Stabilizing Otherwise Unstable Anions with Halogen Bonding

Both hydrogen bonding (HB) and halogen bonding (XB) are essentially electrostatic interactions, but whereas hydrogen bonding has a well‐documented record of stabilizing unstable anions, little is known about halogen bonding's ability to do so. Herein, we present a combined anion photoelectron spectroscopic and density functional theory study of the halogen bond‐stabilization of the pyrazine (Pz) anion, an unstable anion in isolation due to its neutral counterpart having a negative electron affinity (EA). The halogen bond formed between the σ‐hole on bromobenzene (BrPh) and the lone pair(s) of Pz significantly lowers the energies of the Pz(BrPh)₁⁻ and Pz(BrPh)₂⁻ anions relative to the neutral molecule, resulting in the emergence of a positive EA for the neutral complexes. As seen through its charge distribution and electrostatic potential analyses, the negative charge on Pz⁻ is diluted due to the XB. Thermodynamics reveals that the low temperature of the supersonic expansion plays a key role in forming these complexes.