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O©Li5F52-: A Global Minimum with a Planar Pentacoordinate Oxygen.

Williams García-Argote1,2, William Tiznado1,3, Luis Leyva-Parra1

  • 1Centro de Investigación para el Diseño de Materiales (CEDEM), Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andrés Bello, Avenida República 275, 8370146 Santiago, Chile.

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Researchers identified a stable planar pentacoordinate oxygen (ppO) motif in the O©Li5F52- cluster. This discovery, driven by electrostatic forces, confirms the second such system and highlights possibilities for realizing ppO structures.

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Area of Science:

  • Inorganic Chemistry
  • Computational Chemistry
  • Quantum Chemistry

Background:

  • Planar pentacoordinate oxygen (ppO) motifs are rare and theoretically challenging to stabilize.
  • Previous research has explored various cluster structures, but confirmed examples of ppO are limited.

Purpose of the Study:

  • To systematically investigate dianionic clusters (O©M5X52-) for viable planar pentacoordinate oxygen (ppO) motifs.
  • To identify and characterize the structural, bonding, and electronic properties of potential ppO systems.

Main Methods:

  • High-throughput computational screening across a wide combinatorial space of M (Li-Cs) and X (F-I) elements.
  • Density Functional Theory (DFT) calculations for structural optimization and energy analysis.
  • Analysis of bonding characteristics and magnetic responses.

Main Results:

  • The starlike D5h-O©Li5F52- cluster was identified as the only true global minimum among the investigated structures.
  • Detailed analyses confirmed that electrostatic interactions are the primary stabilizing force, rather than multicenter covalent bonding.
  • The D5h-O©Li5F52- cluster represents the second confirmed system exhibiting planar pentacoordinate oxygen.

Conclusions:

  • The D5h-O©Li5F52- cluster provides a new, experimentally verifiable example of planar pentacoordinate oxygen.
  • This study demonstrates that ppO motifs can be achieved through strong electrostatic confinement.
  • The findings open avenues for designing novel inorganic compounds with unique structural and electronic properties.