Assembly of Dy(60) and Dy(30) 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 [Dy(60)(H(2)L(1))(24)(OAc)(71)(O)(5)(OH)(3)(H(2)O)(27)]·6H(2)O·6CH(3)OH·7CH(3)CN (Dy(60)) by using a multidentate chelate-coordinated diacylhydrazone ligand. Two Dy(30) cages are included in the Dy(60) structure, which are connected via an OAc(−) moiety. The core of Dy(60) is composed of 8 triangular Dy(3) and 12-fold linear Dy(3) units. We further change the alkali added in the reaction system and successfully obtain a single cage-shaped cluster [Dy(30)(H(2)L(1))(12)(OAc)(36)(OH)(4)(H(2)O)(12)]·2OH·10H(2)O·12CH(3)OH·13CH(3)CN (Dy(30)) with a perfect spherical cavity, which could be considered an intermediate in Dy(60) formation. Time-dependent, high-resolution electrospray ionization mass spectrometry (HRESI-MS) is used to track the formation of Dy(60). A possible self-assembly mechanism is proposed. We track the formation of Dy(30) and the six intermediate fragments are screened.