【作者】 宁德宽；

【导师】 冯守华；

【作者基本信息】 吉林大学 ， 无机化学， 2009， 博士

【摘要】 本论文主要研究以碘化亚铜为构造单元来构筑新型配位聚合物同时研究配位聚合物的合成和结构,旨在将简单的结构单元和桥连配体有效的链接。本论文在水热条件下,合成出来六个碘化亚铜化合物,并对他们进行了结构表征和性质研究。在水热条件下,合成了以水为配位基团的碘化亚铜化合物Cu4I4·4H2O(CM1);以多氮齿配体三聚氰胺(C3H6N6)、三乙烯二胺(C6H12N2)、2-氨基嘧啶(C4H5N3)合成了一系列化合物CuI(C3H6N6)(CM2)、Cu3I4(C8H17N2)(CM3)、(CuBr)7I4(C10H22N2)4·H2O(CM4)、I3(C6H8N3)(CM5)和Cu12I18(C6H8N3)6(CM6)。同时,我们发现在CM3、CM4、CM5、CM6的合成反应中存在着两种原位反应,并且形成了新的配体C8H17N2、C10H22N2和C6H8N3(C8H17N2=N-乙基-三乙烯二铵,C10H22N2=N,N’-二乙基-三乙烯二铵,C6H7N3=2,3-二氢咪唑[1,2-α]-嘧啶鎓阳离子)。利用单晶X-射线衍射等多种表征手段对系列合成产物的结构与相关性能进行表征及测试。论文还阐述了上述化合物的合成条件与方法,热稳定性以及对原位合成反应机理进行讨论,为含氮配体碘化亚铜配位聚合物的进一步研究奠定了基础。更多还原

【Abstract】 Metal–organic frameworks (MOFs) have been one of interesting fields in material science based on metal-ligand coordinative covalent bonding is of great interest, mostly motivated by their intriguing structural features. According to 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. As the properties of the coordination polymers is determined by their chemical constituents and framework topologies, seeking the coordination polymers with novel topoly has been considered as the exploiting the funcyional properties of the coordiation polymers.Although many research groups get a lot of great fruits in design, synthesis and functional development according to the principle of the crystal engineering. However, the synthesis mechanism is still not known clearly. So studying deeply and accumulating abundant experimental facts is necessarily, finally to predict and control the framework constructed wihe organic ligands. Cu+ have the ability to join with two, three and four ions, and X- have special ability to coordinate to metal, so Cu+ and X- will generate lots of new compounds. In this work, we have designed and synthesized several coordination polymers of copper iodide based through controlling reaction conditions. We discuss here the syntheses and structural features of these novel compounds and the structural relationships among them. We also study their physical properties.In the first chapter, the concepts, methods, histories and new developments of coordination polymers and copper halides are concisely introduced. Taking into consideration the international studies, we have focused our study on the influence of the changes caused by the coordination position or conformation of organic component on the structure of inorganic-organic hybrid compound. 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 synthesized two copper iodides with two organic ligands. Compound Cu4I4·4H2O(CM1) constructed by Cu4I4 and water molecule. Although the structure of CM1 is very simple, oxygen coordinated to Cu+ is rare. So synthesis of CM1 lays a foundation for synthesis of copper halides with oxygen containing ligands. CuI(C3H3N6)(CM2) was constructed by one-dimension ladder chain and organic ligand. Two compounds show photoluminescence at room temperature in the solid state.In the third charter, we synthesized two low-dimention copper iodides, and we found in situ reaction of DABCO in these two compounds. Compound Cu3I4(C8H17N2)(CM3) constructed by an ion copper iodide chain and single alkylation DABCO. Compound (CuBr)7I4(C10H22N2)4·H2O(CM4) constructed by an ion copper iodide chain and double alkylation DABCO. Cu+ and X- adopt several complex structures.In charter four, we report two examples of the simultaneous redox of Cu2+ to Cu+ and X7+ to X-, and self-assembly under solvothermal conditions I3(C6H8N3)(CM5) and Cu12I18(C6H8N3)6 (C6H7N3=2,3-dihydroimidazo[1,2-α]-pyrimidine). We found an in situ cycloaddition of 2-amino-pyrimidin and EtOH.更多还原