Double-Propeller-like Heterometallic 3<i>d</i>–4<i>f</i> Clusters Ln<sub>18</sub>Co<sub>7</sub>
Hui‐Jie Lun, Ming‐Hao Du, Donghui Wang, Xiang‐Jian Kong, La‐Sheng Long, Lan‐Sun Zheng
Abstract
Two high-nuclearity lanthanide-transition metal clusters with the general formula [Ln18CoIICoIII6(OH)14(CO3)9(CH3CH2COO)6(dea)12(H2O)30]·(NO3)8·Cl4·(CH3CH2OH)6·(H2O)12 (Ln18Co7, Ln = Gd (1) and Dy (2)) have been obtained by reacting CoCl2·6H2O, Ln(NO3)3·6H2O, and a mixture of ligands consisting of propionate and diethanolamine (H2dea). Crystal structural analysis exhibits two three-blade propellers composed of the CoIII3Ln9 units connected by one CoII ion and three CO32– ions, which assemble into a double-propeller-like structure (Ln18CoIICoIII6). Magnetocaloric effect (MCE) studies indicate that Gd18Co7 exhibits a large entropy change (−ΔSm) of 36.9 J kg–1 K–1.