An ab initio study of some halogen-bonded complexes containing cyclic ethers

Abstract

The binary complexes formed between the dihalogens fluorine, chlorine and bromine, and the cyclic ethers oxirane, oxetane, tetrahydrofuran and tetrahydropyran, have been studied by means of ab initio calculations at the second-order level of Møller–Plesset perturbation theory. The properties of interest are the interaction energies, the intermolecular geometries, the perturbations of the intramolecular dihalogen and ether geometries, the wavenumber shifts of the dihalogen and ether molecules, and the variations of the natural atomic charges resulting from complexation. The trends observed are discussed in terms of the physical properties of the interacting monomers, such as the polarizabilities of the dihalogen molecules and the gas phase basicities of the ethers.

GRAPHICAL ABSTRACT

KEYWORDS:

• Ab initio calculations
• halogen-bonded complexes
• molecular structures
• interaction energies
• vibrational spectra

Acknowledgements

Any opinion, findings and conclusions or recommendations expressed in this material are those of the author and do not necessarily reflect the views of the National Research Foundation. The author acknowledges the University of KwaZulu-Natal Research Fund for financial assistance, the Centre for High Performance Computing (South Africa) for the use of computing facilities, and Dr Anton Lopis for invaluable technical assistance.

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

This work was supported by the National Research Foundation of South Africa under grant number 2053648.