We designed M1⋅⋅⋅C6H5X⋅⋅⋅HM2 (M1=Li+, Na+; X=Cl, Br; M2=Li, Na, BeH, MgH) complexes to enhance halogen–hydride halogen bonding with a cation–π interaction. The interaction strength has been estimated mainly in terms of the binding distance and the interaction energy. The results show that halogen–hydride halogen bonding is strengthened greatly by a cation–π interaction. The interaction energy in the triads is two to six times as much as that in the dyads. The largest interaction energy is −8.31 kcal mol−1 for the halogen bond in the Li+⋅⋅⋅C6H5Br⋅⋅⋅HNa complex. The nature of the cation, the halogen donor, and the metal hydride influence the nature of the halogen bond. The enhancement effect of Li+ on the halogen bond is larger than that of Na+. The halogen bond in the Cl donor has a greater enhancement than that in the Br one. The metal hydride imposes its effect in the order HBeH<HMgH<HNa<HLi for the Cl complex and HBeH<HMgH<HLi<HNa for the Br complex. The large cooperative energy indicates that there is a strong interplay between the halogen–hydride halogen bonding and the cation–π interaction. Natural bond orbital and energy decomposition analyses indicate that the electrostatic interaction plays a dominate role in enhancing halogen bonding by a cation–π interaction.
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