Metal to Ligand Interactions and Hydrogen Bonding in the Design of Metallosupramolecular Compounds: Effect of pH and Aprotic Solvents on the Nature of Materials Based on Bis(4-pyridylthio)methane and Copper(II) Chloride

The ligand 4bpytm [4bpytm = bis(4-pyridylthio)methane] in strongly acidic media afforded H(2)4bpytm(NO3)(2). The reaction of CuCl2 center dot 2H(2)O with 4bpytm at low pH values afforded three supramolecular compounds: H(2)4bpytm[CuCl4] (1) and the monomeric complexes [CuCl3(H(4)bpytm)(4bpytm)] (2) and [CuCl2(H4bpytm)(2)]center dot Cl-2 (3). Nevertheless, the same reaction using aprotic solvents under microwave irradiation afforded the ID coordination polymers [CuCl2(4bpytm)]center dot 2dmf (4.dmf) and [CuCl2(4bpytm)]center dot 2dmso (4.dmso). The 3D supramolecular organization through weak interactions has been analyzed for all of the compounds, and their thermal behavior and structural dynamics after solvent release were also investigated for 4.dmf and 4. dmso. X-ray structural analysis of these complexes showed that the synthetic conditions used represent an effective method to obtain metal organic square grid networks with cavities.