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Cl©Li 5 Cl 5 - : A Star-like Superhalogen Anion Featuring a Planar Pentacoordinate Chlorine at the Center.

Li-Xia BaiCai-Yue GaoJin-Chang GuoSi-Dian Li
Published in: Molecules (Basel, Switzerland) (2024)
Among the known planar pentacoordinate atoms, chlorine is missing due to its large radius and high electronegativity. Herein, we report the first star-like superhalogen anion D 5 h Cl©Li 5 Cl 5 - ( 1 ), which contains a planar pentacoordinate chlorine (ppCl) at the center. Computer structural searches and high-level calculations reveal that 1 is a true global minimum (GM) on the potential energy surfaces. Molecular dynamics simulations indicate it is kinetically stable against isomerization or decomposition. Although detailed chemical bonding analyses reveal one delocalized 6c-2e σ bond over the Cl©Li 5 central unit and five delocalized 3c-2e σ bonds along the periphery, while aromaticity has very little beneficial effect on stability, instead, ionic interaction dominates the stability of the system. More encouragingly, with the large HOMO-LUMO energy gap of 7.66 eV and vertical detachment energy of 7.87 eV, the highly chemically inert 1 can be viewed as a typical superhalogen anion and is possible to be synthesized and characterized in future experiments.
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