Bai Li-Xia, Gao Cai-Yue, Guo Jin-Chang, Li Si-Dian
Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
Molecules. 2024 Aug 12;29(16):3831. doi: 10.3390/molecules29163831.
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 Cl©LiCl (), which contains a planar pentacoordinate chlorine (ppCl) at the center. Computer structural searches and high-level calculations reveal that 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 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 can be viewed as a typical superhalogen anion and is possible to be synthesized and characterized in future experiments.
在已知的平面五配位原子中，由于氯的半径大且电负性高，所以不存在。在此，我们报道了首个星形超卤素阴离子Cl©LiCl（），其中心含有一个平面五配位氯（ppCl）。计算机结构搜索和高水平计算表明，在势能面上是一个真正的全局最小值（GM）。分子动力学模拟表明，它在动力学上对异构化或分解是稳定的。尽管详细的化学键分析揭示了在Cl©Li中心单元上有一个离域的6c - 2e σ键，沿周边有五个离域的3c - 2e σ键，但芳香性对稳定性的有益影响很小，相反，离子相互作用主导了体系的稳定性。更令人鼓舞的是，由于具有7.66 eV的大HOMO - LUMO能隙和7.87 eV的垂直脱附能，高度化学惰性的可以被视为典型的超卤素阴离子，并且有可能在未来的实验中被合成和表征。
