Trapping an octahedral Ag₆ kernel in a seven-fold symmetric Ag₅₆ nanowheel

High-nuclearity silver clusters are appealing synthetic targets for their remarkable structures, but most are isolated serendipitously. We report here six giant silver-thiolate clusters mediated by solvents, which not only dictate the formation of an octahedral Ag₆⁴⁺ kernel, but also influence the in situ-generated Mo-based anion templates. The typical sevenfold symmetric silver nanowheels show a hierarchical cluster-in-cluster structure that comprises an outermost Ag₅₆ shell and an inner Ag₆⁴⁺ kernel in the centre with seven MoO₄^2- anion templates around it. Electrospray ionization mass spectrometry analyses reveal the underlying rule for the formation of such unique silver nanowheels. This work establishes a solvent-intervention approach to construct high-nuclearity silver clusters in which both the formation of octahedral Ag₆⁴⁺ kernel and in situ generation of various Mo-based anion templates can be simultaneously controlled.