AUTHOR=Cyraniak Adrianna , Faron Dawid , Freza Sylwia , Anusiewicz Iwona , Skurski Piotr 

TITLE=Superhalogen Anions Supported by the Systems Comprising Alternately Aligned Boron and Nitrogen Central Atoms

JOURNAL=Frontiers in Chemistry

VOLUME=10

YEAR=2022

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2022.863408

DOI=10.3389/fchem.2022.863408

ISSN=2296-2646

ABSTRACT=<p>Using DFT/(B3LYP/wB97XD/B2PLYPD) and OVGF electronic structure methods with flexible atomic orbital basis sets, we examined the series of polynuclear superhalogen anions matching the (BF<sub>3</sub>(BN)<sub><italic>n</italic></sub>F<sub>4<italic>n</italic>+1</sub>)<sup>–</sup> formula (for <italic>n</italic> = 1-10,13,18-20) containing alternately aligned boron and nitrogen central atoms decorated with fluorine ligands. It was found that the equilibrium structures of these anions correspond to fully extended chains (with each B and N central atom surrounded by four substituents arranged in a tetrahedral manner) and thus mimic the globally stable fully extended (all-<italic>trans</italic>) conformations of higher n-alkanes. The vertical electron detachment energies of the (BF<sub>3</sub>(BN)<sub><italic>n</italic></sub>F<sub>4<italic>n</italic>+1</sub>)<sup>–</sup> anions were found to exceed 8 eV in all cases and gradually increase with the increasing number of <italic>n</italic>. The approximate limiting value of vertical electron binding energy that could be achieved for such polynuclear superhalogen anions was estimated as equal to ca. 10.7 eV.</p>