Dynamics of fluorinated imide-based ionic liquids using nuclear magnetic resonance techniques†

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Physical Chemistry Chemical Physics Pub Date : 2025-01-13 DOI:10.1039/D4CP03166K
Tawhid Pranto, Carla C. Fraenza, Frederik Philippi, Daniel Rauber, Christopher W. M. Kay, Tom Welton, Steven G. Greenbaum and Sophia Suarez
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Abstract

There is increasing interest in studying molecular motions in ionic liquids to gain better insights into their transport properties and to expand their applications. In this study, we have employed the fast field cycling relaxometry and pulsed field gradient nuclear magnetic resonance techniques to investigate the rotational and translational dynamics of fluorinated imide-based ionic liquids (ILs) at different temperatures. We have studied a total of six ILs composed of the 1-butyl-3-methylimidazolium cation ([BMIM]+) combined with chemically modified analogs of the bis((trifluoromethyl)sulfonyl)imide anion ([NTf2] or [TFSI]). The primary objective of this paper is to broaden the understanding of how the anion's conformational flexibility, fluorination, and mass affect the molecular dynamics of cations and anions. Our results indicate that flexibility has the most significant impact on the rotational and translational motions of ions. Meanwhile, the effect of fluorination and mass is only relevant when conformational flexibility does not change significantly between the ILs being compared.

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核磁共振技术研究氟化亚胺基离子液体动力学
人们对离子液体分子运动的研究越来越感兴趣,以便更好地了解它们的输运性质并扩大它们的应用。在这项研究中,我们采用快速场循环弛豫测量和脉冲场梯度核磁共振技术研究了氟化亚胺基离子液体(ILs)在不同温度下的旋转和平动动力学。我们总共研究了6种由1-丁基-3-甲基咪唑阳离子([BMIM]+)与双((三氟甲基)磺酰)亚胺阴离子([NTf2]−或[TFSI]−)的化学修饰类似物组成的il。本文的主要目的是扩大对阴离子的构象灵活性,氟化和质量如何影响阳离子和阴离子的分子动力学的理解。我们的研究结果表明,柔性对离子的旋转和平移运动有最显著的影响。同时,氟化和质量的影响只有在被比较的离子之间构象柔韧性没有显著变化时才有意义。
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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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