Designed And Synthesized Of Nitrogen-containing Multidentate Ligands And Self-assembly Of Supramolecular Helicates

Design and synthesis of supramolecular structures by self-assemblyhas becoming an active area of coordination chemistry in the past decades.Containing organic ligands and inorganic ions in their structures, thiscategory of materials have significant applications in the areas ofabsorption and separation, catalysis, guest-exchange, chemistry sensorsand photoelectronic materials. Helix is a very common structure in nature,especially presented their diversities of biological functions inbioarchitectures. Chemists can obtain helicates using the approach ofsupramolecur self-assembly by combined organic linear multidentateligands with metal ions, it has significance to explore and simulate thestructures and functions of biological molecules. Herein,nitrogen-containing multidentate ligands have been synthesized and usedto construct helicates with different metal ions, and the influence of thestucture of the ligands and the coordination geometries of the metal ions on the formation of the helical complexes of were investigated. This workincludes three parts.The research background was introduced, mainly focused on thedevelopment of supramolecular assemblies by nitrogen-containingmultidentate ligands.Four multidentate ligands, L1, L2L3and L4, were synthesized by thecombining of3-(2-pyridyl)-pyrazole with2,2’-bipyridine, pyridine andpyrimidine. Eight complexes were prepared by the reactions of theseligands with transitional metal ions, such as Cu+、Cu2+、Ag+、Cd2+and Ni2+,the structures were determined by X-ray single crystal diffraction. Theproperties of these complexes in solution such as ESI-MS and UV-Visspectroscopy,1H NMR for the diamagnetic complexes (Cu+、Ag+、Cd2+)，and the redox behavior for Cu+and Cu2+complexes were invastigated. Andinfluences of the configuration of the ligands and the coordinationgeometry of the metal ions on the formation of the helical complexes werediscussed.Porous organic polymers were prepared by click reaction andcharacterized by PXRD, solid-state13C NMR and N2adsorption-desorption isotherms. The materials exhabit high BET surface areas (up to645m2g-1) and considerable quantity adsorption of CO2. The applications of these materilas are undergoing.