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<p>Using density functional theory (DFT) and the quantum theory of atoms in molecules (QTAIM) we investigate the molecular structure and chemical bonding in six silafullerane clusters with a caged chloride ion, Cl<sup>−</sup>@Si<sub>20</sub>Y<sub>20</sub> (Y = H, F, Cl, Br, CN, Me). The encapsulation of chloride in silafullerane provokes the shrinkage of the cage and an elongation of the covalent bonds between the silicon atoms and the exohedral groups. The vibrational analysis indicates that the cage breathing mode frequency becomes blue-shifted upon anion encapsulation. QTAIM reveals the presence of closed shell interactions between the confined chloride ion and the silicon atoms of the cage. Furthermore, electron charge density is partially transferred from the trapped anion to the exohedral substituents the amount of which is determined by the electron charging ability of each substituent. The silicon atoms of the cage form a layer of positive charge that separates the chloride ion from the negatively charged exohedral substituents. Thus, the binding of the anion in silafulleranes is governed by strong electrostatic interactions that are operative at the Cl<sup>−</sup>/Si<sub>20</sub> and Si<sub>20</sub>/Y<sub>20</sub> interfaces.</p>

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Chloride trapped in silafulleranes: structure and bonding revealed by the quantum theory of atoms in molecules

  • 期刊论文

  • 发表日期：

    2025年9月18日

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  • Fabio Pichierri

摘要

Using density functional theory (DFT) and the quantum theory of atoms in molecules (QTAIM) we investigate the molecular structure and chemical bonding in six silafullerane clusters with a caged chloride ion, Cl−@Si20Y20 (Y = H, F, Cl, Br, CN, Me). The encapsulation of chloride in silafullerane provokes the shrinkage of the cage and an elongation of the covalent bonds between the silicon atoms and the exohedral groups. The vibrational analysis indicates that the cage breathing mode frequency becomes blue-shifted upon anion encapsulation. QTAIM reveals the presence of closed shell interactions between the confined chloride ion and the silicon atoms of the cage. Furthermore, electron charge density is partially transferred from the trapped anion to the exohedral substituents the amount of which is determined by the electron charging ability of each substituent. The silicon atoms of the cage form a layer of positive charge that separates the chloride ion from the negatively charged exohedral substituents. Thus, the binding of the anion in silafulleranes is governed by strong electrostatic interactions that are operative at the Cl−/Si20 and Si20/Y20 interfaces.