Li Yun-Lan, Wang Hai-Ling, Zhu Zhong-Hong, Liang Fu-Pei, Zou Hua-Hong
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.
Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, P. R. China.
Inorg Chem. 2022 Jul 4;61(26):10101-10107. doi: 10.1021/acs.inorgchem.2c01175. Epub 2022 Jun 16.
Lanthanoid metal ions have large ionic radii, complex coordination modes, and easy distortion of coordination spheres, but the design and synthesis of high-nucleation lanthanoid clusters with high stability in solution (especially aqueous solution) are challenging. Herein, a diacylhydrazone ligand (HL) with multidentate chelating coordination sites was used to react with Dy(OAc)·4HO under solvothermal conditions to obtain an example of a 34-nucleus crown-shaped dysprosium cluster Dy(L)(μ-OH)(μ-OH)(μ-O)(OAc)(OCH)(HO) (). Structural analysis showed that the bisacylhydrazone ligand HL with polydentate chelate coordination sites could rapidly capture Dy ions, thereby forming 34-nucleus crown-shaped dysprosium cluster following the out-to-in growth mechanism. Cluster remained stable after immersion in solutions with different pH values (3-14) for 24 h. To the best of the authors' knowledge, high-nucleation lanthanoid clusters with excellent strong acid and base stability and water stability are very rare. Meanwhile, high-resolution electrospray mass spectrometry molecular ion peaks produced by cluster were captured, which proved to be stable also in organic solvents. Magnetic research showed that cluster exhibited frequency-dependent behavior. This work provides a new idea for designing and synthesizing high-nucleation lanthanoid clusters with high stability.
镧系金属离子具有较大的离子半径、复杂的配位模式以及配位球容易变形的特点，但是设计和合成在溶液（尤其是水溶液）中具有高稳定性的高核镧系簇合物具有挑战性。在此，使用一种具有多齿螯合配位位点的双酰腙配体（HL）在溶剂热条件下与Dy(OAc)·4HO反应，得到一个34核冠状镝簇合物Dy(L)(μ-OH)(μ-OH)(μ-O)(OAc)(OCH)(HO)（）的实例。结构分析表明，具有多齿螯合配位位点的双酰腙配体HL能够快速捕获Dy离子，从而按照由外向内的生长机制形成34核冠状镝簇合物。簇合物在不同pH值（3 - 14）的溶液中浸泡24小时后仍保持稳定。据作者所知，具有优异的强酸、强碱稳定性和水稳定性的高核镧系簇合物非常罕见。同时，捕获了簇合物产生的高分辨率电喷雾质谱分子离子峰，这证明其在有机溶剂中也很稳定。磁性研究表明，簇合物表现出频率依赖性行为。这项工作为设计和合成具有高稳定性的高核镧系簇合物提供了新思路。
