The Assemble, Structures And Properties Of Complexes Based On Bispyridyl And Amide Ligands

Metal-organic frameworks (MOFs) are an important class of organic-inorganic hybrid material, not only due to their fascinating structures but also because of their potential applications as functional materials in many fields, such as optical, electronic, magnetic, catalytic, adsorption, exchange and so on. Therefore, coordination polymers have been one of the research emphases in inorganic chemistry and materials chemistry. Till now, various kinds of novel supramolecular architectures have been successfully built. However, structures of complexes could be affected by many factors, compared with the really "crystal engineering", we need much more experiment and further exploration.Because clamp-like pyridine amide ligands have the "arms", we considered to design of the rigid clamp ligands as a nice way to synthesize coordination complexes with microporous structures. And they always have advantages in NLO, electricity, magnetism, ion absorption and catalytic for their structure features and functional groups.The contents include three parts as follows:First, we synthesized ten novel coordination complexes through the self-assembly of a clamp-like ligand, N,N'-bis-(3-pyridyl) isophthalamide(L) with metal salts of Hg (â…¡),Co(â…¡),Zn(â…¡),Cu(â…¡),Cd(â…¡). [HgLCl2]2(1), [HgLBr2]2(2), [HgLI2(DMF)2]n(3), [HgLCl(SCN)]n(4), [CoLCl2]2(5), [ZnLCl2]2(6), [(ZnLSO4)]8n(7), [CuL2SO4] (8), [CdLI2]4n(9), [CdLI2]2(10). The ten complexes show different structures by single crystal X-ray diffraction. The complexes 1,2,5,6 and 10 exhibit 28-macrocyclic ring binuclear structures. The complex 8 is a special cage-like structure; The complexes 3,4 and 9 exhibit 1-D zigzag chain polymer; Complex 7 displays a novel three-dimension structure bridged by sulfate. Comparing with these structures we found that solvent, temperature and ligands play the key role in the direct self-assembly progress.Second, complex 5 dipped in the methanol solution of HgCl2 and CdSO4 respectively. About one month, through X-ray diffraction (XRD), scanning electron microscope (SEM), Energy Dispersive Spectrometer (EDS) and single crystal X-ray diffraction, we obtained complexes 1 and 11. We find that the transformation is a recurrent dissolving-exchange-crystallization process. And it provides a new approach to self-assembly complexes in the future.Third, we measured the ligand and complexes [HgLCl2](1), [HgLBr2]2(2), [HgLI2(DMF)2]n(3), [HgLCl(SCN)]n(4), [ZnLCl2]2(6), [(ZnLSO4)]8n(7), [CdLI2]4n(9) fluorescent properties in the solid state at room temperature. Compared with the ligand, fluorescent properties of complexes become weak. In addition, we also studied some complexes thermal stability and electrochemistry. So we find the complexes structures could influence their properties and it provides the basis for synthesis metal-organic frameworks.