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Solvent dependence of crystal structure and dielectric relaxation in ferromagnetic [MnCr(oxalate)3]− salt
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-06-23 , DOI: 10.1039/d2dt01615j Jia-Bing Wu 1 , Rui-Kang Huang 1, 2 , Kiyonori Takahashi 1, 2 , Takayoshi Nakamura 1, 2
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-06-23 , DOI: 10.1039/d2dt01615j Jia-Bing Wu 1 , Rui-Kang Huang 1, 2 , Kiyonori Takahashi 1, 2 , Takayoshi Nakamura 1, 2
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[MnCr(oxalate)3]− possesses a two-dimensional ferromagnetic network that is an ideal system for the construction of multifunctional molecular materials based on ferromagnetism. This is because additional functions, such as ferroelectricity, can be hybridised by incorporating functional cations between the layers. However, the majority of [MnCr(oxalate)3]− networks readily incorporate solvent molecules upon crystallisation, and it is sometimes difficult to measure the crystal physical properties because of the collapse associated with desolvation. Upon desolvation, the polar crystal (CBA+)([18]crown-6)[MnCr(oxalate)3]−(CH3OH) (1·CH3OH) (CBA+ = 4-carboxybutan-1-aminium) underwent a crystal-to-crystal transformation to form (CBA+)([18]crown-6)[MnCr(oxalate)3]−, 1. Furthermore, this change was accompanied by hydrogen bond reorganisation in the (CBA+)([18]crown-6) supramolecular assembly. Both crystals exhibited ferromagnetic ordering at approximately 5 K. In crystal 1, a “merry-go-round” motion of [18]crown-6 was observed, with an activation energy of 41.41 kJ mol−1, which resulted in dielectric relaxation. This crystal-to-crystal structural transformation provides a strategy for designing multifunctional hybrid materials, in which an additional function arises from molecular motion.
中文翻译：
铁磁 [MnCr(oxalate)3]− 盐中晶体结构和介电弛豫的溶剂依赖性
[MnCr(oxalate) 3 ] -具有二维铁磁网络，是构建基于铁磁性的多功能分子材料的理想系统。这是因为额外的功能，例如铁电性，可以通过在层之间引入功能性阳离子来混合。然而，大多数[MnCr(oxalate) 3 ] -网络在结晶时很容易结合溶剂分子，并且有时由于与去溶剂化相关的坍塌而难以测量晶体的物理性质。去溶剂化后，极性晶体 (CBA + )([18]crown-6)[MnCr(oxalate) 3 ] - (CH 3 OH) (1 ·CH 3 OH) (CBA + = 4-carboxybutan-1-aminium) 经历晶体到晶体的转变形成 (CBA + )([18]crown-6)[MnCr(oxalate) 3 ] - , 1 . 此外，这种变化伴随着(CBA + )([18]crown-6)超分子组装体中的氢键重组。两种晶体在大约 5 K 时都表现出铁磁有序性。在晶体1中，观察到 [18]crown-6 的“旋转木马”运动，活化能为 41.41 kJ mol -1，这导致介电弛豫。这种晶体到晶体的结构转变为设计多功能杂化材料提供了一种策略，其中分子运动产生了额外的功能。
更新日期：2022-06-23
中文翻译：
铁磁 [MnCr(oxalate)3]− 盐中晶体结构和介电弛豫的溶剂依赖性
[MnCr(oxalate) 3 ] -具有二维铁磁网络，是构建基于铁磁性的多功能分子材料的理想系统。这是因为额外的功能，例如铁电性，可以通过在层之间引入功能性阳离子来混合。然而，大多数[MnCr(oxalate) 3 ] -网络在结晶时很容易结合溶剂分子，并且有时由于与去溶剂化相关的坍塌而难以测量晶体的物理性质。去溶剂化后，极性晶体 (CBA + )([18]crown-6)[MnCr(oxalate) 3 ] - (CH 3 OH) (1 ·CH 3 OH) (CBA + = 4-carboxybutan-1-aminium) 经历晶体到晶体的转变形成 (CBA + )([18]crown-6)[MnCr(oxalate) 3 ] - , 1 . 此外，这种变化伴随着(CBA + )([18]crown-6)超分子组装体中的氢键重组。两种晶体在大约 5 K 时都表现出铁磁有序性。在晶体1中，观察到 [18]crown-6 的“旋转木马”运动，活化能为 41.41 kJ mol -1，这导致介电弛豫。这种晶体到晶体的结构转变为设计多功能杂化材料提供了一种策略，其中分子运动产生了额外的功能。
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