Solid-State 1H and 13C NMR Studies of New Ionic Plastic-Crystals with Branched Structures: [NEtxMe(3-x)(i-Pr)][BEt(4-y)Mey] (x = 1–3. y = 0, 1.)

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-11-18 DOI:10.1039/d4cp04064c

Katsumi Nagai, Yuuna Okubo, Hisashi Honda

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Abstract

Eight salts of [NEt_xMe_(3-x)(i-Pr)][BEt_(4-y)Me_y] (x = 1–3. y = 0, 1.) were prepared to reduce Coulombic interactions in the crystals. These novel ionic plastic crystals exhibited low activation energies for isotropic rotational motion (E_{a rot}) and ion diffusion (E_{a diff}). The lattice constant a in the cubic structure indexed to a CsCl-type was larger than that of the corresponding plastic crystals of [NEt_xMe_(4-x)][BEt_(4-y)Me_y] (nonbranched sample). Solid-state ₁H and ₁₃C nuclear magnetic resonance (NMR) spectra of the salts revealed that both cations and anions undergo isotropic reorientation motions in the plastic crystalline phase. This result is consistent with the differential scanning calorimetry data, which showed that the compounds have large entropy changes at the transition temperature between the ordinal and plastic crystalline phases, except for [NEt₂Me(i-Pr)][BEt₃Me] and [NEt₃(i-Pr)][BEt₃Me].. The E_{a rot}and E_{a diff} values were estimated using ₁H NMR spin-lattice relaxation time (T₁) and electrical conductivity measurements, respectively.

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具有支化结构的新型离子塑性晶体的固态 1H 和 13C NMR 研究：[NEtxMe(3-x)(i-Pr)][BEt(4-y)Mey] (x = 1-3. y = 0, 1.)

制备了八种[NEtxMe(3-x)(i-Pr)][BEt(4-y)Mey]盐（x = 1-3.y = 0，1.），以减少晶体中的库仑相互作用。这些新型离子塑性晶体的各向同性旋转运动活化能（Ea rot）和离子扩散活化能（Ea diff）都很低。CsCl 型立方结构的晶格常数 a 比 [NEtxMe(4-x)][BEt(4-y)Mey] 的相应塑性晶体（非支化样品）的晶格常数 a 大。这些盐的固态 1H 和 13C 核磁共振（NMR）光谱显示，阳离子和阴离子在塑性结晶相中都发生了各向同性的重新定向运动。这一结果与差示扫描量热数据一致，后者显示除了 [NEt2Me(i-Pr)][BEt3Me] 和 [NEt3(i-Pr)][BEt3Me] 外，其他化合物在序晶相和塑性结晶相之间的转变温度下具有较大的熵变。Ea rot 值和 Ea diff 值分别通过 1H NMR 自旋晶格弛豫时间（T1）和电导率测量值估算得出。

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

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.