Series of the Largest Dish-Shaped Dysprosium Nanoclusters Formed by In Situ Reactions.

A three-dimensional supermolecule structure is easily formed due to the diverse coordination modes of high-oxidation-state lanthanide metal ions. However, the design and construction of zero-dimensional (0 D) dish-shaped high-nuclearity lanthanide clusters are difficult. Herein, for the first time, we synthesized a series of the largest dish-shaped high-nuclearity lanthanide nanoclusters ( 1 - 4 ) by in situ tandem reactions under solvothermal one-pot conditions. The formation of 1 and 2 involved an in situ reaction of aldehydes and amines, while the condensation reactions between aldehydes occurred in 3 and 4 . Based on the structural characteristics of the dish-shaped lanthanide clusters, we proposed two possible assembly mechanisms involving Dy ₁ → Dy ₇ → Dy ₁₃ → Dy ₁₉ (planar epitaxial growth mechanism) and Dy ₁ → Dy ₁₂ → Dy ₁₈ → Dy ₁₉ (planar internal growth mechanism).