Double-chain planar D2h B4H2, C2h B8H2, and C2h B12H2: conjugated aromatic borenes

Abstract

Based upon comprehensive theoretical investigations and known experimental observations, we predict the existence of the double-chain planar D_2h B₄H₂(1), C_2h B₈H₂(3), and C_2h B₁₂H₂(5) which appear to be the lowest-lying isomers of the systems at the density functional theory level. These conjugated aromatic borenes turn out to be the boron hydride analogues of the conjugated ethylene D_2h C₂H₄(2), 1,3-butadiene C_2h C₄H₆(4), and 1,3,5-hexatriene C_2h C₆H₈(6), respectively, indicating that a B₄ rhombus in B_2nH₂ borenes (n = 2, 4, 6) is equivalent to a CC double bond unit in the corresponding C_nH_n+2 hydrocarbons. Detailed canonical molecular orbital (CMO), adaptive natural density partitioning (AdNDP), and electron localization function (ELF) analyses unravel the bonding patterns of these novel borene clusters and indicate that they are all overall aromatic in nature with the formation of islands of both σ- and π- aromaticity. The double-chain planar or quasi-planar C_2v B₃H₂⁻(7), C₂ B₅H₂⁻(8), and C_2h B₆H₂(9) with one delocalized π orbital, C_2v B₇H₂⁻(10), C₂ B₉H₂⁻(11), and C_2h B₁₀H₂(12) with two delocalized π orbitals, and C_2v B₁₁H₂⁻(13) with three delocalized π orbitals are found to be analogous in π-bonding to D_2h B₄H₂(1), C_2h B₈H₂(3), and C_2h B₁₂H₂(5), respectively. We also calculated the electron affinities and ionization potentials of the neutrals and simulated the photoelectron spectroscopic spectra of the monoanions to facilitate their future experimental characterization. The results obtained in this work enrich the analogous relationship between hydroborons and their hydrocarbon counterparts and help to understand the high stability of the theoretically predicted all-boron nanostructures which favor the formation of double-chain substructures.