What drives enhanced chloride recognition of squaramide-based receptors over urea and thiourea? A computational exploration in the gas-phase and various solvents

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-03-20 DOI:10.1016/j.comptc.2025.115191

Yasin Gholiee

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引用次数: 0

Abstract

Significant progress in anion recognition has been achieved through the development of synthetic receptors. Urea-, thiourea-, and squaramide-based molecules, known for hydrogen-bonding capabilities, have gained prominence in supramolecular chemistry. The superior anion recognition of squaramide-based receptors, compared to urea- and thiourea-based ones, is repeatedly attributed to the crucial involvement of CH fragments. This study computationally investigates chloride recognition by nine symmetric urea-, thiourea-, and squaramide-based receptors, focusing on solvent effects, interactions, and intrinsic affinity. The findings suggest that while CH fragments aid anion recognition in squaramide-based receptors, the absence of steric repulsion and the presence of attractive forces between amide NH groups in squaramide, unlike in urea and thiourea receptors, significantly enhances anion-binding ability. Although solvation energy becomes less favorable from urea to squaramide, negative gas-phase Gibbs free energy drives complex formation. The accuracy of computational results is validated by excellent correlation between experimental and calculated formation constants.

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.