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Abstract <p>This study explores the halogen bonding interactions between dibenziodonium cation and flexible triethylene glycol derivatives (HO<sup>1</sup>CH<sub>2</sub>H<sub>2</sub>O<sup>2</sup>CH<sub>2</sub>H<sub>2</sub>O<sup>3</sup>CH<sub>2</sub>H<sub>2</sub>O<sup>4</sup>H and PhO<sup>1</sup>CH<sub>2</sub>H<sub>2</sub>O<sup>2</sup>CH<sub>2</sub>H<sub>2</sub>O<sup>3</sup>CH<sub>2</sub>H<sub>2</sub>O<sup>4</sup>Ph through a combination of <sup>1</sup>H NMR titration and quantum chemical calculations. NMR studies in CDCl<sub>3</sub> revealed a significantly higher binding affinity for the unsubstituted glycol over its phenyl-substituted analogue, with association constants of 160 and 3.04 M<sup>–1</sup>, respectively. This disparity, alongside the absence of binding in the competitive solvent DMSO, highlights the critical influence of ligand substituents and solvation. DFT calculations elucidated the thermodynamic preference for macrocyclic-type coordination via non-vicinal oxygen atoms (O<sup>1</sup>, O<sup>3</sup> and O<sup>1</sup>, O<sup>4</sup> modes) over chelation at vicinal sites. This preference is attributed to the geometric requirement for simultaneous engagement of the iodonium cation σ-holes. These results provide key design principles for tuning supramolecular recognition and catalysis based on iodonium-based halogen bond donors.</p>

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A Combined NMR and DFT Study of the Binding Modes and Affinities of Dibenziodonium Triflate with Triethylene Glycols

  • 期刊论文

  • 发表日期：

    2025年11月1日

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  • Yana V. Safinskaya,
  • Aleksey V. Kovalenko,
  • Mikhail V. Il’in

摘要

Abstract

This study explores the halogen bonding interactions between dibenziodonium cation and flexible triethylene glycol derivatives (HO1CH2H2O2CH2H2O3CH2H2O4H and PhO1CH2H2O2CH2H2O3CH2H2O4Ph through a combination of 1H NMR titration and quantum chemical calculations. NMR studies in CDCl3 revealed a significantly higher binding affinity for the unsubstituted glycol over its phenyl-substituted analogue, with association constants of 160 and 3.04 M–1, respectively. This disparity, alongside the absence of binding in the competitive solvent DMSO, highlights the critical influence of ligand substituents and solvation. DFT calculations elucidated the thermodynamic preference for macrocyclic-type coordination via non-vicinal oxygen atoms (O1, O3 and O1, O4 modes) over chelation at vicinal sites. This preference is attributed to the geometric requirement for simultaneous engagement of the iodonium cation σ-holes. These results provide key design principles for tuning supramolecular recognition and catalysis based on iodonium-based halogen bond donors.