Li Ning-Fang, Wang Qin, Li Jia-Nian, Yu Ya-Ting, Xu Yan
College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, P. R. China.
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China.
Inorg Chem. 2022 May 9;61(18):7180-7187. doi: 10.1021/acs.inorgchem.2c00802. Epub 2022 Apr 27.
Assembling and studying high-nuclearity 3d-4f metal clusters represent a pregnant and challenging research hotspot. Based on anionic template and ligand-controlled hydrolytic methods, two heterometallic metal clusters, formulated as [GdNi(DTA)(CO)(CHCOO)(SiO)(CHCHOH)(μ-OH)(μ-OH)(HO)]·Cl·30HO and [EuNi(DTA)(CO)(CHCOO)(SiO)(CHCHOH)(μ-OH)(μ-OH)(HO)]·Cl·46HO (abbreviated as , , HDTA = thiodiglycolic acid), are successfully obtained, which both feature similar double-shell-shaped structures with a building unit encapsulating a aggregation. The structural analysis illustrates that the SiO anion, serving as the anionic template in this work, is reported for the second time in 3d-4f metal clusters. In terms of the magnetic properties, large amounts of Gd and Ni ions contribute to the MCE of compound , along with 38.15 J kg K at Δ = 7.0 T for 2.0 K. It is worth mentioning that compound exhibits an excellent magnetic entropy change at low fields (-Δ = 19.10 J kg K at 2.0 K for Δ = 2.0 T). In addition, exhibits preferable solvent and thermal stability.
组装和研究高核3d-4f金属簇是一个富有潜力且具有挑战性的研究热点。基于阴离子模板和配体控制的水解方法，成功获得了两个异金属金属簇，其化学式分别为[GdNi(DTA)(CO)(CHCOO)(SiO)(CHCHOH)(μ-OH)(μ-OH)(HO)]·Cl·30HO和[EuNi(DTA)(CO)(CHCOO)(SiO)(CHCHOH)(μ-OH)(μ-OH)(HO)]·Cl·46HO（简称为，，HDTA = 硫代二乙醇酸），它们都具有相似的双壳状结构，其中一个构建单元包裹着一个聚集体。结构分析表明，SiO阴离子作为本工作中的阴离子模板，在3d-4f金属簇中是第二次被报道。在磁性能方面，大量的Gd和Ni离子对化合物的磁热效应有贡献，在2.0 K时，Δ = 7.0 T时的磁热效应为38.15 J kg K。值得一提的是，化合物在低场下表现出优异的磁熵变（在2.0 K时，Δ = 2.0 T时，-Δ = 19.10 J kg K）。此外，表现出较好的溶剂稳定性和热稳定性。
