Design, Synthesis And Self-assembly Of Supramolecular Coordination System With Novel N-containing Heterocyclic Ligands

The design and synthesis of supermolecular complexes featuring special structures are not only a hot topic, but also an important theme of coordination chemistry all along. However, the structures of the complexes could be controlled by many factors, such as ligand structures and the variable coordination geometries of metal ions and also by the intermolecular interactions and the reaction conditions. This work mainly focused on the study of how the coordination bond strength affecting the structures of coordination compounds, and the rational design of some special coordination compounds through making use of the character of the ligand structures and the properties of metal ions. During this period, some interesting metal-organic frameworks (MOFs) with nano-tube like structure and metal clusters have been produced and structurally examined. This thesis is divided into four chapters.In chapter 1, the study background of this work is concisely introduced with the emphasis on the intermolecular interactions in the forming of the coordination compounds and some examples of constructing MOFs and nanotubes, and we also summarize the driving force in the self-assemble of several metal porphyrins.In chapter 2, the porphyrin ligand was synthesized. The reactions of ligand with Zn(OAc)2 have been carried out under different solvothermal conditions. Three coordination compounds (1-3) were obtained. Then the DFT calculation, the study of binding ability and ESP were carried out.In chapter 3, two similar ligands were synthesized. Two coordination polymers (4 and 5) were obtained with the ligands. The main objective of this work is to obtain compounds with same local topological network, which is based on the rational designable ligands with special coordination sites. The complex 4 behaves a 3D nanotube like structure, and the complex 5 display a 2D ladderlike structure with the same local topology as compound 4.Chapter 4 gives the detail of the synthesis, crystal structures of complexes 6 and 7. The two complexes were all metal clusters. We have analyzed their structures which were assembled through hydrogen bonds, and their H-bond topology was described.