Anti-Electrostatic CH-Ion Bonding in Decorated Graphanes.

State-of-the-art computations combined with Ziegler-Rauk energy decomposition analyses are employed to introduce a new class of anti-electrostatic ion-σ bonds with considerable stability and a substantial contribution from charge transfer and dispersion between ions and finite-size functionalized graphane flakes, G-XYs. G-XYs have diverse electric multipolar moments that are comparable with those of newly synthesized all-cis-hexa-halocyclohexanes. The strong, long-range electrostatic and Pauli repulsions between some G-XYs and certain ions induce a gas-phase energy barrier to the physisorption of ions on the surface of G-XYs. However, the repulsive interactions can be overbalanced by the strong orbital interactions operating in the formation of ion-σ complexes at short range, leading to covalent-type intermolecular bonds as strong as -34 kcal mol-1 .