Assembly of Dy₆₀ and Dy₃₀ cage-shaped nanoclusters

Rapid kinetics, complex and diverse reaction intermediates, and difficult screening make the study of assembly mechanisms of high-nuclearity lanthanide clusters challenging. Here, we synthesize a double-cage dysprosium cluster [Dy₆₀(H₂L¹)₂₄(OAc)₇₁(O)₅(OH)₃(H₂O)₂₇]·6H₂O·6CH₃OH·7CH₃CN (Dy₆₀) by using a multidentate chelate-coordinated diacylhydrazone ligand. Two Dy₃₀ cages are included in the Dy₆₀ structure, which are connected via an OAc^- moiety. The core of Dy₆₀ is composed of 8 triangular Dy₃ and 12-fold linear Dy₃ units. We further change the alkali added in the reaction system and successfully obtain a single cage-shaped cluster [Dy₃₀(H₂L¹)₁₂(OAc)₃₆(OH)₄(H₂O)₁₂]·2OH·10H₂O·12CH₃OH·13CH₃CN (Dy₃₀) with a perfect spherical cavity, which could be considered an intermediate in Dy₆₀ formation. Time-dependent, high-resolution electrospray ionization mass spectrometry (HRESI-MS) is used to track the formation of Dy₆₀. A possible self-assembly mechanism is proposed. We track the formation of Dy₃₀ and the six intermediate fragments are screened.