Syntheses Of Novel Coordination Polymers And Recognition On Guests

In recent years, coordination polymers?CPs? have received more attention, not only owing to their fascinating structures but also for their potential applications in luminescence, magnetism, ion-exchange, gas storage/separation and so on. In this dissertation, N, N'-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide bi?1,2,4-triazole??XL? and N,N'-dimethyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide bicarboxylic acid?H₂LB? were employed to be ligands. There Cu-XL, four Co-XL, two Zn-XL and eight Ln-LB CPs have been synthesized. The single crystal X-ray diffraction, power X-ray diffraction, TG, elemental analysis, IR, UV, luminescent spectra and magnetic measurements were investigated for these compounds. The main contributions are as following:1. A new ligand?XL? was synthesized, and then nine CPs were designed based on XL ligand and different transition metals. Cu-XL: [Cu?XL??NO₃?₂]_n?1?, {[Cu?XL??4,4'-bpy??NO₃?₂]·CH₃CN}_n?2? and {[Cu?XL?₃]?NO₃?₂·3.5H₂O}_n?3?; compounds 1-3 were obtained by changing reaction conditions such as adding co-ligand, p H and solvent, and these compounds exhibit different EPR properties. Co-XL: [Co?XL?Cl₂]_n?4?, {[Co?XL'??H₂O?₂]·0.5H₂O}_n?5?, [Co_1.5?XL??BDC?_0.5Cl₂]_n?6? and {[Co₃??₃-O??XL?₃Cl₃]OH·11.5H₂O}_n?7?; compounds 4-7 were synthesized based on the different metal salts and ammonium salts. Compound 7 exhibits two-fold interpenetrating 3D cationic framework and the ion-exchange property were investigated, the OH^- ions in the framework is able to exchange with Cr₂O₇^2- ions. Zn-XL: [Zn?XL??BDC?_0.5Cl]_n?8? and {[Zn?XL?]?Cl O4?₂·6H₂O}_n?9?; compound 8 shows a 2D sheet, compound 9 exhibits six-fold interpenetrated cationic framework with 4-conncted sqc6 topology. The anion template plays an import role in the structural diversity. And the luminescence property of compound 9 was studied in response to organic solvents, which reveals acetylacetone exhibits clearly quenching effect and the other solvents have no effects, therefore, 9 is be viewed as a excellent luminescence probe to recognize acetylacetone.2. Another new ligand H₂ LB was prepared, and eight CPs?{Ln?LB??DMA?₂?NO₃?}_n [Ln=Pr?10?, Nd?11?, Sm?12?, Eu?13?, Gd?14?, Tb?15?, Dy?16? and Ho?17?]? were designed and assembled, these compounds exhibit 2D sheets. The magnetic measurements were investigated for compounds 15 and 16. The luminescence of 13 in response to organic solvents has been well studied, acetylacetone exhibits clearly quenching effect and the other solvents have no effects, and the sensitivity of 13 for the sensing of acetylacetone is much lower than that of compound 9, thus 13 is the high-efficient luminescence probe to the acetylacetone. Besides, the luminescence of 13 in response to metal ions has also been researched. Fe³⁺ ion shows the significant quenching effect and Cu²⁺ ion results in a most obviously decrease of the luminescent intensity. The luminescence responsing to the different concentrations of the Fe³⁺ and Cu²⁺ ions has been investigated. The sensitivity of 13 for the sensing of Fe³⁺ and Cu²⁺ ions as little as 1×10^-6 mol·L^-1. By fitting these experimental data, quantitative analysis on the Fe³⁺ and Cu²⁺ ions could be achieved within certain limits by luminescent measurments.