Cosmic Blueprint to Nanoscale Design: Hoag’s Object-Like Polyoxovanadate Encapsulated by a Hierarchical Silver Nanocluster

The pervasive presence of toroidal architectures across scales, from molecular assemblies to cosmic formations, reveals a universal design principle that integrates aesthetic symmetry with functional topology in nature. Yet, constructing such hierarchical toroidal organization at the nanoscale, particularly for metal nanoclusters, remains an unmet challenge. We present an unprecedented wheel-shaped silver nanocluster, [(V₆O₁₉⊂V₂₂O₆₆)@Ag₉₆(^<i>t</i>BuPhC≡C)₅₆(SO₄)₂(DMF)₁₂]⁶⁺ (<b>Ag96</b>), encapsulating an unparalleled hierarchical toroidal [V₆O₁₉⊂V₂₂O₆₆]^30- polyoxovanadate (POV). The hierarchical toroidal [V₆O₁₉⊂V₂₂O₆₆]^30- mirrors the core-shell geometry of Hoag's Object, a rare ring galaxy, with a Lindqvist-type [V₆O₁₉]^8- core enclosed by a macrocyclic [V₂₂O₆₆]^22- shell. This work constitutes a unique astronomical morphology in coinage metal nanoclusters, uncovering the universal principles of hierarchical self-assembly at the nanoscale. Leveraging the flexibility of POVs, we further isolated a bowl-shaped [(SO₄@V₁₅O₄₂)@Ag₄₆(^<i>t</i>BuPhC≡C)₃₁(DMF)₂]⁴⁺ (<b>Ag46</b>), encapsulating an open-cage [SO₄@V₁₅O₄₂]^11- template by regulating the stoichiometric ratio. Due to their distinct structural configurations, these nanoclusters exhibit markedly different photothermal conversion performance when exposed to visible or near-infrared (NIR) lasers. This breakthrough positions POVs as versatile templates for engineering complex metal nanoclusters, opening new frontiers in materials science and nanotechnology.