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Planar Pentacoordinate Bromine in Global Minimum Br6Li5.

Rui Sun1,2, Bo Jin3, Jinzhong Zhao1

  • 1Department of Basic Teaching, Shanxi Agricultural University, 1 Mingxian South Road, Taigu, Shanxi, 030801, People's Republic of China.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|January 25, 2025
PubMed
Summary

Researchers discovered a novel star-like cluster, Br6Li5-, featuring a planar pentacoordinate bromine atom. This unique structure, stabilized by electrostatic forces, offers potential for future spectroscopic studies.

Keywords:
Covalent interactionsElectrostatic interactionsGlobal minimumPlanar pentacoordinate bromineSuperhalogen anion

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Area of Science:

  • Computational Chemistry
  • Inorganic Chemistry
  • Cluster Science

Background:

  • Planar hypercoordinate structures are challenging for electronegative elements like halogens due to delocalized multicenter bonding.
  • Achieving planar hypercoordinate arrangements, especially with halogens, is a significant hurdle in cluster chemistry.

Purpose of the Study:

  • To introduce and characterize a novel star-like cluster, Br6Li5-, featuring a planar pentacoordinate bromine (ppBr) center.
  • To investigate the bonding nature and stability of this unique binary cluster.

Main Methods:

  • Theoretical calculations were employed to determine the global minimum structure of the Br6Li5- cluster.
  • Bonding analyses were performed to understand the nature of interactions within the cluster.
  • Calculations of the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap and vertical detachment energy (VDE) were conducted.

Main Results:

  • A stable star-like cluster, Br6Li5-, with a central planar pentacoordinate bromine (ppBr) atom was identified.
  • The ppBr atom is coordinated by five lithium (Li) atoms, which bridge peripheral bromine atoms.
  • Bonding analysis revealed that electrostatic interactions dominate over covalent interactions in stabilizing the planar pentacoordinate configuration.
  • The cluster exhibits high stability, evidenced by a wide HOMO-LUMO gap (7.73 eV) and high VDE (7.55 eV), despite lacking delocalized bonds.

Conclusions:

  • The Br6Li5- cluster represents a new class of stable planar hypercoordinate compounds featuring a halogen center.
  • Its stability is primarily attributed to strong electrostatic interactions.
  • The cluster is a promising candidate for experimental generation and spectroscopic characterization in the gas phase.