Synthesis, Structures And Properties Of Metal-organic Coordination Polymers Based On Substituted Benzenedicarboxylic Acid

In this dissertation, eighteen novel metal-organic coordination polymers have been synthesized under ambient conditions or hydro(solvo)thermally by reaction of the substituted benzenedicarboxylic acid [5-amino-2,4,6-triiodoisophthalic acid(H2ATIBDC),5-amino-2,4,6-tribromoisophthalic acid (H2B3C) and2-iodine terephthalic acid(H2ITPC)] with metal(II) ions (Cd2+,Zn2+,Pb2+,Co2+,Ni2+) in the presence of N-containing auxiliary ligands, such as4,4-azobipyridine (azpy),1,4-bis(imidazolyl-l-methyl) benzene (1,4-bix) and1,4-bis(imidazolyl)butane (bimb). All the complexes have been structurally characterized by single crystal x-ray diffraction. The reaction conditions and rules of these intriguing complexes were investigated in detail. We found that metal ions, N-containing auxiliary ligands and the ratios of solvents exert a profound influence on the final framework architectures. Moreover, thermal stabilities, the fluorescent properties, powder XRD and gas adsorption properties of some complexes have been studied.1. Six novel metal(Ⅱ)-organic frameworks based on5-amino-2,4,6-triiodoisophthalic acid (H2ATIBDC) and2-iodine terephthalic acid (H2ITPC) in the presence of N-containing auxiliary4,4-azobipyridine(azpy), have been synthesized under ambient conditions. Complexes [Zn(AZPY)(H2O)4](ATIBDC)·0.5(AZPY)·4H2O (1),[Ni(AZPY)(H2O)4]·(ATIBDC)-0.5(AZPY)5H2O (2),[Co(AZPY)(H2O)4]·(ATIBDC)-0.5(AZPY)·5H2O (3) possess one-dimensional structure.The M2+ions are linked by azpy ligands in these two complexes.[Pb(ATIBDC)2(azpy)]·H2O (4) exhibits1D chain structure, two Pb2+atoms are joined by5-amino-2,4,6-triiodoisophthalate.[Pb2(ITPC)2(DMF)(H2O)]·H2O (5) is a three-dimensional(3D) network. In [Cd(ATIBDC)(AZPY)(H2O)2]·2H2O (6), both5-amino-2,4,6-triiodoisophthalate and azpy act as bridging ligands, resulting in the formation of3-fold interpenetrating3D architecture with Schlafli symbol [(66)(64.82)2]. The effect of center metal ion and the ligands on the crystalline architecture have been discussed. 2. Seven novel Co(Ⅱ)/Ni(Ⅱ) coordination polymers7-13constructed based on5-amino-2,4,6-tribromisophthalic acid (H2B3C) in the presence of N-containing auxiliary have been synthesized as follows [Co(B3C)(bimb)](7),[Co2(B3C)2(bix)4(H2O)2]·6H2O (8),[Co(B3C)(btb)(H20)2]·3H20(9),[Co2(B3C)2(bbtz)25(H2O)3]·5H2O (10),[Ni(B3C)(bbtz)(H2O)2]·3H2O (11),[Co(B3C)(azpy)15(H2O)2]·3H2O (12),[Ni(B3C)(azpy)(H2O)2]·3H2O (13). Complex7shows a1D double-chain structure in which both5-amino-2,4,6-tribromisophthalic acid (H2B3C) and azpy act as bridging ligands. Complex8is a2D (4,4) topological network. Complex9is a1D double-chain structure. Complex10exhibits a two dimensional(2D) double layer architecture,5-amino-2,4,6-tribromisophthalic acid (H2B3C) and azpy as bridging ligands. Complex11features a3D framework with Schlafli symbol is (54.62). In complex12, both5-amino-2,4,6-tribromisophthalic acid (B3C2-) and azpy act as bridging ligands, connecting Co2+ions, leading to the formation of3-fold interpenetrating3D4-connected quartz network. The structure of13is similar to that of12, but has different topology with Schlafli symbol (33.42.5). The effect of the ancillary ligands and center metal ions on the crystalline architecture of7-13have been discussed.3. Five new new d10metal-organic frameworks14-18based on5-amino-2,4,6-tribromisophthalic acid (H2B3C) in the presence of N-containing auxiliary ligands, namely,[ZnCl(B3C)(bbtz)](14),[Zn(B3C)(bbtz)(H2O)]·H2O (15),[Cd(B3C)(bbtz)(H2O)]·H2O (16),[Zn(B3C)(azpy)(H2O)3]·0.5(azpy)·2H2O (17),[Cd(B3C)(azpy)(H2O)2]·0.5(azpy)·4H2O (18), have been synthesized. Complex14exhibits a one-dimensional (ID) chain structure. In complex15,5-amino-2,4,6-tribromisophthalic acid (B3C2-) as a chelating ligand to connect Zn2+ions, and azpy as bidentate ligand, resulting in the formation of4-connected3D topology. Schlafli symbol is (52.62.7.10). Complex16shows a3D framework architecture with Schlafli symbol (65.8) in which5-amino-2,4,6-tribromisophthalic acid (B3C2-) acts as a chelating ligand to connect Cd2+ions, and azpy as bidentate ligand. The work here further shows that the cosolvents and center metal ions have great influence on the crystalline architectures of some MOFs. In17,5-amino-2,4,6-tribromisophthalic acid (B3C2-) acts as a bidentate ligand linking Zn2+ions, and azpy as chelating ligand, resulting in the formation of4-connected quartz topology, three similar3D architectures are interpenetrated to afford a3-fold interpenetrating3D architecture. Complex18is similar to that of17. The effects of center metal ion on the crystalline architectures have been studied.