过渡金属对层状杂化金属卤化物(CH3CH2NH3)2[MCl4] (M = Mn和Co)结构和有序-无序相变的影响

IF 1.3 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Shatakshi S Jakhi, Meenal Dhanetwal, V Raghavendra Reddy, Venkatesha R Hathwar
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引用次数: 0

摘要

采用慢蒸发法制备了层状杂化有机-无机金属卤化物(CH3CH2NH3)2[MnCl4]和(CH3CH2NH3)2[CoCl4],研究了晶体结构与有序-无序相变之间的关系。量热数据和跨越相变温度的晶体结构测定确定了有序-无序相变。(CH3CH2NH3)2[MnCl4]在212/222 K(冷却/加热)下经历了从四方I4/mmm到正交Pbca的可逆结构相变,而(CH3CH2NH3)2CoCl4在220/239 K下经历了从正交Pnma到正交P212121的可逆结构相变。这两种化合物在高于相变温度的结构中都是无序的乙基铵阳离子,而在低于相变温度的结构中则变成有序的阳离子。介电结果进一步支持观察到的结构相变。此外,磁测量表明(CH3CH2NH3)2[MnCl4]具有倾斜的反铁磁性,(CH3CH2NH3)2[CoCl4]具有顺磁性。利用Hirshfeld表面分析和电子密度分布的拓扑性质评价了结构差异、分子间相互作用的作用以及过渡金属对相变的影响。准确描述其结构和分子间相互作用对于理解其物理性质和设计多功能杂化有机-无机金属卤化物钙钛矿具有重要意义。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Effect of the transition metal on the structure and order-disorder phase transition in layered hybrid metal halides (CH3CH2NH3)2[MCl4] (M = Mn and Co).

Layered hybrid organic-inorganic metal halides (CH3CH2NH3)2[MnCl4] and (CH3CH2NH3)2[CoCl4] were synthesized by the slow evaporation method to understand the relationship between the crystal structure and order-disorder phase transition. Calorimetric data and crystal structure determination across the phase transition temperature establish the order-disorder phase transition. (CH3CH2NH3)2[MnCl4] undergoes the reversible structural phase transition from tetragonal I4/mmm to orthorhombic Pbca at 212/222 K (cooling/heating), whereas (CH3CH2NH3)2CoCl4 demonstrates the phase transition at 220/239 K from orthorhombic Pnma to orthorhombic P212121. Both compounds are characterized by disordered ethyl ammonium cations in the structure above the phase transition temperature, whereas they become ordered cations at temperatures below the phase transition. Dielectric results further support the observed structural phase transitions. Additionally, magnetic measurements show canted antiferromagnetic characteristics for (CH3CH2NH3)2[MnCl4] and paramagnetic behaviour is observed for (CH3CH2NH3)2[CoCl4]. The structural differences, the role of intermolecular interactions and the effect of transition metals on the phase transition were evaluated using Hirshfeld surface analysis and the topological properties of electron density distributions. An accurate description of the structure and intermolecular interactions is crucial for understanding the physical properties and designing multifunctional hybrid organic-inorganic metal halide perovskites.

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来源期刊
Acta crystallographica Section B, Structural science, crystal engineering and materials
Acta crystallographica Section B, Structural science, crystal engineering and materials CHEMISTRY, MULTIDISCIPLINARYCRYSTALLOGRAPH-CRYSTALLOGRAPHY
CiteScore
3.60
自引率
5.30%
发文量
0
期刊介绍: Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.
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