Illuminating the Performance of Electron Withdrawing Groups in Halogen Bonding.

Autor: Devore DP; Department of Chemistry and Biochemistry, Baylor University, One Bear Place 97348, Waco, TX, 76798-7348, USA.; Present address: Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75205, USA., Ellington TL; Department of Chemistry and Biochemistry, Baylor University, One Bear Place 97348, Waco, TX, 76798-7348, USA.; Present address: Department of Chemistry and Physics, University of Tennessee Martin, 554 University Street, Martin, TN 38238, USA., Shuford KL; Department of Chemistry and Biochemistry, Baylor University, One Bear Place 97348, Waco, TX, 76798-7348, USA.
Jazyk: angličtina
Zdroj: Chemphyschem : a European journal of chemical physics and physical chemistry [Chemphyschem] 2024 Dec 16; Vol. 25 (24), pp. e202400607. Date of Electronic Publication: 2024 Nov 03.
DOI: 10.1002/cphc.202400607
Abstrakt: Throughout the halogen bonding literature, electron withdrawing groups are relied upon heavily for tuning the interaction strength between the halogen bond donor and acceptor; however, the interplay of electronic effects associated with various substituents is less of a focus. This work utilizes computational techniques to study the degree of σ- and π-electron donating/accepting character of electron withdrawing groups in a prescribed set of halo-alkyne, halo-benzene, and halo-ethynyl benzene halogen bond donors. We examine how these factors affect the σ-hole magnitude of the donors as well as the binding strength of the corresponding complexes with an ammonia acceptor. Statistical analyses aid the interpretation of how these substituents influence the properties of the halogen bond donors and complexes, and show that the electron withdrawing groups that are both σ- and π-electron accepting form the strongest halogen bond complexes.
(© 2024 The Author(s). ChemPhysChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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