Ligand rigidity as a design principle for planar pentacoordinate fluorine

Area of Science:

• Inorganic Chemistry
• Computational Chemistry
• Materials Science

Background:

• Planar hypercoordinate fluorine species are exceptionally rare due to fluorine's high electronegativity.
• Understanding the stabilization mechanisms for such structures is crucial for advancing chemical bonding theories.

Purpose of the Study:

• To investigate the possibility of stabilizing planar hypercoordinate fluorine.
• To characterize the electronic structure and bonding nature of a novel fluorine-containing cluster.

Main Methods:

• Density functional theory (DFT) calculations were employed to explore potential stable structures.
• Analysis of bonding characteristics, including electrostatic and covalent contributions.
• Calculation of detachment energy to determine superhalogen properties.

Main Results:

• A stable D5h F©Zn5O5- cluster was identified as a global minimum, featuring planar hypercoordinate fluorine.
• The bonding within the cluster is predominantly electrostatic, with a smaller covalent component.
• A high detachment energy of 6.29 eV confirms the cluster's superhalogen nature.

Conclusions:

• The Zn5O5 framework effectively stabilizes planar hypercoordinate fluorine, challenging previous assumptions.
• The identified F©Zn5O5- cluster represents a novel superhalogen with unique electronic properties.
• This discovery provides insights into the formation and stability of exotic chemical species.