| Metal-organic frameworks (MOFs) is one of the most important field of material science, for their intriguing structural features and enormous range of applications in catalysis, adsorbent and molecular recognition. Based on the principle of crystal engineering, it is possible that rational design and synthesis of crystalline materials by selecting certain geometric metal ions and suitable organic ligands. At the same time, crystalline materials can be endowed with optics, electric, magnetism, enantioselective separation and catalysis by selecting functional metal ions and organic ligands with functional groups. Although a lot of MOF have been synthesized, the study of copper halides, which containing lots of single molecular building blocks, is in infance. Compounded to other metal-organic frameworks, high-dimension copper halides structures are rare. In this work, based on the principle of crystal engineering, we have designed and synthesized several coordination polymers of copper halides using redox reaction under hydrothermal condition. We also study their structure and physical properties.In the first chapter, the concepts, methods, histories and new developments of coordination polymers and copper halides are concisely introduced. At the end of this chapter, we pointed out the importance of the search project and summarized the important results obtained in the thesis.In the second chapter, we introduced two 3D zeolite-like coordination polymers of copper iodide Cu4I4(DABCO)4. The X-ray single crystal analysis showed the two compounds had the same molecular formula(α,β). The difference between the two compounds is they contain different topologies. One of the two compounds is 3D four-connected net with 66 topology, the oher contains 654 net, which is never observed in four-connected net. Thus, the compounds represent a new type of zeolite-like structures.In the third charter, two isomers of copper halides of the framework formula (CuI)7(DABCO)2.5 were prepared by solvothermal methods, and their structures were determined by single-crystal X-ray diffraction. Both of the structures contain two types of secondary building units, which are connected differently giving rise to two three-dimensional structures. These two structures both contain FSC topology, which is only predicted by O'Keeffe in theory, and is the first observation, to our knowledge, of FSC topology in coordination polymers. The formations of these structures show a good example of different connectivity between the building units that can form different structures. In addition, the two compounds contain two new clusters of coppoer iodide Cu6I6 and Cu8I8, which never be reported before. On the other hand, three isomers containing the same ladder chain have been synthesized by pH control, which can be seen as a good example of chain transformation in coordination polymers.In charter four, we report two examples of the simultaneous redox of Cu2+ to Cu+ and X7+ to X- (X=Cl, I), and self-assembly under solvothermal conditions affording luminescent copper(I) layer and chain polymer, (CuCl)3C6H7N3 (1) and (CuI)2C6H7N3 (2) (C6H7N3=2,3-dihydroimidazo[1,2-α]-pyrimidine). We found an in situ cycloaddition of 2-amino-pyrimidin and EtOH. (CuCl)3C6H7N3 is constructed by double six-membered ring chain, (CuI)2C6H7N3 is constructed by ladder chain. |
