Study Of Self-assembly Chemistry And Tunable Luminescence Properties Based On Open-chain Polyether-bridged Ligands With N-containing Templates

The chemistry of organic-inorganic coordination polymers and supramolecular complexes has recently become an active area of increasing interest internationally. Self-assembly of organic ligands and inorganic metal ions is one of the most efficient and widely used approaches for the construction of organic-inorganic composite materials. Recently, remarkable progress has been made in the area of molecular inorganic-organic hybrid polymers. The synthesis and characterization of infinite one-, two-, and three-dimensional networks have been an area of rapid growth. In this thesis, a series of flexible open-chain polyether-bridged ligands were synthesized. The coordination chemistry based on these new ligands and metal ions was investigated. 37 new coordination compounds were prepared and fully characterized by IR, elemental analysis, X-ray single-crystal diffraction, TGA, luminescent properties and thermal stability were investigated.I. The coordination chemistry based on a series of shorter open-chain polyether-bridged ligands with N-containing templates and inorganic Co(II),Ni(II) and Pb(II) salts has been investigated. Twelve new coordination polymers were synthesized based on them. The results indicate that the different N-containing templates have great influence on the final structure of the product.II. The coordination chemistry based on a series of longer open-chain polyether-bridged ligands with N-containing templates and inorganic Mn(II),Co(II),Ni(II) and Pb(II) salts has been investigated. Eighteen new coordination polymers were synthesized based on them. The results indicate that the coordination patterns of the ligands, the N-containing template, the weak interaction between molecules have great influence on the final structure of the product. Their luminescent properties were investigated in the solid state.III. A new coordination polymer was synthesized based on L6 with 4, 4'-bpy and Pb(II), interestingly, it was photochromic. The encapsulated 4, 4'-bpy can be selectively leached to generate the hollow oxygen-rich framework, which contains channels with hydrophilic inner surfaces. Furthermore, the dual- and bimodal-emission were successfully realized by intercalation of the different Ln3+ hydrates based on guest-driven approach. In addition, two new similar polymers were synthesized based on L6 and L8, and pilot study has been done.IV. The coordination chemistry based on a series of open-chain polyether-bridged ligands and inorganic Ag(I),Pd(II) and Hg(II) salts has been investigated. Four new coordination polymers were synthesized based on them. The results indicate that the solvent molecule and the weak interaction between molecules have great influence on the final structure of the product.This study demonstrated that the use of the flexible open-chain polyether-bridged ligands as precursors with N-containing templates to bind metal ions, is in fact a new and efficient approach for synthesis of novel supramolecular systems with interesting fluorescent chemical and physical properties. Also, the encapsulated N-containing templates can be selectively leached to generate the hollow oxygen-rich framework and provide the opportunity for the host-guest chemistry study.