[1–5] Sigmatropic rearrangement in the confined cavity of self-assembled nanotube under oriented external electric field

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2025-09-26 DOI:10.1016/j.molliq.2025.128607

Misbah Asif , Ahmed Lakhani , Khurshid Ayub

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引用次数: 0

Abstract

Supramolecular nanotubes, such as the belt[12]pyridine nanotube, provide a confined environment that significantly alters the reactivity of organic reactions through nanoconfinement. This study investigates the confinement effects on the 1,5 sigmatropic rearrangement, focusing on the impact of non-bonding interactions between the 1,3 diene and the belt[12]pyridine nanotube. We utilized density functional theory (DFT) to optimize transition states and evaluate activation energies (Ea), which are found to be reduced to 35.64 kcal/mol compared to the unconfined reaction (36.35 kcal/mol). The application of an oriented external electric field (OEEF) further lowered the activation energy to 33.12 kcal/mol, demonstrating the dual influence of confinement and electric fields on reaction dynamics. The study revealed that the interaction distances and bond lengths between reactants and transition states varied significantly within the nanotube cavity, with noncovalent interaction indices indicating enhanced stabilization. QTAIM and NCI analyses confirmed these interactions, reinforcing the concerted mechanism of the reaction as established by the synchronicity (Sy) calculations, which were found to be 0.95, 0.95, and 0.91 for bare, confined without field, and confined with field reactions. Overall, our findings suggest that employing belt[12]pyridine nanotubes can effectively promote the efficiency of organic reactions, opening new avenues for catalytic applications in confined environments.

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[1-5]定向外电场作用下自组装纳米管受限腔内的sig矩阵重排

超分子纳米管，如带[12]吡啶纳米管，提供了一个封闭的环境，通过纳米限制显著改变有机反应的反应性。本文研究了约束对1,5异位重排的影响，重点研究了1,3二烯与带[12]吡啶纳米管之间的非键相互作用的影响。利用密度泛函理论（DFT）对过渡态进行了优化，并对反应的活化能（Ea）进行了计算，发现反应的活化能（Ea）比无约束反应（36.35 kcal/mol）降低了35.64 kcal/mol。定向外电场（OEEF）进一步降低了反应的活化能至33.12 kcal/mol，表明约束和电场对反应动力学的双重影响。研究表明，在纳米管腔内，反应物与过渡态之间的相互作用距离和键长变化显著，非共价相互作用指数表明稳定性增强。QTAIM和NCI分析证实了这些相互作用，加强了由同步性（Sy）计算建立的反应的协调机制，发现裸反应、封闭无场反应和封闭有场反应的同步性分别为0.95、0.95和0.91。综上所述，我们的研究结果表明，使用带[12]吡啶纳米管可以有效地提高有机反应的效率，为在受限环境下的催化应用开辟了新的途径。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.