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.

中文翻译：

---

调节由杂阴离子驱动的银簇从 Ag37 到 Ag46 纳米轮的组装和扩展

通过阴离子模板驱动的自组装精确控制金属纳米团簇的形状和大小是纳米团簇研究的关键科学目标之一，但目前仍未得到全面了解。在这项工作中，我们报告了银纳米轮Ag37和Ag46的可控合成和原子精确结构，使用同型（Cl ^-离子）和杂阴离子（Cl ^-和 CrO ₄ ^2-离子）模板策略，以及大环对苯基硫杯[4]芳烃和小ⁱ PrS ⁻配体。结构分析表明，在Ag37中，Cl ^-离子充当局部和全局模板，而 CrO ₄ ^2-离子充当局部和 Cl ^-离子充当Ag46中的全局模板，从而产生五角形纳米轮 ( Ag37 ) 和六角形 ( Ag46 ) 纳米轮。_{CrO 4} ^2-离子比Cl ^-离子更大的离子尺寸和更多的负电荷为银原子提供了更多的配位点，并且被认为是驱动纳米轮核显着膨胀的关键因素。此外，通过利用具有扩展苯基的硫杯[4]芳烃的深空腔，Ag46根据有机染料的电荷和大小，已被用作染料吸附的主体材料。成功使用杂阴离子控制明确定义的银纳米轮的膨胀填补了理解杂阴离子在原子水平上决定纳米团簇形状和大小的指导作用方面的知识空白。