Triel bonds within anion···anion complexes

The ability of two anions to interact with one another is tested in the context of pairs of TrX₄^- homodimers, where Tr represents any of the triel atoms B, Al, Ga, In, or Tl, and X refers to a halogen substituent F, Cl, or Br. None of these pairs engage in a stable complex in the gas phase, but the situation reverses in water where the two monomers are held together by Tr⋯X triel bonds, complemented by stabilizing interactions between X atoms. Some of these bonds are quite strong, notably those involving TrF₄^-, with interaction energies surpassing 30 kcal mol^-1. Others are very much weaker, with scarcely exothermic binding energies. The highly repulsive electrostatic interactions are counteracted by large polarization energies.