Isolated [B2(CN)6]2-: Small Yet Exceptionally Stable Nonmetal Dianion.

Abstract

We report the observation of a small, yet remarkably stable, metal-free hexacyanodiborate dianion [B2(CN)6]2- in the gas phase. Negative ion photoelectron spectroscopy (NIPES) was employed to measure its spectra at multiple laser wavelengths, yielding a 1.9 eV electron binding energy (EBE) ─a remarkably high value of electronic stability and a ∼2.60 eV repulsive Coulomb barrier (RCB) for electron detachment. This rationalizes the observation of this dianion, although homolytic charge-separation dissociation into two [B(CN)3]•- is energetically favorable. Quantum chemical calculations demonstrate a D3d staggered conformation for both the dianion and radical monoanion, and the calculated EBE and RCB match the experimental values well. The simulated density of states spectrum reproduces all measured electronic transitions, while the simulated vibrational progressions for the ground state transition cover a much narrower EBE range compared to the experimental band, indicating appreciable auto-photodetachment via electronically excited dianion resonances.