Organic Acids With Transition Metal Supramolecular Complexes Synthesis, Crystal Structure And Characterization

In this paper, five novel ternary supramolecular complexes have been synthesized by the reaction of two oligo-a-pyridylamino ligands (Hdpa and H2tdpa) with copper(II) a,p-unsaturated carboxylate complexes, seven ion mixed-valance and hetero-multinuclear ion complxes self-assembly of [M(C2O4)3]3-. The structures and characters of these compounds were measured and expressed.First, Cu(CH2=C(Me)CO2)2(Hdpa)H2O (1), Cu(CH2=CHCO2)2(Hdpa) H2O (2), and Cu(CH3-CH=CH-COO)2(Hdpa)(H2O) (3) have been prepared and characterized by elemental analysis, thermal analysis, i.r., c.v. and UV - Visible spectroscopy. The crystal structure of 1,2 and 3 have been determinied by single-crystal X-ray diffraction. It showed the structure of complex 1 is similar that of 2 indicating a distorted square planar geometry about the copper(II) atom in them. The water molecular participated in the formtion of the 1D double-chain and 2D layer-columnr supramolecular structure by N-H O and O-H O hydrogen bonds but non-coordinated with copper(II) atom. The copper(II) atom of complex 3 is in a distorted tetrahedron configuration and the water molecular coordinating with copper(II) atom participated in the formtion of the 1D stair double-chain columnr supramolecular structure by hydrogen bonds and stacking along the crystallographic a-axic. Thermal analyses show the complexes have no accurate melting point. Electrochemical studies indicate that the two complexes undergo irreversible reduction in acetonitrile solution.Second, Cu(CH2=C(Me)CO2)2(H2tdpa) (4) and Cu(CH2=CHCO2)2(H2tdpa) (5) have been prepared and characterized by elemental analysis, i.r. and UV - Visible spectroscopy.Thirdly, seven ion mixed-valence and hetero-multinuclear ion complxes with dicarboxylates and transition metal with N, N'-chelate ligand, [Fe(phen)3]3[Fe(C2O4)3]2 17H2O(6), [Fe(phen)3]3[Co(C2O4)3]2 10H2O(7), [Fe(phen)3]3[Cr(C2O4)3]rl6H2O(8), [Co(phen)3]3[Fe(C2O4)3]2 15H2O (9), [Mn(phen)3]3[Fe(C2O4)3]2 13H2O (10), [Co(phen)3]3 [Co(C2O4)3]2 16H2O (11) and [Co(phen)3]3[Cr(C2O4)3]2 17H2O (12), have been prepared and characterized by elemental analysis, i.r. and UV - Visible spectroscopy.