Synthesis, Structure And Characterization Of The Coordination Polymers Based On V-shaped Or Chiral Carboxylate Ligands

Within the last decade, the rational design and synthesis of new metal-organic coordination polymers (MOCPs) have received chemists'considerable attention and intensive research in the areas of coordination chemistry and supramolecular chemistry, not only because of their fascinating framework structures but also owing to their potential applications perspective as functional solid materials in the areas of magnetism, nonlinear optics, electronics, asymmetric catalysis, gas absorption and separation, ion exchange, and so on. In this paper, a series of new coordination polymers have been synthesized by volatilization of solvent, hydrothermal, solvothermal and ionothermal synthetic techniques through selected various V-shaped or chiral carboxylic organic ligands, transition metal ions and N-donor ligands. They have been characterized by elemental analysis,thermogravimetric analysis (TGA), X-ray powder diffraction patters (XRPD), single crystal X-ray diffraction, infrared spectroscopy (IR), and the luminescence and magnetic properties of several coordination polymers have also been researched. This thesis is divided into six chapters.In the first chapter, we introduced briefly the development of coordination chemisty and the basic conception, synthetic method of the coordination polymers and systematically introduced the research progress of coordination polymers based on organic carboxylate ligands as well as the significant meaning and the research progress made in this paper.In the second chapter, three new coordination polymers, [Zn(atibdc)(dpa)]_n (1), [Co(atibdc)(dpa)]_n (2) and [Co(atibdc)(4,4'-bipy)(H2_O)₃]·2DMF·H₂O (3) have been successfully constructed by V-shaped 5-amino-2,4,6-triiodisophthalic acid ligand and znic/cobalt nitrate and auxiliary nitrogen ligands through the self-assembly process. Single-crystal X-ray analysis reveals that the coordination polymers 1 and 2 are heterogeneous crystal structure, which are linked by atibdc ligands to form an infinite 1-D zigzag chain. However,the coordination polymer 3 linked two adjacent cobalt ions via the 4,4'-bipy ligands to form an infinite linear chain. In the third chapter, two novel coordination polymers [Cu(pyala)₂]·H₂O (4) and [Zn(pya)₂]·H₂O (5) have been successfully synthesized by chiral D-3-(4-Pyridyl)-alanine ligand and copper/zinc nitrate via the self-assembly process. Single-crystal X-ray analysis reveals that the coordination polymer 4 and 5 exhibit a 1-D chiral chain structure and three-dimensional (3-D) 5-fold interpenetrated diamondoid structure, respectively.In the fourth chapter, two new coordination polymers (Emim)₂[Co₃(ip)4] (6) and [Co_1.5(tbip)₎(1.5)·2H₂O]·H₂O (7) have been been successfully synthesized by isophthalic acid , 5-tert-butyl-isophthalic acid and cobalt nitrate under ionothermal synthesis conditions. The coordination polymer 6 can be described as a eight-connected CsCl-type network topological structure utilizing trinuclear Co(II) clusters [Co3(ip)4]2- secondary building unit (SBU) as eight-connected nodes and ip ligands as linkers. The coordination polymer 7 can be described as a six-connected NaCl-type network topological structure utilizing trinuclear Co(II) clusters [Co3(tbip)3·4H2O] secondary building unit (SBU) as a six-connected nodes and tbip ligands as linkers. We also researched the magnetism of the coordination polymer 7.In the fifth chapter, two new chiral coordination polymers [Cd₂(tart)₂]_n (8) and [Cu(cphe)₂]·3H₂O (9) have been successfully constructed by D(-)-tartaric acid, L-3-Cyanophenylalanine and cadmium nitrate, copper acetate, respectively. Coordination polymer 8 belongs to orthorhombic crystal system, P2₁2₁2₁ space group,demonstrating an 3-D coordination polymer framework. Coordination polymer 9 belongs to monoclinic crystal system, P2₁ space group. The adjacent Cu(II) atoms are linked by cphe ligand to form a 1-D zigzag chain, which is further connected via strong hydrogen bonds to form a 3-D supramolecular framework.In the sixth chapter, we have summarized the nine coordination polymers that we have synthesized.