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!

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  • Wang, H.-L. et al. Tracking the Stepwise Formation of the Dysprosium Cluster (Dy10) with Multiple Relaxation Behavior. Inorg. Chem. 58, 9169–9174 (2019).
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  • 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).

Zhong-Hong Zhu

Ph.D, Guangxi Normal University