Plasma-Enhanced Magnetic Transition in 3D MnII–NbIV Octacyanidometalate Magnetic Sponge

IF 6.4 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers Pub Date : 2025-08-27 DOI:10.1039/d5qi01246e

Dominik Czernia, Marcin Perzanowski, Wojciech Sas, Beata Nowicka, Dawid Pinkowicz, Alexey Maximenko, Piotr Konieczny

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Abstract

A new magnetic phase with Curie temperature of T_C = 72 K is obtained by exposing a three-dimensional {[Mn^II(H₂O)₂]₂[Nb^IV(CN)₈]⋅4H₂O}_n coordination ferrimagnet (T_C = 49 K) to air, oxygen, nitrogen, and argon-based plasma. The X-ray powder diffraction and X-ray absorption spectroscopy reveal that the unit cell slightly contracts after plasma treatment. Shortening the distance between the magnetic ions results in a 20% enhancement of the superexchange couplings, as estimated by the mean-field approximation model. To explain how plasma modifies the magnetic properties of the studied system, several attempts with heating, UV exposure, and dehydration are used to reproduce the same post-plasma magnetic phase. However, none of them are successful. Samples subjected to heat and UV show partial decomposition of the original compound, while the dehydrated material undergoes a major structural reorganization. Ultimately, the observed changes are attributed to the removal of crystallization water molecules, which apparently could only be achieved through plasma treatment.

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三维mni - nbiv八氰金属酸盐磁性海绵的等离子体增强磁跃迁

将三维{[MnII(H2O)2]2[NbIV(CN)8]⋅4H2O}n配位铁磁体（TC = 49 K）暴露于空气、氧、氮和氩基等离子体中，得到了居里温度为TC = 72 K的新磁相。x射线粉末衍射和x射线吸收光谱显示，等离子体处理后的单位细胞略有收缩。根据平均场近似模型估计，缩短磁性离子之间的距离可使超交换耦合增强20%。为了解释等离子体如何改变所研究系统的磁性，使用了加热、紫外线暴露和脱水等几种方法来重现相同的后等离子体磁相。然而，没有一个是成功的。样品经过高温和紫外线处理后，原始化合物部分分解，而脱水后的物质发生了主要的结构重组。最终，观察到的变化归因于结晶水分子的去除，这显然只能通过等离子体处理来实现。

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