Three Giant Lanthanide Clusters Ln₃₇ (Ln = Gd, Tb, and Eu) Featuring A Double-Cage Structure

Three homometallic high-nuclearity clusters, formulated as [(CO3)2@Ln37(LH3)8(CH3COO)21­(CO3)12(μ3-OH)41(μ2-H2O)5(H2O)40]·(ClO4)21·(H2O)100 (abbreviated as Ln37, Ln = Gd (1); Tb (2); Eu (3), LH3 = 1,2,3-cyclohexanetriol) and featuring a double cage-like structure, were obtained through the reaction of 1,2,3-cyclohexanetriol, acetate ligand, and Ln­(ClO4)3. The largest odd-numbered lanthanide cluster Gd37 exhibits an entropy change (−ΔSm) of 38.7 J kg–1 K–1.经由1,2,3-环己三醇、乙酸根配体与高氯酸镧[Ln(ClO₄)₃]的反应，可制备得到三款同金属高核簇合物，其化学式为[(CO₃)₂@Ln₃₇(LH₃)₈(CH₃COO)₂₁(CO₃)₁₂(μ₃-OH)₄₁(μ₂-H₂O)₅(H₂O)₄₀]·(ClO₄)₂₁·(H₂O)₁₀₀，该类簇合物缩写为Ln₃₇，其中Ln分别为钆（Gd，化合物1）、铽（Tb，化合物2）与铕（Eu，化合物3），LH₃代表1,2,3-环己三醇，且该类簇合物具有双笼状结构。作为目前已报道的最大奇数核镧系簇合物，钆基簇Gd₃₇的熵变（−ΔSₘ）可达38.7 J·kg⁻¹·K⁻¹。