Citation: Ao-Hua Wang, Jun Li, Shi-Hu Du, Jia Liu, Yao Zhang, Muhammad Bilal Ahmed Siddique, Jing Chen, Shi-Bo Cheng. Beyond superhalogen assembly: Field-driven hyperhalogen design via dual-external-field cooperativity[J]. Chinese Chemical Letters, ;2026, 37(1): 111265. doi: 10.1016/j.cclet.2025.111265 shu

Beyond superhalogen assembly: Field-driven hyperhalogen design via dual-external-field cooperativity

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

shibocheng@sdu.edu.cn

Received Date: 26 March 2025
Revised Date: 21 April 2025
Accepted Date: 27 April 2025
Available Online: 27 April 2025

Figures(4)

Traditional strategies for designing hyperhalogens, superatoms with exceptional electron-withdrawing capacity, rely on complex superhalogen assembly, posing significant experimental challenges. Here, we introduce a non-invasive dual external field (DEF) approach combining solvent effects and an oriented external electric field (OEEF) to construct hyperhalogens, as demonstrated by density functional theory (DFT) calculations. Our DEF strategy proves versatile, successfully designing hyperhalogens not only in simplified Ag_n⁻ model systems but also in the experimentally synthesized Ag₂₅ nanocluster. Using the 3D Ag₁₉⁻ structure as a model, we further reveal the DEF's pivotal role in O₂ activation, where solvent-OEEF synergy induces tunable O–O bond elongation and charge transfer, proportional to field strength. Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition, providing a theoretical foundation for tailoring high-performance catalysts through precise active-site modulation.
- Hyperhalogens,
- Dual external fields,
- Silver clusters,
- O₂ activation,
- Charge transfer
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