Electronic properties of the halogen bonds Z3CX···Y− between halide anions and methyl halides

摘要

In this study, the linear halogen bonds Z3CX···Y– (X = Cl, Br; Y, Z = F, Cl, Br) are theoretically investigated. They have large interaction energies—23–160 kJ/mol, and the interactions are closed-shell in nature. In some systems, a blue-shifted halogen bond is formed. Although the electrostatic interaction is important, the intermolecular charge transfer caused by the intermolecular hyperconjugation n(Y−) → σ*(CX) and the intramolecular charge redistribution by the intramolecular hyperconjugation n(Z) → σ*(CX) play important roles in the formation of the halogen bonds.