3D supramolecular network assembly and thermal decomposition of new copper(II) complexes with pyrazine-2,6-dicarboxylic acid

Four new Cu(II) complexes [Cu(pzda)(2,2′-bpy)(H2O)] · 2.5H2O (1), [Cu(pzda)(phen)(H2O)] · H2O (2), [Cu(pzda)(4,4′-bpy)] · H2O (3) and [Cu(pzda)(bpe)0.5(H2O)] (4) were synthesized by hydrothermal reactions of copper salt (acetate or sulphate) with pyrazine-2,6-dicarboxylic acid (H2pzda), and 2,2′-bipyridine (2,2′-bpy), 1,10-phenanthroline (phen), 4,4′-bipyridine (4,4′-bpy) or 1,2-bis(4-pyridyl)-ethane (bpe), respectively. For 1 and 2, they are both monomeric entities which are further assembled into 3D supramolecular networks by hydrogen bonds and π–π stacking interactions. Complex 3 has a 2D metal–organic framework which is connected into 3D supramolecular network by hydrogen bonds. However, for 4, the bpe ligand bridges two Cu(II) ions into binuclear unit, and then the binuclear molecules are assembled into 3D supramolecular network by hydrogen bonds between the coordination water molecule and the carboxylate oxygen atoms. The thermal decomposition mechanism of complexes 1 and 2 cooperated with powder XRD at different temperatures is discussed. The results reveal that once liberation of water molecules takes place the supramolecular network of 1 and 2 collapses.

Graphical abstractUnder hydrothermal reactions four novel Cu(II) complexes of pyrazine-2,6-dicarboxylic acid together with auxiliary ligands were obtained. The results show that the Cu(II) complexes are mononuclear, binuclear and 2D grid structure, respectively. They are further assembled to 3D supramolecular structures. The thermal decomposition of 1 and 2 is discussed in detail.Figure optionsDownload full-size imageDownload as PowerPoint slide