Study On Design, Syntheses And Properties Of Lathanide/Copper Metal-Organic Coordination Polymers

In recent years, according to crystal engineering principles, the design and construction of metal-organic coordination polymers is currently of significant interest in chemistry, material, biology, medicine and so on. It is not only owing to study the synthesis mechanism on assembly, entangle, heterogeneous etc., but also due to their potential applications in microelectronics, nonlinear optical materials, molecular selection, ion exchange, catalysis, biological activity and so on. How to choose and design the suitable building blocks to construct some metal-organic coordination polymers with expected special structure and function is the core task of crystal engineering, and also is one of the challenging projects nowadays. In this paper, we report the preparations, crystal structures and properties of metal-organic coordination polymers generated from ligand with O and N, in order to study on the effect factors (metal ions, organic ligand, temperature, pH value and templated etc.) of these reactions.1. Under solvothermal condition, two chalcanthite-like compounds, [Cu(im)₄SO₄]n (1) and [Cu(bpy)(H₂O)₂SO₄]_n (2), were synthesized by using 2,2'-bipyridine, imidazole, sulfate. They were further characterized by elemental analysis, IR, Uv-vis reflection spectra, inductively coupled plasma (ICP), TGA, X-ray powder diffraction and X-ray crystallography diffraction. Compound 1 exhibits a 1D zigzag chain structure, while 2 being 1D linear chain, which is resulted from different ligands. The relation between crystal structure and acidity of synthesis system were investigated. Uv-vis reflection spectra of two compounds indicate that the absorption bands in visible region are from copper( II) ions d-d transitions.2. By the "node and spacer", a double-T-shaped ligand (Biphenyl-3,3', 4, 4'-tetracarboxylic acid) as the spacer has been first used to direct the assembly of a 2D coordination polymer with brickwall network topology, which exhibits an interesting framework dynamic upon de-/resolvation. It might be suitable and promising for the construction of compounds with novel structures.3. Two serials of 3D lanthanide-organic coordination polymers (Compound 4, 5, 6, 7, 8) were synthesized. Compound 4, 5, 6 were obtained by in situ hydrolysis of DMF, similar reported examples is relatively rare. Compound 7, 8 were obtained by using imidazole as template molecular. These findings show that it is suitable and efficient to construct metal-organic coordination polymers.