Planar tetracoordinate fluorine in a FMg₄Se₄^- cluster

Area of Science:

• Computational Chemistry
• Materials Science
• Inorganic Chemistry

Background:

• Planar hypercoordination is a challenging area in chemistry due to the preference for delocalized bonding.
• Highly electronegative elements, like fluorine, rarely achieve planar hypercoordinate configurations.
• Previous predictions for planar tetracoordinate fluorine clusters are limited.

Purpose of the Study:

• To theoretically predict a novel cluster featuring a planar tetracoordinate fluorine atom.
• To investigate the structural and electronic properties of the predicted cluster.
• To assess the stability and potential for experimental realization of the FMg4Se4- cluster.

Main Methods:

• Density Functional Theory (DFT) calculations were employed.
• The electronic structure, including HOMO-LUMO gap and vertical detachment energy, was analyzed.
• Dynamic stability of the predicted cluster was evaluated.

Main Results:

• A star-like D4h-symmetry cluster, FMg4Se4-, featuring a planar tetracoordinate fluorine (ptF) was successfully predicted.
• The planar configuration is stabilized by electrostatic interactions between the central ptF and the Mg4Se4 framework.
• The cluster exhibits favorable electronic properties with a HOMO-LUMO gap of 5.85 eV and a vertical detachment energy of 5.24 eV.
• The FMg4Se4- cluster demonstrated dynamic stability.

Conclusions:

• The theoretical prediction of FMg4Se4- represents a significant advancement in the study of planar hypercoordination, particularly for fluorine.
• The cluster's unique structure and electronic properties make it a compelling candidate for experimental investigation.
• This research opens new avenues for synthesizing and characterizing novel hypercoordinate compounds involving highly electronegative elements.