Consideration on crystal growth, crystal structure, and molecular dynamics of [NH2(CH3)2]2ZnCl4 crystals

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics Pub Date : 2025-04-25 DOI:10.1016/j.chemphys.2025.112746

Ae Ran Lim

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引用次数: 0

Abstract

The physical properties of the eco-friendly organic–inorganic perovskite-type A₂MeX₄ crystal are crucial for its potential application. [NH₂(CH₃)₂]₂ZnCl₄ single crystals were obtained and no phase transition temperature existed before melting. This material also exhibits excellent thermal stability up to 500 K. The ¹H nuclear magnetic resonance (NMR) chemical shifts of CH₃ remain nearly constant with increasing temperature, whereas the ¹H NMR chemical shifts of NH₂ increase due to changes in the hydrogen bond NH⋯Cl; this is related to the changes in the Cl surrounding the Zn in the ZnCl₄ anion. At elevated temperatures, the reduction in line width is ascribed to the enhanced internal molecular motion, with both ¹H and ¹³C molecular motions becoming increasingly active as the temperature rises. The high activation energy values for ¹H and ¹³C are nearly the same; the [NH₂(CH₃)₂]⁺ groups undergoes a tumbling motion as a whole cation.

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[NH2(CH3)2]2ZnCl4晶体生长、结构及分子动力学研究

生态友好型有机-无机钙钛矿型A2MeX4晶体的物理性质对其潜在的应用至关重要。得到[NH2(CH3)2]2ZnCl4单晶，熔化前不存在相变温度。这种材料也表现出优异的热稳定性高达500k。随着温度的升高，CH3的1H核磁共振（NMR）化学位移几乎保持不变，而NH2的1H核磁共振化学位移由于氢键NH⋯Cl的变化而增加；这与ZnCl4阴离子中Zn周围Cl的变化有关。在高温下，线宽的减小归因于内部分子运动的增强，随着温度的升高，1H和13C分子运动变得越来越活跃。1H和13C的高活化能值几乎相同；[NH2(CH3)2]+基团作为一个整体进行翻滚运动。

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

Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

4.60

自引率

4.30%

发文量

278

审稿时长

39 days

期刊介绍： Chemical Physics publishes experimental and theoretical papers on all aspects of chemical physics. In this journal, experiments are related to theory, and in turn theoretical papers are related to present or future experiments. Subjects covered include: spectroscopy and molecular structure, interacting systems, relaxation phenomena, biological systems, materials, fundamental problems in molecular reactivity, molecular quantum theory and statistical mechanics. Computational chemistry studies of routine character are not appropriate for this journal.