Topić Edi, Šenjug Pavla, Barišić Dario, Lončarić Ivor, Pajić Damir, Rubčić Mirta
Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, Zagreb 10000, Croatia.
Department of Physics, Faculty of Science, University of Zagreb, Bijenička cesta 32, Zagreb 10000, Croatia.
Cryst Growth Des. 2023 May 9;23(6):4262-4272. doi: 10.1021/acs.cgd.3c00066. eCollection 2023 Jun 7.
Tetrachlorocuprate(II) hybrids of the three anisidine isomers (-, -, and -, or 2-, 3-, and 4-methoxyaniline, respectively) were prepared and studied in the solid state via X-ray diffraction and magnetization measurements. Depending on the position of the methoxy group of the organic cation, and subsequently, the overall cation geometry, a layered, defective layered, and the structure comprising discrete tetrachlorocuprate(II) units were obtained for the -, -, and -anisidinium hybrids, respectively. In the case of layered and defective layered structures, this affords quasi-2D-layered magnets, demonstrating a complex interplay of strong and weak magnetic interactions that lead to the long-range ferromagnetic (FM) order. In the case of the structure with discrete CuCl ions, a peculiar antiferromagnetic (AFM) behavior was revealed. The structural and electronic origins of magnetism are discussed in detail. To supplement it, the method for calculation of dimensionality of the inorganic framework as a function of interaction length was developed. The same was used to discriminate between -dimensional and "almost" -dimensional frameworks, to estimate the organic cation geometry limits for layered halometallates, and to provide additional reasoning behind the observed relation between cation geometry and framework dimensionality, as well as their relation to differences in magnetic behavior.
制备了三种茴香胺异构体（分别为邻、间、对茴香胺，即2-、3-和4-甲氧基苯胺）的四氯铜酸盐（II）杂化物，并通过X射线衍射和磁化测量对其固态进行了研究。根据有机阳离子甲氧基的位置以及随后的整体阳离子几何结构，分别为邻、间、对茴香铵杂化物获得了层状、缺陷层状以及包含离散四氯铜酸盐（II）单元的结构。在层状和缺陷层状结构的情况下，这提供了准二维层状磁体，展示了强磁相互作用和弱磁相互作用之间的复杂相互作用，导致了长程铁磁（FM）有序。在具有离散CuCl离子的结构的情况下，揭示了一种特殊的反铁磁（AFM）行为。详细讨论了磁性的结构和电子起源。为了补充这一点，开发了一种计算无机骨架维度作为相互作用长度函数的方法。该方法用于区分一维和“几乎”一维骨架，估计层状卤金属酸盐的有机阳离子几何结构极限，并为观察到的阳离子几何结构与骨架维度之间的关系以及它们与磁行为差异的关系提供额外的推理。
