Wang Qin, Yu Ya-Ting, Wang Ji-Lei, Li Jia-Nian, Li Ning-Fang, Fan Xinrong, 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. 2023 Feb 20;62(7):3162-3169. doi: 10.1021/acs.inorgchem.2c04065. Epub 2023 Feb 3.
The self-assembly of the high-nuclearity Ln-exclusive nanoclusters is challenging but of significance due to its aesthetically pleasing architectures and far-reaching latent applications in magnetic cooling technologies. Herein, two novel high-nuclearity lanthanide nanoclusters were successfully synthesized under solvothermal conditions, formulated as {[Gd(IN)(HCOO)(μ-O)(μ-OH)(HO)]·4HO} and {[Eu(IN)(HCOO)(CHCOO)(μ-O)(μ-OH)(HO)]·5HO} (abbreviated as and , HIN = isonicotinic acid). Both of them possess novel and exquisite windmill-shaped cationic cores in the family of high-nuclearity Ln-exclusive nanoclusters. Remarkably, the adjacent second building units are interconnected into a three-dimensional (3D) metal-organic framework by IN ligands. As expected, the abundant existence of Gd ions endows with a favorable magnetic entropy change at 2.0 K for Δ = 7.0 T (-Δ = 40.0 J kg K), and displays the typical luminescence of Eu ions.
高核纯镧系纳米团簇的自组装具有挑战性，但因其美观的结构以及在磁制冷技术中深远的潜在应用而具有重要意义。在此，在溶剂热条件下成功合成了两种新型高核镧系纳米团簇，其化学式为{[Gd(IN)(HCOO)(μ-O)(μ-OH)(HO)]·4HO}和{[Eu(IN)(HCOO)(CHCOO)(μ-O)(μ-OH)(HO)]·5HO}（简称为 和 ，HIN = 异烟酸）。它们在高核纯镧系纳米团簇家族中均具有新颖且精致的风车形阳离子核。值得注意的是，相邻的二级构筑单元通过IN配体相互连接形成三维（3D）金属有机框架。正如预期的那样，大量Gd离子的存在使 在2.0 K时具有良好的磁熵变，Δ = 7.0 T（-Δ = 40.0 J kg K），并且 表现出Eu离子的典型发光特性。
