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 H24bpytm(NO3)2. The reaction of CuCl2.2H2O with 4bpytm at low pH values afforded three supramolecular compounds: H24bpytm[CuCl4] (1) and the monomeric complexes [CuCl3(H4bpytm)(4bpytm)] (2) and [CuCl2(H4bpytm)2]·Cl2 (3). Nevertheless, the same reaction using aprotic solvents under microwave irradiation afforded the 1D coordination polymers [CuCl2(4bpytm)]·2dmf (4.dmf) and [CuCl2(4bpytm)]·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.

配体(ligand)4bpytm[4bpytm=双(4-吡啶硫基)甲烷(bis(4-pyridylthio)methane)]在强酸性介质中反应得到H24bpytm(NO3)2。二水合氯化铜(CuCl2·2H2O)与4bpytm在低pH值条件下反应，得到三种超分子化合物：H24bpytm[CuCl4]（化合物1）、单核配合物[CuCl3(H4bpytm)(4bpytm)]（化合物2）以及[CuCl2(H4bpytm)2]·Cl2（化合物3）。不过，当使用非质子溶剂并辅以微波辐射进行该反应时，可得到一维配位聚合物[CuCl2(4bpytm)]·2二甲基甲酰胺(dmf)（4·dmf）与[CuCl2(4bpytm)]·2二甲基亚砜(dmso)（4·dmso）。针对所有化合物，本研究分析了其通过弱相互作用构建的三维超分子有序结构；同时针对4·dmf与4·dmso，探究了其在溶剂脱除后的热行为与结构动力学。对上述配合物的X射线晶体结构分析表明，本研究采用的合成策略可有效制备带有空腔的金属有机方格网格网络。