Syntheses, Crystal Structures And Properties Of Complexes Of Some Transition Metal With Triazole Carboxylate And Phosphonate Derivative

In this paper, by'treating 2-(1H-1,2,4-triazole)-1-acetic acid (Htrza) or 1-aminoethylidenediphonic acid (aedpH4) with some transition metal ions directly or under the help of some subsidiary ligands, five complexes have been successfully obtained at room temperature or under hydrothermal conditions and characterized by single-crystal X-ray diffraction analysis, Furthermore, their IR,UV/Vis,thermal stability,catalytic proprety and electric properties were also investigated.The results are outlined as follows:(1)Treatment of Htrza and a subsidiary ligand (2,2'-bipy or 4,4'-bipy) with Cu(Ⅱ) afforded three coordination polymers{[Cu(trza)(2,2'-bipy)(H20)]·(C104)}n(1), {[Cu(trza)(2,2'-bipy)(H2O)]·(BF4)}n(2) and{[Cu(trza) (4,4'-bipy)]·(H20)·(ClO4)}n(3). The reaction of aedpH4 with Cu(Ⅱ) and Ni(Ⅱ) produced two coordination polymers {Cu[CH3C(NH3)(PO3H)(PO3)]}n(4) and {Ni1.5[CH3C(NH3)(PO3H2)2(H2O)][CH3C(NH2)(PO3)2(H2O)]·H2O}n(5).(2) The above five coordination polymers were characterized by single-crystal X-ray diffraction analysis. The X-ray diffraction analyses showed that both of polymer 1 and 2 display one-dimensional chain, Polymer 3 exhibits two-dimensional layered network. In polymer 1 and 2 there areπ-πstacking interactions,which further link one-dimensional chain to form a two-dimensional layered network. In polymer 3 there areπ-πstacking interactions and hydrogen bonds, which further link two-dimensional layered network to form three-dimensional supramolecular network structures.Polymer 4 and 5 are also two-dimensional layered network, which are interlinked by hydrogen bonds, forming three-dimensional supramolecular network structure.(3) The IR spectra of polymer 1-5,UV-Vis absorption spectra of polymer 1 and thermal stability of polymer 4 and 5 were investigated.(4) The catalytic activities of polymer 1-4 in water to oxidative coupling of 2,6-dimethylphenol were investigated. The study suggests that the coordination environment of the copper center of complexes have important influences on their catalytic activities. Polymer 3 in which Cu(Ⅱ) is five coordinated have high conversion and selectivity.(5) The electrochemical study on complex 3 in DMF displays that its redox process in the potential range of -1.6～0.2V is quasi-reversible (2Cu(Ⅱ)(?)2Cu(Ⅰ)) and controlled by the diffusion,the electron transfer number n is 2.