Exploring the Performance Improvement of Magnetocaloric Effect Based Gd-Exclusive Cluster Gd60

Despite wide potential applications of Gd-clusters in magnetocaloric effect (MCE) owing to f7 electron configuration of Gd­(III), the structural improvement in order to enhance MCE remains difficult. A new approach of the situ hydrolysis of acetonitrile is reported, and the slow release of small ligand CH3COO– is realized in the design and synthesis of high-nuclearity lanthanide clusters. A large lanthanide-exclusive cluster complex, [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96(H2O)56]­(NO3)15Br12(dmp)5·30CH3OH·20Hdmp (1-Gd60), was isolated under solvothermal conditions. To the best our knowledge, cluster 1 possesses the high metal/ligand ratio (magnetic density) and the largest magnetic entropy change (−ΔSmmax = 48.0 J kg–1 K–1 at 2 K for ΔH = 7 T) among previously reported high-nuclearity lanthanide clusters.