Abstract
Three series of porous lanthanide metal‐organic coordination polymers, namely [Cu(bpy)Ln~3~(ip)~5~(Hip)(H~2~O)] [Ln = Er (1 a), Y (1 b), Eu (1 c); bpy = 2,2′‐bipyridine, H~2~ip=isophthalic acid], [Cu~3~(bpy)~2~Ln~2~(ip)~6~(H~2~O)~5~] [Ln = Yb (2 a), Gd (2 b), Tb (2 c)], and [Cu~3~Ln~2~(ip)~6~] [Ln = Eu (3 a), Gd (3 b)] have been synthesized hydrothermally by the reaction of the combination of 3d–4f metal centers and N‐/O‐donor ligands. X‐ray diffraction analyses reveal that polymers 1 a–c and 2 a–c, as well as 3 a, b are isomorphous in structure. Polymers 1 a–c consist of 3D α‐Po networks based on a inorganic rod‐shaped secondary building units (SBUs) of {Er~6~Cu~2~(bipy)~2~(O~2~C)~11~} which are 27.03 Å in length. Polymers 2 a–c also contain 3D α‐Po networks, constructed from shorter (14.79 Å) but similarly rod‐shaped SBUs of {Yb~2~Cu~3~(bpy)~2~(O~2~C)~12~}. The structure also contains hydrogen‐bonded (H~2~O)~6~ chains which can be reversibly dehydrated/rehydrated. Polymers 3 a, b contain metal carboxylate substructures which have 2D (6,3) topologies; these layers are bridged by the ip^2−^ ligands to give an overall 3D network which contains two sorts of cavities. This series of Ln–Cu coordination polymers are further characterized by antiferromagnetic behavior.