heteroanions in dictating the shape and size of nanoclusters at the atomic level.
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