Four high-nuclearity lanthanide–transition metal clusters, formulated as [Ln₄₅M₇(OH)₆₈(CO₃)₁₂(CH₃COO)₂₆(CH₃CH₂COO)₆(H₂O)₇₀]·(ClO₄)₂₅·(H₂O)_x (abbreviated as Ln₄₅M₇: 1, Gd₄₅Co₇; 2, Gd₄₅Ni₇; 3, Dy₄₅Co₇; 4, Dy₄₅Ni₇; x ≈ 50), were obtained with the mixed protecting ligands acetate and propionate. Structural analysis shows that the cluster cationic core contains 52 metal ions featuring a bowl-like structure. 12 CO₃²⁻ and 3 ClO₄⁻ anions play the role of mixed anion templates. Magnetic studies reveal that the two isotropic Gd-containing clusters Gd₄₅Co₇ and Gd₄₅Ni₇ exhibit a large magnetocaloric effect (MCE), while the anisotropic Dy-containing clusters Dy₄₅Co₇ and Dy₄₅Ni₇ show slow relaxation of magnetization.

中文翻译：

---

由混合配体保护的 四个3d–4f Ln ₄₅ M ₇杂金属团簇†

四个高核镧系-过渡金属簇，公式为[Ln ₄₅ M ₇（OH）₆₈（CO ₃）₁₂（CH ₃ COO）₂₆（CH ₃ CH ₂ COO）₆（H ₂ O）₇₀ ]·（ClO ₄）₂₅ ·（H ₂ O）_x（缩写为Ln ₄₅ M ₇：1，Gd ₄₅ Co ₇ ; 2，Gd ₄₅ Ni ₇ ; 3，Dy ₄₅ Co ₇ ; 4，Dy ₄₅ Ni ₇ ; X ≈50），用该混合的配体保护得到乙酸酯和丙酸酯。结构分析表明，簇状阳离子核包含52个具有碗状结构的金属离子。12 CO ₃ ^2-和3- CLO ₄ ^-阴离子起到混合的阴离子模板的作用。磁性研究表明，两个各向同性的含Gd团簇Gd ₄₅ Co ₇和Gd ₄₅ Ni ₇表现出较大的磁热效应（MCE），而各向异性的含Dy团簇Dy ₄₅ Co_图7和Dy ₄₅ Ni ₇表现出缓慢的磁化弛豫。