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Li4F4-: Planar tetracoordinate fluorine in a highly viable binary mono-anionic cluster.

Bo Jin1, Miao Yan1, Lin-Yan Feng1

  • 1Department of Chemistry, Xinzhou Normal University, 1 East Dunqi Street, Xinzhou 034000, Shanxi, People's Republic of China.

The Journal of Chemical Physics
|April 22, 2025
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Summary

Researchers report the first planar tetracoordinate fluorine (ptF) anionic species, Li4F4-. This stable cluster, a global minimum, opens new avenues for studying hypercoordinate fluorine chemistry.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Materials Science

Background:

  • Planar hypercoordinate fluorine is challenging due to fluorine's high electronegativity, limiting electron delocalization.
  • Previous research has not reported simple, planar tetracoordinate fluorine (ptF) anionic species suitable for photoelectron spectroscopy.

Purpose of the Study:

  • To introduce the first binary mono-anionic cluster featuring a planar tetracoordinate fluorine (ptF) center.
  • To investigate the structural, dynamic, and electronic properties of this novel anionic species.

Main Methods:

  • Theoretical calculations were employed to determine the global minimum (GM) structure of the Li4F4- cluster.
  • Analysis of stability included assessing dynamic stability and energy barriers to isomerization.
  • Electronic structure was examined to understand the bonding contributions stabilizing the ptF center.

Main Results:

  • The first binary mono-anionic Li4F4- cluster with a C2v symmetric ptF center was identified as the global minimum.
  • The cluster exhibits good dynamic stability with significant energy barriers against interconversion to other isomers.
  • The neutral Li4F4 species adopts a cubic structure, contrasting with the planar anionic form, resembling bulk LiF.

Conclusions:

  • The stability of the ptF moiety in Li4F4- is primarily driven by electrostatic interactions, with a minor covalent contribution, not aromaticity.
  • The Li4F4- cluster is a highly viable species with significant potential for experimental detection and characterization.
  • This discovery advances the understanding of hypercoordinate bonding involving fluorine.