Two 3D Supramolecular Polymers Constructed from an Amino Acid and a High‐Nuclear Ln6Cu24 Cluster Node

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Abstract
The first successful attempt to construct 3D supramolecular frameworks with high‐nuclear 3d–4f heterometallic clusters as a node is reported. The self‐assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35‐nuclear complex {Sm6Cu29} 1 with a primitive cubic net‐like structure and 36‐nuclear complex {Nd6Cu30} 2 with a face‐centred cubic network type structure. Glycine and L‐proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X‐ray structure analyses show that 1 crystallizes in the triclinic P$\bar 1$ space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) Å, α=89.453(1), β=66.290(1), γ=68.572(1)°, V=7003.0(5) Å3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) Å, V=34 119.7(5) Å3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans‐Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.