| Summary: | 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 <i>D</i><sub>5<i>h</i></sub> Cl©Li<sub>5</sub>Cl<sub>5</sub><sup>−</sup> (<b>1</b>), which contains a planar pentacoordinate chlorine (ppCl) at the center. Computer structural searches and high-level calculations reveal that <b>1</b> 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<sub>5</sub> 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 <b>1</b> can be viewed as a typical superhalogen anion and is possible to be synthesized and characterized in future experiments.
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