Giant Crown-Shaped Dy34 Nanocluster with High Acid-Base Stability Assembled by an out-to-in Growth Mechanism

作者：Li, Yun-Lan; Wang, Hai-Ling; Zhu, Zhong-Hong^*; Liang, Fu-Pei^*; Zou, Hua-Hong^*

来源：Inorganic Chemistry, 2022, 61(26): 10101-10107.

DOI：10.1021/acs.inorgchem.2c01175

• LANTHANIDE CLUSTERS
• MAGNETS
• SERIES

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 (H2L1) with multidentate chelating coordination sites was used to react with Dy(OAc)(3)center dot 4H(2)O under solvothermal conditions to obtain an example of a 34-nucleus crown-shaped dysprosium cluster [Dy-34(L)(8)(mu(2)-OH)(mu(3)-OH)(21)(mu(3)-O)(14)(OAc)(31)(OCH3)(2)(H2O)(15)](OAc)(3) (1). Structural analysis showed that the bisacylhydrazone ligand H2L1 with polydentate chelate coordination sites could rapidly capture Dy-III ions, thereby forming 34-nucleus crown-shaped dysprosium cluster 1 following the out-to-in growth mechanism. Cluster 1 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 1 were captured, which proved to be stable also in organic solvents. Magnetic research showed that cluster 1 exhibited frequency-dependent behavior. This work provides a new idea for designing and synthesizing high-nucleation lanthanoid clusters with high stability.

• 单位
  桂林理工大学