The effect of the hydrogen fluoride chain on the aromaticity of C6H6 in the C6H6···(HF)1–4 complexes

The effect of the hydrogen fluoride chain ((HF)_n) on the aromaticity and π character of C–C bonds of C₆H₆ in the C₆H₆···(HF)_n (n = 1–4) complexes were investigated using density functional theory employing RM05 functional. It was found that the binding energy between C₆H₆ and different (HF)_n chains showed a maximum at n = 3 (C₆H₆···(HF)₃). Also, the π–hydrogen interaction (πHI) and the bifurcated fluorine interaction (BFI) increased and decreased the π character of the C–C bond of C₆H₆, respectively. In addition, the change of aromaticity of the C₆H₆ due to the interaction with the HF chains was also studied using three different aspects such as aromatic fluctuation index (FLU), average two centre index (ATI) and proton nuclear magnetic resonance (HNMR) spectrum. The most change in the aromaticity happens when the C₆H₆ interacts with (HF)₃ chain. The variation of aromaticity with the binding energy and the summation of two-body terms were investigated and very good linear correlations were observed.