Lu Huangjie, Diefenbach Kariem, Li Zi-Jian, Bao Hongliang, Guo Xiaofeng, Wang Jian-Qiang, Albrecht-Schmitt Thomas E, Lin Jian
Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, 2019 Jia Luo Road, Shanghai 201800, People's Republic of China.
University of Chinese Academy of Sciences, No. 19(A) Yuquan Road, Shijingshan District, Beijing 100049, People's Republic of China.
Inorg Chem. 2020 Sep 21;59(18):13398-13406. doi: 10.1021/acs.inorgchem.0c01765. Epub 2020 Jul 29.
The synthesis of a large family of heterobimetallic lanthanide copper sulfates was realized via stoichiometric hydrothermal reactions among LnO, CuO, and HSO, giving rise to four distinct phases, namely LnCu(SO)(OH) (Ln = Sm-Ho) (), LnCu(SO)(OH) (Ln = Tm-Lu) (), LnCu(SO)(OH) (Ln = Nd-Gd, except Pm) (), and LnCu(SO)(OH) (Ln = Dy-Lu) (), with completely different topologies. The passage from and to and across the 4f series, respectively, can be ascribed to the effect of lanthanide contraction, which progressively induces shrinking of the Ln-O distance, reduction in the Ln coordination number, and eventually structural transitions. The incorporation of identical 3d-4f metal ions into different spin-lattices, in conjunction with substitution of diverse Ln cations within the same spin-lattice, gives rise to tunable magnetic properties varying from ferromagnetic ordering in and to antiferromagnetic ordering in , and to paramagnetic correlations found in and .
通过氧化镧（LnO）、氧化铜（CuO）和硫酸（H₂SO₄）之间的化学计量水热反应，实现了一大类异双金属镧系铜硫酸盐的合成，产生了四个不同的相，即LnCu(SO₄)(OH)（Ln = Sm - Ho）（）、LnCu(SO₄)(OH)（Ln = Tm - Lu）（）、LnCu(SO₄)(OH)（Ln = Nd - Gd，除Pm外）（）和LnCu(SO₄)(OH)（Ln = Dy - Lu）（），它们具有完全不同的拓扑结构。分别从4f系列中的 和 到 和 的转变可归因于镧系收缩效应，该效应逐渐导致Ln - O距离缩短、Ln配位数减少，并最终导致结构转变。将相同的3d - 4f金属离子掺入不同的自旋晶格中，以及在同一自旋晶格中取代不同的Ln阳离子，产生了可调节的磁性，从 和 中的铁磁有序到 中的反铁磁有序，以及在 和 中发现的顺磁相关性。
