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Updated: May 23, 2025

Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique
Published on: November 3, 2017
Alkali-Noble Metal Synergy in F©Li4M4- (M = Ag, Au): A Novel Ionic Framework for Stabilizing Planar Tetracoordinate
Miao Yan1, Lin-Yan Feng1, Chang-Qing Miao1
1Department of Chemistry, Xinzhou Normal University, Xinzhou, Shanxi 034000, China.
Abstract:
Planar tetracoordinate fluorine (ptF) has long been considered elusive due to the high electronegativity and lone-pair rigidity of fluorine. Herein, we report the star-like ptF clusters in noble metal-bridged clusters F©Li4M4- (M = Ag, Au) via a purely ionic mechanism. Combining density functional theory (DFT) and coupled-cluster calculations, these D4-symmetric global minima feature a central F- electrostatically confined by a Li4 square with Ag/Au bridges optimizing the cavity size. Natural bond orbital analysis shows that there is a substantial charge transfer between F and Li, while covalency is almost negligible. Born-Oppenheimer molecular dynamics simulations reveal their excellent dynamic stability at room temperature. The high vertical detachment energies (3.62 and 5.07 eV) classify them as superhalogen anions. Notably, the stability of these clusters is not reliant on aromaticity; rather, it is primarily governed by electrostatic interactions. This work expands the field of ptF chemistry and highlights the role of noble metals as geometric enablers for ionic hypercoordination.
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