Substituent effects on the halogen and pnictogen bonds characteristics in ternary complexes 4-YPhNH2···PH2F···ClX (Y = H, F, CN, CHO, NH2, CH3, NO2 and OCH3, and X = F, OH, CN, NC, FCC and NO2): A theoretical study

Abstract

The synergistic relationship between pnictogen and halogen non-covalent interactions in 4-YPhNH2···PH2F···ClX (Y = H, F, CN, CHO, NH2, CH3, NO2 and OCH3; X = F, OH, CN, NC, FCC and NO2) complexes were explored using Aug-ccpVDZ basis set and M06-2X and M06-2X-GD3, B2PLYP-GD3 and mPW2PLYP-GD2 functionals. The effects of the substituents included at pnictogen bond and halogen bond segments on the correlation between BEs and pnictogen as well as halogen bond distances, electron density at both non-covalent interactions, charge transfer energies between components and the NMR properties were evaluated. The energy analysis indicates that the pnictogen bond interaction has a much greater stabilizing effect than the halogen bond one. In addition, the auxiliary effect of a pnictogen bond on a halogen bond is more pronounced than that of a halogen bond on a pnictogen bond. The synergistic relationship between pnictogen and halogen non-covalent interactions in 4-YPhNH2···PH2F···ClX (Y = H, F, CN, CHO, NH2, CH3, NO2 and OCH3; X = F, OH, CN, NC, FCC and NO2) complexes were explored using Aug-cc-pVDZ basis set and M06-2X and M06-2X-GD3, B2PLYP-GD3 and mPW2PLYP-GD2 functionals.