FK4H4-: Planar Tetracoordinate Fluorine Stabilized by Multicenter Ionic Bonding

Inorg Chem. 2024 Oct 21;63(42):19949-19955. doi: 10.1021/acs.inorgchem.4c03460. Epub 2024 Oct 8.

Abstract

Planar tetracoordinate fluorine (ptF) species are very exotic and scarce due to high electronegativity of fluorine. Herein we report the ternary square ptF cluster, D4h FK4H4-, which is composed of a F center, a square K4 ring, and four outer H bridges. It is a true global minimum (GM) structure and possesses good dynamic stability. Bonding analyses indicate that there are four lone pairs for the central F atom, along with four K-H-K three-center two-electron (3c-2e) σ bonds for the peripheral K4H4 ligand ring. The stability of ptF is dominated by multicenter ionic bonds rather than the supposed σ aromaticity of the system. Excitingly, it is a pseudohalogen anion with the VDE 3.57 eV at the CCSD(T) level. The merge of ptF with pseudohalogen anion character makes the FK4H4- cluster an exotic species, which will motivate theoretical and experimental studies on novel ptF species as well as superhalogens.