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Insight into understanding magnetic transition quite sensitive to nonmagnetic impurity in a one-dimensional S = ½ regular linear chain system
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2022-05-24 , DOI: 10.1039/d2qi00809b Dong-Sheng Shao 1 , Wan-Wan Yao 1 , Jin Zhang 1 , Yin Qian 1 , Xiao-Ming Ren 1, 2, 3
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2022-05-24 , DOI: 10.1039/d2qi00809b Dong-Sheng Shao 1 , Wan-Wan Yao 1 , Jin Zhang 1 , Yin Qian 1 , Xiao-Ming Ren 1, 2, 3
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A series of isomorphic salts [CN-BzPy][CuxNi1−x(mnt)2] (x = 0–1; CN-BzPy+ = 1-(4′-cyanobenzyl)pyridinium, mnt2− = maleonitriledithiolate) were prepared and characterized by microanalysis (C, H and N elements), IR and Raman spectroscopy, TG, and powder X-ray diffraction techniques. All salts crystallize in the monoclinic space group P21/n with similar cell parameters, and both [M(mnt)2]− (M = Ni or Cu) anions and CN-BzPy+ cations form segregated and regular stacks. The thermal stabilities of the salts are enhanced with reducing cell volume in [CN-BzPy][CuxNi1−x(mnt)2] (x = 0–1). Intriguingly, a spin-Peierls-type transition occurs at TC ≈ 191 K in the parent salt [CN-BzPy][Ni(mnt)2]; however, this vanishes in solid solutions even at x = 0.005, indicating that it is quite sensitive to being doped by a nonmagnetic impurity. Both the overlap integral of magnetic orbitals and spin density distribution analyses demonstrate that the antiferromagnetic couplings in a [Ni(mnt)2]− stack are realized mainly through spatial dipole–dipole type interactions between the NiS4 cores of adjacent [Ni(mnt)2]− anions, which are strongly related to the intermolecular Ni⋯Ni, Ni⋯S and S⋯S separations. The functions of the shortest intermolecular Ni⋯Ni, Ni⋯S and S⋯S distances as x changes indicate that a sharp increase occurs in a solid solution even at too low a concentration of nonmagnetic impurity (x = 0.005), suggesting that the spin-Peierls-state collapsing in solid solution is relevant to the sudden increase of intermolecular Ni⋯Ni, Ni⋯S and S⋯S distances between neighboring [Ni(mnt)2]− anions, leading to a rapid alteration of magnetic dipole–dipole interactions.
中文翻译：
深入了解一维 S = ½ 规则线性链系统中对非磁性杂质非常敏感的磁跃迁
一系列同晶盐 [CN-BzPy][Cu x Ni 1− x (mnt) 2 ] ( x = 0–1; CN-BzPy + = 1-(4'-氰基苄基)吡啶鎓, mnt 2- = 马来腈二硫醇盐)通过微量分析（C、H 和 N 元素）、IR 和拉曼光谱、TG 和粉末 X 射线衍射技术制备和表征。所有盐在单斜晶系空间群P 2 1 / n中结晶，具有相似的晶胞参数，[M(mnt) 2 ] - (M = Ni 或 Cu) 阴离子和 CN-BzPy +阳离子形成隔离和规则的堆叠。随着 [CN-BzPy][Cu x Ni 1− x (mnt) 2 ] ( x = 0–1)中电池体积的减小，盐的热稳定性得到增强。有趣的是，在母盐 [CN-BzPy][Ni(mnt) 2 ] 中T C ≈ 191 K时发生自旋-Peierls 型跃迁；然而，即使在x = 0.005 时，这也会在固溶体中消失，这表明它对被非磁性杂质掺杂非常敏感。磁轨道的重叠积分和自旋密度分布分析都表明 [Ni(mnt) 2 ] -堆栈主要通过相邻[Ni(mnt) 2 ] -阴离子的NiS 4核之间的空间偶极-偶极型相互作用实现，这与分子间Ni⋯Ni、Ni⋯S和S⋯S分离密切相关。最短分子间 Ni⋯Ni、Ni⋯S 和 S⋯S 距离随x变化的函数表明，即使在非磁性杂质浓度过低（x = 0.005）的情况下，固溶体中也会发生急剧增加，这表明自旋-固溶体中的Peierls态坍塌与相邻[Ni(mnt) 2 ]之间的分子间Ni⋯Ni、Ni⋯S和S⋯S距离的突然增加有关-阴离子，导致磁偶极 - 偶极相互作用的快速改变。
更新日期：2022-05-24
中文翻译：
深入了解一维 S = ½ 规则线性链系统中对非磁性杂质非常敏感的磁跃迁
一系列同晶盐 [CN-BzPy][Cu x Ni 1− x (mnt) 2 ] ( x = 0–1; CN-BzPy + = 1-(4'-氰基苄基)吡啶鎓, mnt 2- = 马来腈二硫醇盐)通过微量分析（C、H 和 N 元素）、IR 和拉曼光谱、TG 和粉末 X 射线衍射技术制备和表征。所有盐在单斜晶系空间群P 2 1 / n中结晶，具有相似的晶胞参数，[M(mnt) 2 ] - (M = Ni 或 Cu) 阴离子和 CN-BzPy +阳离子形成隔离和规则的堆叠。随着 [CN-BzPy][Cu x Ni 1− x (mnt) 2 ] ( x = 0–1)中电池体积的减小，盐的热稳定性得到增强。有趣的是，在母盐 [CN-BzPy][Ni(mnt) 2 ] 中T C ≈ 191 K时发生自旋-Peierls 型跃迁；然而，即使在x = 0.005 时，这也会在固溶体中消失，这表明它对被非磁性杂质掺杂非常敏感。磁轨道的重叠积分和自旋密度分布分析都表明 [Ni(mnt) 2 ] -堆栈主要通过相邻[Ni(mnt) 2 ] -阴离子的NiS 4核之间的空间偶极-偶极型相互作用实现，这与分子间Ni⋯Ni、Ni⋯S和S⋯S分离密切相关。最短分子间 Ni⋯Ni、Ni⋯S 和 S⋯S 距离随x变化的函数表明，即使在非磁性杂质浓度过低（x = 0.005）的情况下，固溶体中也会发生急剧增加，这表明自旋-固溶体中的Peierls态坍塌与相邻[Ni(mnt) 2 ]之间的分子间Ni⋯Ni、Ni⋯S和S⋯S距离的突然增加有关-阴离子，导致磁偶极 - 偶极相互作用的快速改变。
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