Structural Diversity of Infinite 3d–4f Heterometallic Cluster Compounds Driven by Various Lanthanide Radii

The syntheses, structures, and characterization of six Ln³⁺–Cu²⁺–glycine (Hgly) coordination polymers are described in this paper. They represent three types of structures. Type I (Ln=La ( 1 ), Pr ( 2 ), and Sm ( 3 )) is a 1D catenarian polymer comprising [Ln₂] nodes bridged by four cis‐Cu(gly)₂ linkers. Type II (Ln=Eu ( 4 ) and Dy ( 5 )) is a 2D open framework with a 4⁴‐net, composed of novel [Ln₆Cu₂₂] cluster nodes linked by trans‐Cu(gly)₂ linkers. Furthermore, the inner structures of the [Ln₆Cu₂₂] nodes, and the connection mode between the nodes and linkers are slightly different for 4 and 5 . Type III (Ln=Er ( 6 )) is a 3D open framework with a novel 3⁶?4¹⁸?5³?6 topology, made up of [Er₆Cu₂₄] cluster nodes and trans‐Cu(gly)₂ linkers. The rich variety of the resulting structures owes itself mainly to the interselection between the dynamic control of metalloligands and cationic components. A transition from frequency dependence to frequency independence is observed in the field‐induced magnetization lag for 1 – 3 . The frequency dependence at low temperatures may come from the antiferromagnetic Cu? Cu interaction through the [Ln₂] nodes, whereas the frequency independence may be due to the disappearance of the antiferromagnetic Cu? Cu interaction at high temperatures.