Interplay between σ Holes, Anion···H−C, and Cation−π Interactions in Dibromo[2,2]paracyclophane Complexes

Theoretical calculations were performed to investigate the interplay between σ−hole, anion−HC and cation−π interactions in the complexes of dibromo[2,2]paracyclophane (DBr[2,2]PCP) with alkali (Li⁺, Na⁺, K⁺), alkaline
earth metal cations (Be²⁺, Mg²⁺, and Ca²⁺), and halogen anions (F−, Cl−, and Br−) using the wave function (MP2) and density functional theory (M06-2X and B3LYP) methods with the 6-311++G(d,p) basis set. The study reveals that DBr[2,2]PCP behaves as amphoteric molecule with a predominance of basic character. It prefers to interact with hard cations and hard anions such as Be²⁺ and F− through cation−π and anion···HC interactions, respectively. Substitution of Br by F and Cl atoms in DBr[2,2]PCP decreases slightly the interaction energies of DX[2,2]PCP-halogen complexes (X = F, Cl, and Br) by 2.0 and 0.3 kcal/mol (M06-2X), respectively. The anion−HC interactions in DBr[2,2]PCP complexes are ∼10 kcal/mol stronger (B3LYP; ∼15 kcal/mol at M06-2X and 7 kcal/mol at MP2) than the σ−hole interactions.