Cluster‐Based Cu II –Azide Polymers: Synthesis, Structure, Magnetic Properties, and Effect of Polyamines on Crystal Structures

Three new cluster‐based Cu II –azide coordination polymers, [Cu 8 (N 3 ) 16 (222‐tet) 2 ] n ( 1 ), [Cu 10 (N 3 ) 20 (dien) 2 ] n ( 2 ), and [Cu 12 (N 3 ) 24 (Me 5 dien) 2 ] n ( 3 ) as well as a 1D polymer [Cu 2 (N 3 ) 4 (dien)] n ( 4 ) were prepared by hydrothermal reactions of Cu II ions with NaN 3 in the presence of various polyamines. Single‐crystal X‐ray diffraction studies reveal that 1 has a 1D chain structure based on an octanuclear cluster unit {Cu 8 (N 3 ) 16 (222‐tet) 2 }. Complexes 2 and 3 are 3D polymers and in both cases the azido anions display five different bridging modes (μ‐1,1, μ‐1,3, μ‐1,1,1, μ‐1,1,3,μ‐1,1,1,3). Compound 4 is a 1D chain that represents the first example of a Cu II –azide compound that contains cis ‐EE, double EO, and terminally bonded azido ligands. The magnetic susceptibility data, measured from 2 to 300 K, showed ferromagnetic couplings in 1 , 2 , and 4 and antiferromagnetic interaction in 3 . The magnetic data of 1 and 4 were fitted with rough models, giving the exchange coupling constants J = 4.19 cm –1 for 1 and J = 25.31 cm –1 for 4 .