Syntheses, Structure And Property Studies Of Coordination Polymers Constructed Through Derivatives Of 4, 5-Diazafluoren-9-one

Metal-organic coordination polymers-a new kind of functional molecule materials- have attracted much more attentions for their flexible tailoring, various topologies and promising application in ion-exchange, adsorption, molecular recognization, catalysts along with optics, electrics, magnetism and enantioslective separation. According to the principle of crystal engineering, it is possible that rational design and synthesis of porous crystalline materials by selecting certain geometric metal ions and special organic ligands; At the same time, coordination polymers can be endowed with optics, electric, magnetism, enantioselective separation and catalysis by selecting functional metal ions and organic ligands with functional groups. To today, there have been a lot of reports on coordination polymers, which generally constructed from various N-containing chelating bidentate ligand such as phen and Dafo. It is also important to synthesize the novel structure N-containing ligands which have widely developing space and potential application. Through modifying or synthesis the novel N-containing ligands and selecting suitable secondary multi-carboxylic ligands, a series of novel funditional materials with a range of special optics, electrics, magnetism properties can be designed and synthesized. In this filed, it is noteworthy that many hybrid compounds have been gotten by C. N. R. Rao, Kitagawa, Yaghi. A strategy based on selecting different size, different shape aromatic carboxylic and neutral N-containing ligands has been applied for the design and synthesis of new functional coordination polymers of porous and interpenetrating coordination polymers. Here, Three new polypyridine ligands of 4,5-diazafluorene-9-one oxime(L1), 2-(4,5-Diazafluoren-9-ylideneamino)phenol(L2) and 4-(4,5-Diazafluoren-9-ylideneamino) benzoic acid(L3) have been successfully synthesized. From the viewpoint of molecular design, two rigid polycarboxyl ligands have been introduced into the complexes as the secondary ligands. A novel Three-Dimensional coordinaton polymer[Zn₂(L1) (tp)_1.5(OH)](H₂O) 1 has been constructed with L1 in the presence of an additional terephthalate. It is noteworthy that the structure consisits of interpenetrating six-connected topology nets. In its most symmetrical form this net consists of nodes with a chair form(Zn4O₂)building of μ3-O bridge and Zn(II) and has a primitive cubic unit cell building of terephthalate. At the same time another three-dimensional coordination coordination polymer[Zn₂(L1)(btec)_0.5(OH)₂] 2 have been obtained bridging in 1,2,4,5-benzenete- tracarboxylate. The presence of μ2-O bridge result in the increment of the dimension of polymers. Tortile octagonal Zn₄O₄ building of μ2-O is edge-bridged by four carboxylates to give a novel topology structure. Viewed along the c zxis, there are channels(10.8A×8.15A)in the structure filled by L1 ligands. Amino acid is a kind of well-exploited ligand and it has more coordinated sites, so it is of great interest in biochemisty and other fields. Here a flexible ligand 4-acetamidobenzic acid was used for ligand to form complex.Two 3-dimensional suparmolecular coordination polymer [Cd(CH₃CONHC₆H₄COO)₂·4(H₂O)]·2(H₂O) 3 and [Zn(CH₃CONHC₆H₄ COO)₂·4(H₂O)]·2(H₂O) 4 have been got in the condition of existing of the transition metal Zn(II) and Cd(II). The crystal structure of the compound was determined by X-ray diffraction. The result shows that the crystal possesses three 3-dimensional infinite network structure constructed by many kinds hydrogen bond, forming the supramolecule. The various kinds of hydrogen bond in the compound and their effect on the crystal structure are discussed. At last the spectra studies are here.