Self‐Assembly of Heterometallic [Ln^III₂Co^II₅] Clusters: Magnetic Properties and Efffcient Conversion of CO₂ with Epoxides and Amines

Three heterometallic [Ln^III ₂Co^II ₅] clusters with the formulas [Ln^III ₂Co^II ₅(L₁)₂(L₂)₂(L₃)₂(OAc)₄(NO₃)₂]·4CH₃CN (Ln^III = Gd (1), Tb (2), and Dy (3); HL₁ = (E)-1-((2-hydroxy-3-methoxybenzylidene)amino)naphthalen-2-ol, HL₂ = 1-aminonaphthalen-2-ol, and HL₃ = trimethylopropane) have been obtained via self-assembly of mixed ligands strategy. Significantly, cluster 1 displays a larger magnetocaloric effect (MCE) (-ΔS_m = 36.83 J kg^-1 K^-1 at 2.0 K and 7.0 T), while cluster 3 shows slow magnetic relaxation behavior under zero dc field. Moreover, clusters 1-3 as heterogeneous catalysts can effectively convert CO₂ with epoxides and benzylamine to form oxazolidinones under mild conditions. To our knowledge, it is the first reported bifunctional heterometallic heptanuclear clusters which show well magnetic behaviors and can effectively catalyze CO₂ with epoxides and amines under mild conditions simultaneously.