Theoretical investigation of substituent effects on the relative stabilities and electronic structure of [BnXn]2- clusters

Abstract

In this study, we provide a theoretical evaluation of relative stabilities and electronic structure for [B_nX_n]^2- clusters (n = 10, 12, 13, 14, 15, 16). Structural and electronic characteristics of [B_nX_n]^2- clusters are examined by comparison with the [B₁₂X₁₂]^2- counterparts with a focus on the substituent effects (X = H, F, Cl, Br, CN, BO, OH, NH₂) on the electronic structure, electron detachment energies, formation enthalpies, and charge distributions. For the electronic structure and electron detachment energies, substituent effects on boron clusters are shown to follow a very similar trend to the mesomeric and inductive effects (± M and ± I) of π-conjugated systems, and the most stable derivatives in terms of HOMO/LUMO and electron detachment energies are calculated for CN and BO substituents due to strong -M effects. In the case of formation enthalpies for larger boron clusters (n ≥ 13), the icosahedral barrier is shown to increase with the halogen and CN substitution, whereas it is possible to reduce the icosahedral barrier for the cases of X = OH and NH₂. It is shown that this reduction results from destabilizing the [B₁₂X₁₂]^2- cluster with electronic (+ M) and symmetry effects induced by OH and NH₂ ligands.

Keywords: Boron clusters; Icosahedral barrier; Inductive effect; Mesomeric effect; Substitution.