A Single-Ligand-Protected Eu60-nGd(Tb)n Cluster: A Reasonable New Approach to Expand Lanthanide Aggregations

Lanthanide (Ln) high-nuclearity clusters express charming structures and extensive potential applications, nevertheless the progress of successfully obtaining Ln clusters is still untoward. Herein, two fascinating and classical 60-metal configurations were obtained based on mixed-lanthanide and solvothermal conditions, formulated [Ln60(CO3)8(μ3-OH)96(H2dmp)24(Hdmp)12] Br12(NO3)8(CH3OH)x(H2O)y (abbreviated as mixed-Ln60; for compound 1, Ln60 = Eu52.7Gd7.3, x = 8, y = 43; for compound 2, Ln60 = Eu52.2Tb7.8, x = 15, y = 30; H2dmp- or Hdmp2- = 2,2-dimethylol propionic acid = L). Crystallographic study showed that 60-metal core of compounds 1 and 2 are protected by a single type of organic ligand without extra auxiliary ligand to complete the coordination sphere, which are the firstly reported in the containing Ln high-nuclearity clusters. Besides, the synthesis of 1 and 2 provides a practical way to obtain more analogues of Ln high-nuclearity clusters, featuring the original structure of metal frame, which is expected to break the ion radius limit in synthesis.