Coordination Polymers Of Novel Porphyrins Containing Eight Pyridyl Units

Porphyrins play vital roles in many biological processes, such as light harvesting, oxygen transportation, and catalysis. Porphyrin-based coordination polymers with novel structures and intriguing properties have attracted widespread interests, due to their promising applications in various areas such as hydrogen storage, molecular sorption and sensing, and heterogeneous catalysis. In this thesis, two novel octapyridyl porphyrin ligands5,10,15,20-tetrakis(4,4’-dipyridylaminophenylene)porphyrin (TDPAP) and5,10,15,20-tetrakis (3,5-di(4-pyridyl)phenyl)porphyrin (TDPPP) were designed and synthesized for the construction of novel coordination polymers.In chapter1, a short review on recent advances, especially the design strategies for construction of porphyrin-based coordination polymers was given. On this basis, the research ideas of this thesis were described.In chapter2, TDPAP was synthesized. Its protonated form1were obtained, and four coordination polymers2-5were constructed from the coordination with Mn(II), Cu(II), Zn(II) and Cd(II), respectively. These compounds exhibit a rich structural diversity, including hydrogen bonded ID chains,3D structure formed by the interpenetrated2D networks,2D structure with50-and70-membered metallomacrocycles and stair-like2D structure. And TDPAP was demonstrated to coordinate with4-7metal centers, and the4,4’-dipyridyl-aminophenylene moieties may rotate around the porphyrin framework, resulting in its good conformational flexibility. Furthermore, intermolecular π...π stacking interactions and hydrogen bonds were observed. The solid state emission measurements indicate that the emission behavior can be effectively modulated by the protonation and metal coordination effects.In chapter3, TDPAP was synthesized and used to coordinate with Cu(II), Zn(II) and Cd(II) to afford complexes6-8. Crytal7exhibits an interesting3D structure formed by the π...π stacking interactions.6and8have similar structures, i.e.,2D networks formed by the linkage of wave-type double-chains and porphyrins, with TDPPP utilizing its six pyridyl moieties.In chapter4, the results of this thesis were summarized with an outlook on the future researches.