The N⋯HF Interactions in the X-Pyridazine⋯(HF)2Complexes: Substituent Effects and Energy Components

[摘要] The effects of substituents on the N⋯HF interactions in the X-pyridazine⋯(HF)n(X = N(CH3)2, NHCH3, NH2, C2H5, CH3, OCH3, OH, CN, OF, NO2, F, Br, Cl, andn=1, 2) complexes have been studied at the B3LYP/6-311++G(d,p) level of theory. In all complexes, the binding energies increase for the electron-donating substituents and decrease for the electron-withdrawing substituents. A negative cooperativity is observed for two hydrogen bond interactions. There are meaningful relationships between the Hammett constants and the energy data and the results of population analysis in the binary and ternary complexes. Symmetryadapted perturbation theory (SAPT) analysis was also carried out to unveil the nature of hydrogen bond in the complexes2and3. The electron-donating substituents increase the magnitude of the SAPT interaction energy components and the electron-withdrawing substituents decrease those components. The highest/lowest change is observed for theEexch/Edispcomponent. The effect of C2H5(or CH3) on different components is higher than OCH3in the complex2while the trend is reversed in the complex3. It is demonstrated that the electrostatic interaction plays a main role in the interaction, although induction and dispersion interactions are also important.

[学科分类] 物理化学和理论化学