Li Yun-Lan, Wang Hai-Ling, Zhu Zhong-Hong, Li Juan, Zou Hua-Hong, Liang Fu-Pei
School of Chemistry and Pharmaceutical Sciences, State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Guangxi Normal University, Guilin 541004, P. R. China.
State Key Laboratory of Luminescent Materials and Devices, School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, P. R. China.
Inorg Chem. 2021 Nov 1;60(21):16794-16802. doi: 10.1021/acs.inorgchem.1c02667. Epub 2021 Oct 20.
The serialized expansion of high-nuclear clusters usually includes the controlled variable method and changes only a single variable. However, changing both variables will greatly increase the complexity of the reaction simultaneously. Therefore, the use of a two-component regulation reaction is rare. Herein, we used a diacylhydrazone ligand (HL) with multidentate chelating coordination sites for the reaction with Gd(NO)·6HO under solvothermal conditions to obtain an example of 16-nucleus disc-shaped cluster with a brucite structure. The overall structure of cluster can be regarded as an equilateral triangle, which is formed by three (L) ions that can be regarded as "sides" and wrap the four-layer metal center Gd(III) ions. Notably, upon simultaneous regulation of the substituent of the ligand and the coordination anion, heptanuclear gadolinium cluster was obtained. Cluster can be regarded as a butterfly structure, which was formed by connecting two GdL molecules that were not in the same plane and through the central Gd(III) ion as an intersection. Moreover, hexanuclear gadolinium cluster was obtained by changing the ligand substituent and adding an auxiliary ligand. Cluster can be regarded as a chair structure, which was composed of two molecules of diacylhydrazone ligand (L) wrapping vacant cubane shared by four vertices. This study was the first to construct a series of high-nuclear gadolinium clusters through two-component regulation manipulation. The study of the magnetocaloric effect showed that the maximum values of -Δ for clusters were 34.05, 29.04, and 24.32 J kg K, respectively, when = 2 K and Δ = 7 T.
高核簇的序列化扩展通常包括控制变量法，且仅改变单个变量。然而，同时改变两个变量会极大地增加反应的复杂性。因此，使用双组分调控反应的情况很少见。在此，我们使用具有多齿螯合配位位点的二酰腙配体（HL）在溶剂热条件下与Gd(NO)·6HO反应，得到了一个具有水镁石结构的16核盘状簇的例子。簇的整体结构可视为一个等边三角形，它由三个可视为“边”的（L）离子形成，并包裹着四层金属中心Gd(III)离子。值得注意的是，在同时调控配体的取代基和配位阴离子时，得到了七核钆簇。簇可视为一个蝴蝶结构，它是由连接两个不在同一平面的GdL分子并通过中心Gd(III)离子作为交点形成的。此外，通过改变配体取代基并添加辅助配体得到了六核钆簇。簇可视为一个椅子结构，它由两个二酰腙配体（L）分子包裹由四个顶点共享的空立方烷组成。本研究首次通过双组分调控操作构建了一系列高核钆簇。磁热效应研究表明，当=2 K且Δ=7 T时，簇的-Δ最大值分别为34.05、29.04和24.32 J kg K。
