Synthesis, Structure And Properties Of Coordination Bridging Supramolecular Polymer Constructed Through Polycarboxyl

The research of supramolecular and metal coordination complexes is involved in many fields including Organic, Inorganic, solid chemistry, and it is the integration of research with foundation and application. Recently, this area has become the advanced study of crystal chemistry and material chemistry among the internationality. In recent years, much attention has been paid to the designs, synthesis, crystal structures and properties of the carboxylic acid coordination polymer, due to the extensive application of the carboxylic acid coordination polymer, such as catalysis,non-linear optical materials, magnetic materials and porous materials. So, the rational design and coordination polymers based on carboxylate ligand synthesis of novel metal-organic have attracted considerable attention.In this research, four new coordination compounds have been designed and synthesized, with all of them studied systematically by Elemental Analysis, IR and single crystal X-ray diffraction. The results show that the synthesized complexes can be divided into three types, such as one-dimensional (1-D), two-dimensional (2-D) and three-dimensional (3-D) systems. Their crystal structures and spectral properties were characterized.Three new compounds on the basis of 2, 2', 3, 3'--azobenzenetetracarboxylic acid (H4ABTC) of different configurations have been synthesized at room temperature and structurally characterized including one 2-D layered structures constructed by 2, 2', 3, 3'-azobenzenetetracarboxylic acid, and two 3-D frameworks constructed by transition metals. [C₁₆H₁₀N₂O₈]·2H₂O (1) [Mn₂(ABTC) (Phen)₂ (H₂O)4]·3H₂O(2) [Cu(ABTC)_0.5(H₂O)]·0.5H₂O (3) [Zn₂(C₈H₂O₈)(H₂O)₄]_n (4) [Zn(C₁₂H₆N₂O₄)(H₂O)₂] (5)Compounds 1 and 3 have two-dimensional and three-dimensional structures that are only constructed by ABTC and transition metals.1. Compound 1 shows that the structure is located on a centre of symmetry. The two benzene rings are parallel, but not coplanar. The ABTC ligands and the water molecule are linked by hydrogen bands, forming a three-dimensional network.2. The compound 2, [Mn₂(ABTC)(Phen)₂(H₂O)₄]·3H₂O, is a three-dimensional metal-organic polymer. The Mn atom is six-coordinated in a distorted octahedral arrangement. All the Mn atoms are connected by the phen and ABTC ,forming a complicated three-dimensional network.3. The structure of the compound 3,[Cu(ABTC)_0.5(H₂O)]·0.5H₂O,is an assembling of double layers that stacks as ABAB related by a center of symmetry. The polymer exhibits interesting three-dimensional (3D) mesomeric networks assembled from helix-linked sheets.4. Compound 4 [Zn₂(C₈H₂O₈)(H₂O)₄]_n, lies on a center of inversion. Two delocalized carboxylate groups are each connected to two different diaquazinc units, whereas the other two localized carboxylate are each bonded to one different diaquazinc unit. And the metal atom is five-coordinate.5. In the compound 5, [Zn(C₁₂H₆N₂O₄)(H₂O)₂]_n, the Zn atom, located on a twofold axis, is six-coordinated in a distorted octahedral arrangement, with two N atoms and two O atoms of two symmetry-related dcbp ligands located in the equatorial plane,while the two O atoms of the water molecules occupy the axial positions. The dcbp ligand acts as a bridging ligand, linking adjacent Zn ions and forming a one-dimensional infinite chain parallel to the b axis. Hydrogen bonds involving the coordinated water molecules connect adjacent chains to form layers parallel to the (001) plane.The fluorescence of the three compounds 1-3, the exciton are 240nm 298nm 290nm, the emanant are 390nm 403nm 407nm.In these compounds, the O atoms of carboxylate and the water molecules are connected by the hydrogen bonds.Take these compounds more stabilization.