Synthesis, Structures, and Magnetic Properties of Three Series of Discrete or 1D Compounds based on Pyramidal [LnCu4] (Ln = Gd and Dy) Cluster and Formate Ligand

Abstract

AbstractWith formate as ligand, one discrete dragonfly‐like 3d–4f cluster showing beautiful pyramidal metal skeleton, [GdCu4(HCOO)5(μ3‐OH)4(NO3)2(H2O)7](H2O) (1Gd), was obtained by a self‐assembly reaction of Gd(NO3)3, Cu(NO3)2, and formate ligand. The two nitrates could be treated as the “wings” of the “dragonfly”, and the formate with a free oxygen atom could be regarded as the “tail”. When using perchlorate instead of nitrate, two series of 1D compounds based on the similar pyramidal [LnCu4] unit, linear {[GdCu4(HCOO)5(μ3‐[OH)4(H2O)8](ClO4)2(H2O)2}n (2Gd) and zigzag {[LnCu4Na2(HCOO)4(μ3‐OH)4(H2O)9(ClO4)5](H2O)2}n [Ln = Gd, (3Gd); Dy, (3Dy)] were synthesized by controlling the formate amount. They used μ5‐η1:η4 formate or [Na2(ClO4)4]2– unit as connectors to link the neighboring [LnCu4] units together, respectively. Magnetic analyses reveal that these four compounds all show ferromagnetic interactions, and 3Dy displays slow relaxation of the magnetization.