Joint X-ray spectroscopic and quantum-chemical study of the electronic structure of pentafluorophenylalkyl ethers

Abstract

The high resolution X-ray emission O-Kα spectra of pentafluorophenylalkyl ethers C6F5OR (R=Et, Pri, and But) exhibit differences related to a change in the electronic structure of the compounds as R is varied. The search for stable conformers was performed by the semiempirical PM3 method. The most probable structures of C6F5OR were determined by the comparison of the experimental and theoretical X-ray spectra plotted for each conformer usingab initio calculations in the 6–31 G basis set. Substituent R in pentafluorophenylalkyl ethers is situated outside of the ring plane. The fluorination of the benzene ring changes the energy level of the lone electron pair of oxygen relative to the levels of orbitals of the ring and substituent R and leads to an increase in the efficiency of interactions in the σ-system.