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.本研究通过1,2,3-环己三醇(1,2,3-cyclohexanetriol)、乙酸配体(acetate ligand)与高氯酸稀土(Ln(ClO4)3)的反应，合成了3例同金属高核簇合物，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（缩写为Ln37，其中Ln分别为钆(Gd，化合物1)、铽(Tb，化合物2)、铕(Eu，化合物3)，LH3为1,2,3-环己三醇），该类簇合物具有双笼状结构。其中，最大的奇数核稀土簇Gd37的熵变(-ΔSm)为38.7 J·kg⁻¹·K⁻¹。