Measuring Electronic Structure of Multiply Charged Anions to Understand Their Chemistry: A Case Study on Gaseous Polyhedral closo-Borate Dianions.

Research on multiply charged anions (MCAs) in the gas phase has been intensively performed during the past decades, mainly to understand fundamental molecular physics phenomena, for example, intramolecular Coulomb repulsion and existence of the repulsive Coulomb barrier. However, the relevance of these investigations with respect to understanding MCAs' chemistry appears often vague. Here, we discuss how insights into the electronic structure obtained from negative ion photoelectron spectroscopy (NIPES) combined with theoretical calculations and collision-induced dissociation can provide a fundamental understanding of the intrinsic chemical reactivity of MCAs and their fragments. This is exemplified in our studies on polyhedral closo-borate dianions [BnXn]2- (n = 6, 10, 11, 12; X = H, F-I, CN) and their fragment ions. For example, the rational design of closo-borate dianions with specific electronic properties is described, which leads to generating highly reactive fragments. Depending on the dianionic precursor, these fragments are tuned to either bind noble gases effectively or activate small molecules like CO and N2. The intrinsic electronic properties of closo-borate dianions are further compared to their electrochemistry in solutions, revealing solvent effects on the redox potentials. Neutral host molecules such as cyclodextrins are found to bind strongly to [BnXn]2-, and gas phase NIPES provides insights into the intrinsic host-guest interactions. Finally, outlooks including the direct NIPES of molecular fragment ions that cannot be generated in the condensed phase and their utilization in preparative mass spectrometry are discussed.