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

Abstract

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 (- Δ S_m^max = 48.0 J kg^-1 K^-1 at 2 K for Δ H = 7 T) among previously reported high-nuclearity lanthanide clusters.