Designation and Exploration of Halide–Anion Recognition Based on Cooperative Noncovalent Interactions Including Hydrogen Bonds and Anion−π

Abstract

A novel urea-based anion receptor with an electron-deficient aromatic structural unit, N-p-nitrophenyl-N-(4-vinyl-2-five-fluoro-benzoic acid benzyl ester)-phenyl-urea (FUR), was designed to probe the potential for halide-anion recognition through the cooperation of two distinct noncovalent interactions including hydrogen bonds and anion-π in this work. The nature of the recognition interactions between halide-anion and the designed receptor was theoretically investigated at the molecular level. The geometric features of the hydrogen bond and anion-π of the FUR@X(-) (X = F, Cl, Br, and I) systems were thoroughly investigated. The binding energies and thermodynamic information on the halide-anion recognitions show that the presently designed FUR might selectively recognize anion F(-) based on the cooperation of the N-H···F(-) hydrogen bond and anion-π interactions both in vacuum and in solvents. IR and UV-visible spectra of free FUR and FUR@F(-) have been simulated and discussed qualitatively, which may be helpful for further experimental investigations in the future. Additionally, the electronic properties and behaviors of the FUR@X(-) systems were discussed according to the calculations on the natural bond orbital (NBO) data, molecular electrostatic potential (MEP), and weak interaction regions.

Solvent and Substituent Effects on the Phosphine + CO2 Reaction

“…The general solvent effects consider the solvent as bulk and are studied empirically using solvent scales (Kamlet et al [4], Reichardt [5], Abraham [6], Catalán [7]), as well as theoretically using the polarizable continuum model, PCM (Tomasi et al [8]), the conductor-like screening model, COSMO (Orozco and Luque [9]), and Density Functional Solvation Model, DGSOL (Zhu et al [10]). Note that several authors have studied solvent effects on weak interactions using the PCM approximation [11][12][13][14][15][16].…”

Copper(II) Complex of a Urea‐functionalized Pyridyl Ligand: Synthesis, Crystal Structure, and Acetate Binding Properties

“…The binding, recognition, and self‐assembly of anions has become a fascinating aspect of supramolecular chemistry due to the importance of the anions such as oxyanions and halide anions in physiology, biology and environment . Thus, in recent years, the design and synthesis of simple receptors that can bind anions specifically is the forceful chemical research subject .…”

Four faces of the interaction between ions and aromatic rings

“…The tunable physico‐chemical properties of these ion−aromatic‐ring (IAR) interactions have been exploited in the fields of drug design, protein engineering, and host‐guest chemistry . The IAR interactions offer improved selectivity, in some cases involving cooperative effects, which can facilitate the design of artificial ion transporters and sensors …”