Studies On The Cu-CO Complexes Bridged By Pyridinecarboxylic Acid And Metal Complexes With Pyridylacetic Acid

Coordination polymers have attracted much attention for their intriguing structures, unique properties and potential applications in NLO, magnetic and supraconductive materials, catalysts, biological simulation, absorption, separation, and so on.Pyridinecarboxylic acids have been extensively used in the preparation of metal complexes. Carbonyl complexes of copper are important chemical species from both industrial and academic points of view as they are involved in the synthesis of methanol, and in the removal of CO from industrial streams. They have been extensively used in bioinorganic and catalysis fields. In this thesis, the studies on the Cu-CO complexes have been reviewed. Reaction of copper salt with pyridinecarboxylic acid ligand in the presence of Mo(CO)6, two Cu-CO coordination polymers bridged by pyridinecarboxylic acid have been synthesized, which are the first example of coordination polymers containing carbonyl-bridged copper units, as well as the first example of organic ligands supported two-dimensional copper(I) carbonyl polymers; Using pyridylacetic acid as ligands, four metal complexes have been synthesized. All of them were characterized by elemental analysis, Infrared (IR) spectroscopy, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Main work is listed as follows:1. A two-dimensional Cu(â… )-CO coordination polymer [Cu2(CO)(4-C5H4NCOO)2]n (1) has been synthesized with 4-pyridinecarboxylic acid, Mo(CO)6 and copper salt by solvothermal process. Complex (1) crystallizes in the Orthorhombic space group Pbcn with a = 13.728(3) A, b = 7.050(2) A, c = 13.559 ?. There are dinuclear copper structure units in the complex (1), the coordination number of two Cu(â… ) ions in each unit is five and the geometry is distorted trigonal bipyramids. The 4-pyridinecarboxylate acid ligand adoptsμ3-N,O,O bridging coordination mode, and two adjacent Cu(â… ) ions in each unit are bridged by symmetricalμ2-CO.2. A two-dimensional Cu(â… )-CO coordination polymer [Cu2(CO)(3-C₅H₄NCOO)₂]n (2) has been synthesized with 3-pyridinecarboxylic acid, Mo(CO)6 and copper salt by solvothermal process. Complex (2) crystallizes in the Monoclinic space group C2/c with a = 13.668(14) A, b = 8.401(9) A, c = 12.406(13)A,β= 96.961(13)°. There are dinuclear copper structure units in the complex (2), the coordination number of two Cu(â… ) ions in each unit is five and the geometry is distorted trigonal bipyramids. The 3-pyridinecarboxylate acid ligand adoptsμ3-N,O,O bridging coordination mode, and two adjacent Cu(â… ) ions in each unit are bridged by symmetricalμ2-CO .3. A two-dimensional coordination polymer [Cu(C₇H₆NO₂)₂(H₂O)₂]n (3) has been obtained from a solvothermal reaction of 3-pyridylacetic acid, Mo(CO)₆ with Cu(ClO₄)₂·6H₂O. Complex (3) crystallizes in the Monoclinic space group P21/n with a = 9.0672(18) A, b = 8.6022(17) A, c = 9.601(2) A,β= 101.335(3)°. In the complex (3), the coordination number of Cu(â…¡) ion in each unit is six and the geometry is distorted octahedron. The pyridyl nitrogen and carboxylate of the 3-pyridylacetate ligand adopt unidentate coordination modes.4. Three two-dimensional coordination polymers [M (C7H6NO2)2(H2O)2]n(M = 4:Mn2+;5:Co²⁺;6:Ni²⁺)have been obtained from the solvothermal reaction of 3-pyridylacetic acid with Mn(ClO₄)₂·6H₂O, Co(ClO₄)₂·6H-2O, and Ni(ClO₄)₂·6H₂O. All crystals crystallize in the Monoclinic space group P21/n with (4): a = 9.260(2) A, b = 8.7283(18) A, c = 9.671(2) A,β= 106.788(3)°; (5): a = 9.1669(15) A, b = 8.6848(14) A, c = 9.577(2) A,β= 105.963(2)°; (6): a = 9.116(2) A, b = 8.644(2) A, c = 11.260(3) A,β= 125.540(2)°. Metal ions in each unit in these complexes are six- coordinatied with distorted octahedronal geometry. The pyridyl nitrogen and carboxylate of the 3-pyridylacetate ligand adopt unidentate coordination modes.