Based On Polyoxometalates Or Coordination Polymers Functional Materials:Syntheses And Properties

This thesis focuses on the design and synthesis based on polyoxometalates ?POMs? or coordination polymer functional materials. Their structures have been characterized by elemental analysis, single crystal X-ray diffraction and IR analysis method, and some of these compounds were studied on the catalytic activity and fluorescence properties.The experiment results as follows:1. A sandwich type polyoxometalate K₁₀[Co₄?H₂O?₂(PW₉O₃₄)₂] ?abbreviated Co₄?PW₉?₂? has been synthesized. In recent years, this polyoxometalate has been widely used in the field of catalysis, especially in water oxidation, which showed excellent catalytic properties. However, Co₄?PW₉?₂ has not applied in oxidative desulfurization under neutral conditions. We prepared by ionic exchange of K₁₀[Co₄?H₂O?₂(PW₉O₃₄)₂] and cationic surfactant trimethylstearyl-ammonium chloride STA·Cl. Surfactants encapsulated POM ?STA?₁₀[Co₄?H₂O?₂(PW₉O₃₄)₂]?SEP? as catalyst,30% H₂O₂ as oxidant, ionic liquid 1-Butyl-3-methylimidazolium hexafluorophosphate ?[Bmim]PF₆? as extractant, catalytic oxid ative desulfurization in model oil, sulfur compounds include DBT, BT and 4,6-DMDBT. n?H₂O₂?/n?DBT?/n?SEP? molar ratio of 80:20:1, the efficiency of desulfurization could reach 100% DBT removal in 40 min at 60?. We found sulfur removal efficiency follows the order of DBT>4,6-DMDBT>BT. The catalyst could be recycled conveniently and reused for at least six times without significantly reducing desulfurization efficiency. This system provides a simple, easy and efficient method for industrial application.2. Three new coordination compounds have been solvethermal synthesized based on Cu^?/Zn^? and flexible ligands: [Zn?o-bbtz??nip?]_n ?1? [Zn?m-bbtz??nip?]_n ?2? {[Cu?o-bbtz??nip?]H₂O}_n?3?Compound 1 and 2 represent 4⁴-sql network structure, Compound 1 shows a 2D?3D polythreading motif by ?…? stacking interactions. Compound 2 features a 2D?2D polycatenated network by ?…? stacking interactions. It is noteworthy that the ID chains in 3 are connected into 2D layers by the ?…? interactions. Then, these 2D layers are further connected to form a 3D supramolecular network via hydrogen bonding interactions. The isomeric bis?triazole? ligands adopts completely different conformations of cis and trans in compounds 1-3. An trans conformation was found in compounds 1 and 2, while a cis conformation was in compound 3. The former contributes to the formation of a highly undulated sheet and the latter to the loop. This result shows that isomer bis?triazole? ligand can fine-tune themselves to match with the coordination preference of metal centers and lower the energetic arrangement in the self-assembly process. The luminescent properties of 1 and 2 have also been investigated.