Effects of methylation in acceptors on the hydrogen bond complexes between 2,2,2-trifluoroethanol and cyclic ethers

In order to explore the effect of methylation on the stability and spectral shift of hydrogen bond complexes, the complexes of 2,2,2-trifluoroethanol (TFE) with propylene oxide (PO) and isobutylene oxide (IBO) were investigated by Fourier transform infrared (FTIR) spectroscopy and ab initio computations. The comparable OH-stretching red shifts were observed upon complexation, and an enhancement of the OH-stretching band is shown with the partial pressure of monomers increasing. The OH-stretching frequency of TFE is red shifted by 180 and 201 cm ⁻¹ with PO and IBO, respectively. By using quantum chemical calculations, we predicted the geometric parameters, binding energies, and spectral shifts of TFE–PO/IBO hydrogen bond complexes. The calculated and observed spectral shifts follow the same trends. Compared with the TFE–ethylene oxide (EO) complex, the strength of the hydrogen bond in complex increases with the addition of methyl group, which likely results from the increase in basicity of the hydrogen bond acceptor. By combining the experimental integrated absorbance and the calculated IR intensity of the OH-stretching vibrational transition, the equilibrium constant for the complex formation was determined. In addition, atoms-in-molecules (AIM) and natural bond orbital (NBO) analyses were carried out to explain the red shift and the nature of the interaction in these complexes.