| The coordination polymer, synthesized with metal and polypyridyl ligands or its derivatives as raw materials, are more and more important for their various structures and extensive uses. The use foreground of these complexes will be extensive in the field of molecular discernment, molecular catalysis, self-assemble, anti-tumour medicine and nucleic acid probe etc. The selection of multifunctional organic ligands and metal ion is crucial to the construction of desirable frameworks. It is of great importance to study of the relationship between design, structure and property and establish proper synthetic strategies and rules leading to desirable supramolecular systems through controlling the assembly process of metal-organic frameworks.In the thesis, A novel polypyridyl ligand 2-(pyridin-3-y1)-1H-imidazo[4,5-f] [1,10]phenanthroline (pyip) has been synthesized. Pyip ligand is good candidate for the construction of novel MOFs for the large conjugated aromatic rings. 16 lanthanide/transition complexes based on pyip ligand were designed and constructed, characterized by elemental analyses, IR spectra, X-ray single crystal diffraction, and luminescence analyses. The results are following:(1) A novel complex 1 has been designed and synthesized with lanthanide metal ion in solution reactions with pyip ligand, [Nd(pyip)2(NO3)3]-4H2O (1); Five new complexes 2-6 have been designed and constructed with transition metal ions by hydrothermal methods, [Cu(pyip)Cl]n (2), [Cu2(pyip)2(OH)2]·4H2O (3), [Mn(pyip)2(H2O)2]·2(ClO4) (4), [Cd(pyip)2(CH3COO)2] (5), [Cd(pyip)2(OH)2]·H2O (6). Among of them, complexes 1, 4, 5, 6 are mononuclear complexes, 2 is one-dimensional chain, 3 is a binuclear complex. Pyip ligand has been found different coordination modes: one is chelate bidentate, the other is bridging monodentate and chelate bidentate. In addition, complexes 5 and 6 exhibit broad photoluminescence.(2) Introducing aromatic dicarboxylic acids auxiliary ligands, three new complexes 7-9 have been synthesized with ZnⅡ ions by hydrothermal methods, [Zn(pyip)(pdc)(H2O)]·2H2O (7), [Zn4(pyip)4(pdc)4]·2[Zn(pyip)2(OH)2]·14H2O (8), [Zn(pyip)(1,4-bdc)(H2O)]n (9) (H2pdc = pyridine-2,6-dicarboxylic acid, 1,4-H2bdc = benzene-1,4-dicarboxylic acid), 7 is mononuclear complex, 8 is comprised of two distinct and crystallographically independent motifs packed together: A(tetranuclear complex) and B(mononuclear complex), 9 is a one-dimensional zigzag chain.(3) Introducing aliphatic dicarboxylic acids auxiliary ligands, seven new complexes 10-16 have been synthesized with d10 transition metal ions (ZnⅡ,CdⅡ) by hydrothermal methods, {[Cd2(pyip)2(ox)2(H2O)][Cd(pyip)(ox)]}n·4nH2O (10), [Cd(pyip)(ox)]n·nH2O (11), [Cd2(pyip)2(suc)2]n·1.5nH2O (12), [Cd(pyip)(glu)]n (13), [Zn(pyip)(glu)]n (14), [Cd3(pyip)2(adip)3]n (15), [Zn(pyip)2(adip)2]n·2.5nH2O (16) (H2ox = oxalic acid, H2suc = succinic acid, H2glu = glutaric acid, H2adip = adipic acid). Among of them, 10 consist of two different 1D infinite chains: a 1D linear chain A units and a 1D zigzag chain B units, which display an interdigitated 1D+1D structure. 11 is a one-dimensional zigzag chain, of which the fundamental unit is same to polymer B in complex 10.12 and 16 have the same one-dimensional double chains with binuclear nodes. 13 is a two-dimensional network with binuclear nodes and 15 is a two-dimensional network with trinuclear nodes. 14 is a one-dimensional wave-like chain. In a comparison of the structures of coordination polymers 13,15 and 14,16, it was found that the final structure of coordination polymers can be tuned by the size of metal ions on carboxyl coordination modes. The photoluminescence behaviour of complexes 7-16 were studied. |
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