Design, Syntheses, Structures And Quantum Chemistry Research On A Series Of Transition Metal Complexes

In recent years, supramolecular complexes constructed by carboxylic acids through both covalent bond and weak interactions have attracted great interest of chemists. This is because of their intriguing structural frameworks but also account for their potential applications in catalysis, electronic and magnetic materials, microporous materials and nonlinear optics materials. SOD is a kind of metalloenzyme, which exists widely in the body of aerobionts and plays an important role. The investigation of SOD mimics complexes with Schiff bases (in particular derived from the salicylaldehyde) are developed rapidly. In this thesis, a series of complexes based on multicarboxylic acids and Tri(2-aminoethyl)amine have been successfully synthesized in solution conditions, their structure and properties were investigated.1. Four metal complexes were synthesized in the solution with the main liganaliphtiacids (succinate/ glutarate) and the auxiliary ligand Hdmpz: [Zn(Hdmpz)₂(O₂C(CH₂)₂CO₂)]_n (1), Ni₃(Hdmpz)₄(HOOC(CH₂)₂CO₂)₂(O₂C(CH₂)₂CO₂)₂(CH₃OH)₂ (2), HB(C₅H₇N₂)₃Ni(C₄H₅O₄)(C₅H₈N₂)₂·2H₂O (3),Co₃(Hdmpz)₂(HOOC(CH₂)₃CO₂)₂(O₂C(CH₂)₃CO₂)₂(CH₃OH)₄ (4). IR spectra and single crystal X-ray diffraction analysis show that complex 1 is a polymer that is interconnected by bridging succinate moieties in chelating bidentate coordination modes with Zinc. Complexes 2 and 3 are tri-nuclear structures; both of them have two types of bridging–coordinated modes of carboxylate ligands (μ₃–η²â€“η² ,μ₂–η¹â€“η¹). Moreover, 3 is nickel succinate complex containing poly(pyrazolyl)borate, thereinto, complex 3 is coordinated by bridging succinate moiety in chelating monodentate coordination modes with nickel.And there are rich intra- or intermolecular hydrogen bonds and weak interactions in the crystals of 1–4, thereby forming a set of supramolecular frameworks.2. Two metal complexes were synthesized in the solution with the main rigid ligand Acids(Pyridine-2,6-dicarboxylic acid) and the auxiliary ligand Hdmpz: [Co(2,6–PDC)(Hdmpz)₃]·H₂O (5), [Zn(2,6–PDC)(Hdmpz)₂] (6). IR spectra and single crystal X-ray diffraction analysis show that complex 5 and 6 are in a six-coordinated mode, which features anomalistic octahedral geometry. In addition, there are hydrogen bonds and weak interactions in the crystals of 5, 6.3. Two complexes were synthesized in the solution with Salicylidene tri(2-aminoethyl)amine (7) and Salicylidene tri(2-aminoethyl)amine manganese (8) complexes. X-ray diffraction analysis show that complex 8 is in a six coordinated mode with anomalistic octahedral geometry.