Regulating the assembly and expansion of the silver cluster from the Ag37 to Ag46 nanowheel driven by heteroanions† † Electronic supplementary information (ESI) available: Synthesis details, IR, UV-vis, and PXRD data, details of the data collection and structure refinements, and crystal data. CCDC 2206151 and 2206152 for Ag46 and Ag37. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d2sc06436g

ABSTRACT: 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 CrO42− 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 CrO42− 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 CrO42− 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. A heteroanion self-assembly strategy for regulating the shape and expanding the size of the silver cluster from Ag37 to Ag46 with a macrocyclic (p-phenyl-thiacalix[4]arene) ligand has been presented.

SUBMITTER: Gupta R 

PROVIDER: S-EPMC9891368 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature