A single-ligand-protected Eu60−nGd(Tb)n cluster: a reasonable new approach to expand lanthanide aggregations

Abstract

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, namely [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 = Eu_52.7Gd_7.3, x = 8, y = 43; for compound 2, Ln₆₀ = Eu_52.2Tb_7.8, x = 15, y = 30; H₂dmp⁻ or Hdmp²⁻ = 2,2-dimethylol propionic acid = L). The crystallographic study showed that the 60-metal core of compounds 1 and 2 are protected by a single type of organic ligand without any extra auxiliary ligand to complete the coordination sphere, which are the first to be 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 the metal frame, which is expected to break the ionic radius limitation in the synthesis.