Study On Design, Synthesis And Catalytic Application Of Coordination Polymers

Coordination compounds, especially coordination polymers, have various advantages compared with traditional catalysts, such as rational designable; porous together with large surface area; heterogeneous and reusable etc. In this dissertation, a series of coordination compounds (polymers) were designed and synthesized. The catalytic properties of part compounds were investigated. The dissertation was divided into the following parts:Firstly, a family of Polyoxometalates (POMs) buit up from polyanion of [WZn{Mn(H2O)}2(ZnW9O34)2]12- were designed and synthesized, including two clusters and two polymeric solids. The structures have been characterized by single X-ray diffraction analysis. The catalytic property of the ionic liquid salt of [WZn{Mn(H2O)}2(ZnW9O34)2]12- has been inverstigated for selectively oxidation of for (E)-3-phenylprop-2-en-1-ol. Coordination polymer [Co(H2O)6]2{[Co(H2O)4]2 [Co(H2O)5]2WZn[Mn(H2O)]2(ZnW9O34)2}·10H2O can selectively oxidize styrene at room temperature with H2O2 as oxidant.Secondly, according to the coordination preferences of transition metal ions, we have modified serine molecule with pyridyl unit to generate an effective bridging linker, (S)-3-hydroxy-2-(pyridin-4-ylmethylamino)propanoic acid (L). Basically, the additional pyridyl group together with the carboxylate group of L ligand can bridge transition metal ions to form extended solid-state materials, while the remaining unit can act as functional group for special applications. Most important of all, the second homochiral center can be generated when the amino group is coordinated to the metal ion, which is a subsequent induction of the neighboring homochiral carbon center. Further more, the metal ion can be chelated by the amino group and the carboxylate group together with two chiral centers, which act as the third chiral center in some cases. We investigate its catalytic properties of Mannich reaction and 1,2-addition of a,β-unsaturated ketones (aldehyde).Thirdly, Cu(Pyacac)2 have been used as a functional ligands for the synthesis of some coordination polymers for catalytic applications. The catalytic experiments showed that the catalytically active center of Cu(Pyacac)2 was maintained during the transformation process. However, the crystal structure has not been characterized because of the bad quality of the crystals.Finally, two metal-crown compounds were synthesized during the synthesis of some coordination polymers. The Ru" compound exhibited good catalytic property for alkenylation of aromatic C-H bonds with terminal alkynes.