Abstract
Three, PO4 3-/HPO4 2- and AsO4 3--incorporated, new tetranuclear complexes of copper(II) and zinc(II) ions have been synthesized and fully characterized. In methanol-water, reactions of H3cpdp (H3cpdp = N,N'-Bis[2-carboxybenzomethyl]-N,N'-Bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol) with copper(II) chloride in the presence of either NaOH/Na2HPO4·2H2O or KOH/Na2HAsO4·7H2O lead to the isolation of the tetranuclear complexes Na3[Cu4(cpdp)2(μ4-PO4)](OH)2·14H2O (1) and K2[Cu4(cpdp)2(μ4-AsO4)](OH)·162/3H2O (2), respectively. Similarly, the reaction of H3cpdp with zinc(II) chloride in the presence of NaOH/Na2HPO4·2H2O yields a tetranuclear complex, Na(H3O)2[Zn4(cpdp)2(μ4-HPO4)]Cl3·121/2H2O (3). All complexes are characterized by single-crystal X-ray diffraction and other analytical techniques, such as Fourier transform infrared and UV-vis spectroscopy, thermogravimetric and electrochemical studies. The solid-state molecular framework of each complex contains two monocationic [M2(cpdp)]+ (M = Cu, Zn) units, which are exclusively coordinated to either phosphate/hydrogen phosphate or arsenate groups in a unique mode. All three complexes exhibit a μ4:η1:η1:η1:η1 bridging mode of the PO4 3-/HPO4 2-/AsO4 3- groups, with each bridging among four metal ions. The thermal properties of all three complexes have been investigated by thermogravimetric analysis. Low-temperature magnetic studies of complexes 1 and 2 disclose moderate antiferromagnetic interactions mediated among the copper centers through alkoxide and phosphate/arsenate bridges. Electrochemical studies of complexes 1 and 2 in dimethylformamide using cyclic voltammetry reveal the presence of a fairly assessable one-electron metal-based irreversible reduction and one quasireversible oxidation couple.