M(BO)$_{k+1}^-$ Anions: Novel Superhalogens Based on Boronyl Ligands

TL;DR

This study introduces new boronyl-based superhalogen anions with high stability and unique structures, expanding the understanding of superhalogen properties and potential applications in superatomic and boron chemistry.

Contribution

It reports the design and characterization of novel boronyl-based superhalogen anions with detailed structural, energetic, and electronic properties using high-level ab initio methods.

Findings

Anions are stable against fragmentation.

VDE ranges from 4.44 to 7.81 eV, higher than halogens.

Linear correlation between orbital gap and VDE.

Abstract

Superhalogens have been a subject of continuous attraction for the last four decades due to their unusual structures and interesting applications. In the quest for new superhalogens based on boronyl (BO) ligands, we investigate M(BO)$_{k+1}^-$ anions using high-level ab initio CCSD(T) and B3LYP density functional method for M = Li, Na, K, Be, Mg, Ca, B, and Al. Their structures are linear for M = Li, Na, K, trigonal planar M = Be, Mg, Ca, and tetrahedral for M = B, Al. These anions are energetically and thermodynamically stable against various fragmentations. Their superhalogen property has been established due to their higher vertical detachment energy (VDE) than halogen, being in the range 4.44-7.81 eV. For a given k, the stability and VDE of M(BO)$_{k+1}^-$ anions decrease with the increase in the size of M, which is due to a decrease in the charge delocalization on BO moieties. There exists a linear correlation between frontier orbitals energy gap and VDE with the coefficient, R$^2$ = 0.93888. It was also noticed that BO ligand, due to lower dimerization energy, can be preferably used as an inorganic analog of CN. We believe that these findings should be interesting for researchers working in superatomic chemistry as well as in boron chemistry. Keywords: