Citation: Jun Li, Shi-Hu Du, Yao Zhang, Jia Liu, Jing Chen, Shi-Bo Cheng. Shell-independent superhalogen formation in aluminum-based clusters via boron Lewis acid ligands functionalization[J]. Chinese Chemical Letters, ;2026, 37(1): 111177. doi: 10.1016/j.cclet.2025.111177 shu

Shell-independent superhalogen formation in aluminum-based clusters via boron Lewis acid ligands functionalization

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School of Chemistry and Chemical Engineering, Shandong University, Ji'nan 250100, China

shibocheng@sdu.edu.cn

Received Date: 25 February 2025
Revised Date: 24 March 2025
Accepted Date: 2 April 2025
Available Online: 3 April 2025

Figures(5)

The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl₁₂ can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
- Superhalogen,
- Superatomic states,
- Lewis acid ligand,
- Electronic shell occupancy,
- Electronic property
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