Synthesis, crystal structures, spectroscopic, thermal analysis, electrochemical and solution studies of two new mixed metal coordination polymers based on dipicolinic acid and 3,4-diaminopyridine

• Two novel heterobimetallic 2D coordination polymers were synthesized.
• Two coordination compounds are studied both in the solid state and solution.
• Cyclic voltammograms were carried out with carbon paste electrode.

Two new 2D heteronuclear coordination polymers with Ni(II), Zn(II) and Ca(II), namely {(dapH)2[CaM2(pydc)4(H2O)2]·2H2O}n (M = Ni (1) and M = Zn (2)) where [pydcH2 = pyridine-2,6-dicarboxylic acid (dipicolinic acid), dap = 3,4-diaminopyridine] have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermal (TG/DTG/DTA) analysis, electrochemical as well as X-ray single crystal diffraction. The compounds 1 and 2 display isostructural features and crystallized in the monoclinic P21/n space group. Both of the compounds contain cationic and anionic fragments and two uncoordinated water molecules. In 1 and 2 (pydc)2− acts as tridentate ligands and connected to calcium ions through carboxylate bridging. Then each dipicolinate ligand bridges one calcium to a M(II) atom.The equilibrium constants of the binary, ternary and quaternary complexes of ligands or proton transfer system with metal ions in an aqueous solution were investigated by a potentiometric pH titration method.

Two new 2D heteronuclear coordination polymers with Ni(II), Zn(II) and Ca(II), with dipicolinic acid and 3,4-diaminopyridine were synthesized and characterized. In these new supramolecular coordination polymers, existent species join together with the cooperation of multiple inter/intra-molecular classical O–H⋯O, N–H⋯O and non-classical C–H⋯O hydrogen bonds (H-bonds), offset face to face π–π, edge to face C–H⋯π and C–O⋯π stacking interactions in the form of various homo/hetero-synthons leading to three-dimensional supramolecular networks.Figure optionsDownload as PowerPoint slide