Modification of Structure and Magnetic Properties in Coordination Assemblies Based on [Cu(cyclam)] 2+ and [W(CN) 8 ] 3?

摘要

The 1D {[Cu II (cyclam)] 3 [W V (CN) 8 ] 2 . 5H 2 O} n ( 1·5H 2 O ) (cyclam = 1,4,8,11-tetraazacyclotetradecane) coordination polymer of ladder topology can be obtained in water-alcohol solution from [Cu(cyclam)] 2+ and [W(CN) 8 ] 3? building blocks. Upon dehydration, 1·5H 2 O undergoes a single-crystal-to-single-crystal structural transformation to the anhydrous {[Cu II (cyclam)] 3 [W V (CN) 8 ] 2 } n ( 1 ) form, which retains the same topology, but is characterized by shorter Cu-W distances and significantly more bent CN-bridges. The deformation of the coordination skeleton is reflected in magnetic properties: the predominant intra-chain interactions change from ferromagnetic in 1·5H 2 O to antiferromagnetic in 1 . The reaction between the same building blocks in water solution under slow diffusion conditions leads to the formation of a 0D {[Cu II (cyclam)(H 2 O)] 2 [Cu II (cyclam)][W V (CN) 8 ] 2 } . 3H 2 O pentanuclear assembly ( 2·3H 2 O ).