Valence-delocalized trithorium nanocluster superatoms with open-shell exalted diamagnetism

Quantum-confined nanoclusters can be described by the jellium model, which emphasizes closed-shell electron configurations, but an open-shell variation with jellium aromaticity has been proposed. Such clusters are termed superatoms because they behave like an atom, and they exhibit unusual properties. Superatoms feature metal-metal bonding; hence, since their discovery 40 years ago, superatoms have exclusively involved main group or transition metals, with actinides only considered computationally as dopants owing to actinide-actinide bonding being exceedingly rare. Here we report trithorium nanoclusters exhibiting three-centre-one-electron actinide-actinide bonding. Experimental and computational analysis demonstrates Robin-Day Class III 6d-orbital valence delocalization in these clusters. These S = 1/2 clusters are paramagnetic, but in external applied magnetic fields they exhibit exalted diamagnetism, evidencing actinide open-shell jellium aromaticity superatom character. Exalted diamagnetism is not normally associated with a single unpaired electron, but with a 1S¹ magic number, the valence delocalization enables exalted diamagnetism, which is aromaticity, via superatom ring currents.