Ligand and Anion Effects on the Morphology of Aqueous Substructures Entrained within One-Dimensional [CuL4X] Coordination Polymer Matrices (L = 2,4‘-Bipyridine, 4-Phenylpyridine; X = SO42-, SiF62-)

Abstract

The one-dimensional (1-D) coordination polymers [Cu(2,4‘-bpy)4SO4]·6H2O (1), [Cu(4-phpyr)4SO4]·5H2O (2), [Cu(2,4‘-bpy)4SiF6]·4.5 H2O (3), and [Cu(4-phpyr)4SiF6]·4.5H2O (4) (2,4‘-bpy = 2,4‘-bipyridine, 4-phpyr = 4-phenylpyridine) have been prepared in aqueous solution and characterized via single-crystal X-ray diffraction. The crystal structures of 1−4 manifest zigzag 1-D chains constructed from interdigitated “X-shaped” CuL42+ cations and the relevant counteranions while entraining hydrogen-bonded supramolecular water substructures that serve to connect the 1-D coordination polymer subunits into pseudo three-dimensional (3-D) structures. In 1, 1-D aqueous tapes comprised of water molecule tetramers and individual water molecules are evident. Discrete zero-dimensional (0-D) water clusters are observed in 2, while discrete water molecule chains are manifested in 3 and 4. The markedly different morphologies of the respective aqueous substructures within this family of coordination polymers are dictated by th...