Synthesis of Sb₆₈^8-: Crafting a Homoatomic Antimony Nanotorus

Pure-element cyclic molecules have garnered extensive attention owing to their intriguing structures and promising applications. Among these, carbon-based cyclic molecules such as cyclo[n]carbon (C, n = 10-26) and carbon nanotori have ignited significant interest in both experimental and theoretical investigations. However, systematic investigations of analogous cyclic counterparts of heavier main-group elements are limited, with only a few known by theoretical studies. Furthermore, these corresponding cyclic structures lack synthetic examples in the condensed phase, primarily attributed to their high reactivity resulting from lone electron pairs and the absence of electronic delocalization, which typically aids in stabilizing the structure. In this work, we introduce the pioneering synthesis of a pure antimony-based inorganic nanotorus, denoted as Sb₆₈^8-, facilitated by the incorporation of C₆₀ for oxidation by utilizing wet-chemistry methodologies. The unique nanotorus structure was meticulously examined via single-crystalline X-ray diffraction, unveiling its composition of 68 antimony atoms and forming a tubular structure with approximate dimensions of 18.5 × 18.4 Ų in a square shape. Theoretical calculations further revealed that the nanotorus structure, characterized by 16 delocalized electrons distributed across eight 3c-2e σ bonds, effectively saturated the eight two-coordinated Sb atoms within the cluster. This study unveils an innovative approach to synthesizing cyclic compounds solely from pure elements, departing from traditional methods dependent on chemical vapor deposition or surface synthesis, and heralds a profound paradigm shift in physical science.