Coordination Interaction And Hydrogen-Bonded Driving Supramolecular Complexes And Controllable Self-Assembly Reaction Of Bimetallic Macrorings

The chemistry of organic-inorganic coordination polymers and supramolecular complexes has recently become area of increasing interest. 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 compounds. The synthesis and charaterization of infinite one-, two-, and three-dimensional networks have been an area of rapid growth. In the thesis, a series of novel single and multi-armed oxadiazole and triazole bridging ligands have been synthesized. The self-assembly reaction based on these ligands was investigated. In addition, a 1, 3, 4-oxadiazole bridging ligand end-capped by chelating Schiff-base coordination sites have been designed and synthesized. Controllable self-assembly reaction of bimetallic macrorings was primarily investigated. Totally 44 new coordination interaction and hydrogen-bonded driving compounds were prepared, and fully characterized by IR, MS, TGA, elemental analysis and single-crystal X-ray diffraction.1. The coordination chemistry based on single and multi-armed oxadiazole and triazole bridging ligands with inorganic Ag(I) and Cu(II) salts has been investigated. Thirteen new coordination compounds were synthesized based on them, respectively. The results demonstrated that the bend angle between the two terminal N-donors of the ligands influenced the structures of resulted compounds significantly.2. Synthesis of Cu(II)-bimetallic macrorings, based on 1, 3, 4-oxadiazole bridging ligand end-capped by chelating Schiff-base coordination sites and Cu(AcO)2 was investigated primarily. According to the different coordination patterns of metallic ions, five mixed-metal polymers were synthesized based on bimetallic macrorings, such as 1D nanoscale tube. At the same time, guest adsorption of the guest pyrazine was selective based on bimetallic macrorings and the single crystal structure with host pyrazines was determined by X-ray single-crystal diffraction.3. The coordination chemistry of bent 1, 3, 4-Oxadiazole-bridging ligands with pyridine-N-oxide as terminal groups and transition or thulium metals. Totally 13 new coordination polymers with metals and 10 hydrogen-bonding synthons between L24-L26 and acceptor groups (-COOH, -OH, -NH₂) were synthesized. The luminescent of some compounds and magnetic propertie of 21-22 were investigated.4. One compound 43 generated from 1-(4-pyridyl)butane-1,3-dione and the compound 44 without host waters of 43 were synthesized. The compound can retain single crystallinity.5. Two new type of fulvene ligands containing 1, 3, 4-Oxadiazole rings were synthesized.The results reported herein demonstrate that the use of bent 1, 3, 4-oxadiazole and 1, 2, 4-triazole bridging ligands as precursors to bind metal ions and controllable self-assembly reaction of bimetallic macrorings are in fact a new and efficient approach for synthesis of novel supramolecular networks with interesting chemical and physical properties. It provides a promising and convenient approach to access to the multifunctional materials for selective sorption, recognition, catalysis, luminescence and magnets .