Assembly of Bis-/Single Cage-shaped Dysprosium Nanoclusters (Dy60/Dy30)

Because of the rapid kinetics, the complex and diverse reaction intermediates and the unusual difficulty in screening lead to a huge challenge in the study of the assembly mechanism of high-nuclear lanthanide clusters.

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In recent years, our group used HRESI-MS to track the formation of several lanthanide clusters and proposed their assembly mechanism. For example, the assembly mechanism of Dy-exclusive clusters Dy3, Dy4, Dy10, and Dy12 was proposed.[1-5] 

In our latest paper, we synthesized a double-cage dysprosium cluster Dy60 by using a multidentate chelate-coordinated diacylhydrazone ligand under solvothermal conditions. Two Dy30 cages were included in the Dy60 structure, and the above two cages were connected via OAc-. The core of Dy60 was composed of eight triangular Dy3 and twelve fold linear Dy3 units. We further changed the alkali added in the reaction system and successfully obtained a single caged-shaped cluster Dy30, which could be considered an intermediate in Dy60 formation. Time-dependent, high-resolution electrospray ionization mass spectrometry (HRESI-MS) was used to track the formation of double-cage dysprosium cluster Dy60. Seven intermediate fragments were screened and further combined with the changing trend of intermediate fragments in different time periods. The possible self-assembly mechanism was proposed as follows: H6L1→DyL1→Dy2L1→Dy3L1→Dy4L1→Dy5(L1)2→Dy30(L1)12→Dy60(L1)24. We tracked the formation of Dy30, and the six intermediate fragments were screened. We proposed the following possible assembly mechanism: H6L1→DyL1→Dy2L1→Dy3L1→Dy4L1→Dy5(L1)2→Dy30(L1)12. The assembly mechanism of Dy30 further verified the formation of Dy60. To our knowledge, this work is the first to use HRESI-MS for tracking the formation of cage-shaped Ln(III) clusters. This work provided a set of methods to study the formation tracking and assembly mechanism of high-nuclear lanthanide clusters. It also lays the foundation for the further design and manipulation of high-nuclear lanthanide clusters.


For the details, check out our article "Assembly of Bis-/Single Cage-shaped Dysprosium Nanoclusters (Dy60/Dy30)" in Communications Chemistry!

  • Zhu, Z.-H. et al. A triangular Dy3 single-molecule toroic with high inversion energy barrier: magnetic properties and multiple-step assembly mechanism. Inorg. Chem. Front. 5, 3155–3162 (2018).
  • Wang, H.-L. et al. Tracking the Stepwise Formation of the Dysprosium Cluster (Dy10) with Multiple Relaxation Behavior. Inorg. Chem. 58, 9169–9174 (2019).
  • Ma, X.-F. et al. Formation of nanocluster {Dy12} containing Dy-exclusive vertex-sharing [Dy4(μ3-OH)4] cubanes via simultaneous multitemplate guided and step-by-step assembly. Dalton Trans. 48, 11338–11344 (2019).
  • Wang, H.-L. et al. Step-by-Step and Competitive Assembly of Two Dy(III) Single-Molecule Magnets with Their Performance Tuned by Schiff Base Ligands. Cryst. Growth Des. 19, 5369–5375 (2019).
  • Mo, K.-Q. et al. Tracking the Multistep Formation of Ln(III) Complexes with in situ Schif Base Exchange Reaction and its Highly Selective Sensing of Dichloromethane. Sci. Rep. 9, 12231–12237 (2019).
Go to the profile of Zhong-Hong Zhu

Zhong-Hong Zhu

Ph.D, Guangxi Normal University

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