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Cosmic Blueprint to Nanoscale Design: Hoag's Object-Like Polyoxovanadate Encapsulated by a Hierarchical Silver
Wei-Dan Si1, Hao Liang1, Seung-Hyun Ji2
1Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Lab of Crystal Materials, Shandong University, Ji'nan 250100, People's Republic of China.
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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(tBuPhC≡C)56(SO4)2(DMF)12]6+ (Ag96), 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(tBuPhC≡C)31(DMF)2]4+ (Ag46), 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.
