Self-assembly And Controlled Assembly Of Functional Coordination Complexes Based On N-containing Ligands

This thesis is focused on the research of the porous coordination polymer and supermolecular chemistry, which is a hot research area in inorganic chemistry. Novel supermolecular coordination complexes with predicted structures and functions are assembled from the reactions between metal ions and triphenylamine(TPA) or bipyridylamine(BPA) derivatives. On the basis of crystal structure characterization and functional research, some influencing factors of structural assembly and structure-function relationship of several compounds are systematically investigated in this thesis.In chapter 1, the research background of this work is concisely introduced. According to the latest investigations on porous coordination polymers and the influencing factors of their construction, the research aim as well as the progress of this work have been on line.In chapter 2, one flexible star-shaped ligand tris-(4-cyanophenyl)amine (TCPA) was designed and synthesized. After that, a series of porous coordination polymers with various structures were constructed by the assembly of TCPA and silver salt with different anions. Investigations of the self-assembly of TCPA-Ag(I) system by changing solvents, anions and the ratio of starting materials substantiated that MOFs with different shapes and dimensions can be constructed from TCPA by rotating its molecular "arms". Furthermore, the template effects of balance anions and solvent molecular to the final assembly structures were studied and discussed.In Chapter 3, star-shaped tetrazole ligands with more coordination points were designed and synthesized on the basis of TCPA. We studied the influences of the multiple-site coordination and metal ion coordination modes on the structural controllability of the compounds, and successfully assembled the double helical channel coordination polymers and its isomers. In addition, porous coordination polymer containing octahedron cages are successfully constructed from TCPA by in situ reactions, which avoids the hydrolysis problems in old methods.In chapter 4, a series of bipyridylamine ligands and their complexes with Cu(I) were synthesized by altering the angles of the ligands and increasing the length of the spacers. We analyzed how the shapes and dimensions of the coordination polymers are affected by the angles of ligands, the length of spacers and the coordination modes of bipyridylamine. The relationships between structure and fluorescence properties of these polymers were then discussedIn chapter 5, the reactions between cadmium halides and 4,5-Diazafluoren-9-one ligand with big conjugate plane generated 1 dimensional chains, which further construct 3 dimensional MOFs, especially the porous coordination polymer with nanoscale pore size, viaπ-πstacking interaction.In chapter 6, a briefly conclusion on this work and an outlook to the further study have been noted.