Synthesis,Structures And Properties Of Macrocyclic Oxamido Metalloligands And Coordination Polymers

Metalloligand or "complex-as-ligand" approach is effective in constructing functional coordination polymers with same or different metals. Exposed metal sites are important on many applications of the coordination polymers such as storage, separation, catalysis and sensing. The main research contents of this thesis are as follows:1. Four new mononuclear macrocyclic metalloligands MiL1, CuL5, CuL6and CuL8were synthesized. The electrochemical properties of ML1-4and CuL5-8metalloligands were studied by cyclic voltametry, and their IR and UV-vis spectra were also analysed.The two oxygen atoms of the oxamido group of the metalloligands are active in chelating metal ions, and the metalloligands have a pair of carboxylate functionalities which can coordinate with other metal ions in various modes, thus a variety of coordination polymers may be constructed.2. Three one-dimensional helical coordination polymers that use macrocyclic complexes as the bridging ligand were designed and prepared. X-ray single crystal analyses revealed that exposed metal sites exist in the two helical compounds, which is uncommon for coordination polymers that having1D helical structures.3. One-dimensional zigzag chain and ladder chain of hetero-metallic coordination polymers with macrocyclic complexes as the bridging ligand were prepared, which type of coordination polymers have not been reported for the best of our knowledge. The four coordination polymers were characterized by thermogravimetric analysis and IR spectra. X-ray single crystal analyses revealed that these compounds have rich intermolecular hydrogen bonds and π-π stacking interactions which link the one-dimensional chains to form3D supermilecular network structures.4. Two zero-dimensional complexes using macrocyclic complexes as bridging ligands were prepared. X-ray single crystal analyses revealed that the zero-dimensional complexes have box-like structures. Rich H-bonds and π-π stacking interactions link the zero-dimensional molecules to form3D supramolecular structures.5. Within the process of attempt to design and synthesis of new metalloligands, a1D and a2D coordination polymers with oxalate as the bridging ligand were obtained unexpectedly. The result of the attempt is of guiding significance for future design and synthesis of new metalloligands.