Polyion Covalency: Exotic Species from the Unexplored World of Electrostatically Shielded Molecular Ion Chemistry

Standard quantum chemical methods have been employed to describe a variety of kinetically stable polyionic molecular species that are trapped in appreciable potential wells by chemical bonding forces, despite powerful electrostatic opposition that challenges conventional chemical detection and characterization. The studied species are covalent or dative analogs of “anti‐electrostatic” hydrogen‐bonded (AEHB) species, all illustrating how short‐range quantum covalency can overcome the powerful “shielding” opposition of long‐range electrostatic forces to form highly charged molecular species, analogous to known neutral or singly ionic counterparts. Computational predictions of representative structural, spectroscopic, and NBO‐based electronic signatures of multiply charged analogs of common neutral species (CH₃CH₃, CO₂, FeCO) are provided to suggest the unique material properties characteristic of this shielded domain of polyionic chemical phenomena.