Superhalogens beget superhalogens: a case study of (BO2)n oligomers

Superhalogens belong to a class of molecules that not only mimic the chemistry of halogen atoms but also possess electron affinities that are much larger than that of chlorine, the element with the highest electron affinity in the periodic table. Using BO2 as an example and the synergy between density functional theory-based calculations and photoelectron spectroscopy experiments we demonstrate another unusual property of superhalogens. Unlike halogens, whose ability to accept an electron falls upon dimerization, B2O4, the dimer of BO2, has an electron affinity larger than that of the BO2 building block. This ability of (BO2)2 and subsequent, higher oligomers (BO2)n (n = 3 and 4), to retain their superhalogen characteristics can be traced to the enhanced bonding interactions between oxygen and boron atoms and due to the delocalization of the charge of the extra-electron over the terminal oxygen atoms. These results open the door to the design and synthesis of a new class of metal-free highly negative ions with potential for novel applications.