探索双(4-硝基苯基)方酰胺与卤化阴离子的主客体相互作用:气相和溶液中的计算研究

IF 1.6 4区 化学 Q4 CHEMISTRY, PHYSICAL
Yasin Gholiee
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引用次数: 0

摘要

本研究报告对中性双(4-硝基苯基)方酰胺(SQ)和卤化物阴离子的主-客复合物进行了计算研究。在气相中,计算得出的相互作用能和稳定能表明,从氟化物到碘化物,SQ 与阴离子的内在亲和力不断减弱。研究人员利用天然键轨道(NBO)、分子中原子量子理论(QTAIM)以及化学价的能量分解分析--天然轨道(EDA-NOCV)对相互作用的性质进行了研究。虽然静电相互作用约占总量的 60%,但 EDA-NOCV 分析表明,从(\left[{\text{SQ}} \cdots {\text{I}} \right]^{ - }\ )到(\left[{\text{SQ}} \cdots {\text{F}} \right]^{ - }\ )复合物的轨道相互作用的贡献越来越大。在溶液中,热力学循环分析和吉布斯自由能计算表明,考虑到溶解能对整体稳定性的影响,形成(\left[ {{\text{SQ}} \cdots {\text{F}} \right]^{ - }\ )复合物的倾向性更大。在气相和溶液中观察到的选择性的一致趋势表明,溶解能的变化不会对复合物的稳定性产生显著影响。此外,计算得出的形成常数与实验得出的形成常数之间存在显著的相关性,这也为研究结果提供了支持。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Exploring host–guest interactions of bis(4-nitrophenyl)squaramide with halide anions: a computational investigation in the gas-phase and solution

Exploring host–guest interactions of bis(4-nitrophenyl)squaramide with halide anions: a computational investigation in the gas-phase and solution

A computational study on the host–guest complexes of neutral bis(4-nitrophenyl)squaramide (SQ) and halide anions is reported. In the gas-phase, the calculated interaction and stabilization energies indicates a diminishing intrinsic affinity of SQ for anions from fluoride to iodide. The nature of interactions is investigated using Natural Bond Orbital (NBO), Quantum Theory of Atoms in Molecules (QTAIM) along with Energy Decomposition Analysis-Natural Orbitals for Chemical Valence (EDA-NOCV). While electrostatic interactions account for roughly 60% of the total, EDA-NOCV analysis demonstrated increasing contributions of orbital interactions from \(\left[ {{\text{SQ}} \cdots {\text{I}}} \right]^{ - }\) to \(\left[ {{\text{SQ}} \cdots {\text{F}}} \right]^{ - }\) complexes. In solution, thermodynamic cycle analyses and Gibbs free energy calculations reveal a propensity towards the formation of \(\left[ {{\text{SQ}} \cdots {\text{F}}} \right]^{ - }\), taking into account the influence of solvation energies on the overall stability. The consistent trend observed in selectivity both in the gas phase and in solution suggests that changes in solvation energy do not significantly impact the stability of complexes. The findings were additionally supported by a significant correlation observed between the computed and experimental formation constants.

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来源期刊
Theoretical Chemistry Accounts
Theoretical Chemistry Accounts 化学-物理化学
CiteScore
3.40
自引率
0.00%
发文量
74
审稿时长
3.8 months
期刊介绍: TCA publishes papers in all fields of theoretical chemistry, computational chemistry, and modeling. Fundamental studies as well as applications are included in the scope. In many cases, theorists and computational chemists have special concerns which reach either across the vertical borders of the special disciplines in chemistry or else across the horizontal borders of structure, spectra, synthesis, and dynamics. TCA is especially interested in papers that impact upon multiple chemical disciplines.
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