Synthesis,Crystal Structure And Property Studies On Metal Coordination Polymers With Azobenzoic Dicarboxylic Acid And Chiniofon

Due to the structural diversity and the potential applications in optical material, magnetic material, superconductor material and catalysts, etc., the research on coordination polymers has become the frontier basic and application researches field. This thesis focuses on the synthesis of 14 kinds of coordination polymers with different dimensions, by using azobenzoic dicarboxylic acid, sulfonic acid, bridge and chelate ligand to react with alkaline earth, rare earth and 3d ions under the hydro(solv) thermal condition. Their crystal structures have been revealed through X-ray single crystal diffraction methods. Meanwhile, they have been characterized by IR, TGA, fluorescence spectra. This thesis consists of 5 chapters.Chapter 1 is the preface, describing a brief introduction on the development, the present research statement and the coordination modes of several kinds of important ligands and the progress we have made. In chapter 2, four 1D coordination polymers {[Co(4,4'-Azo)(py)2(H2O)2]·2py}n (1), [Zn(4,4'-Azo)(py)2]n (2), {[Cu(4,4'-Azo)(py)(H2O)]·0.5H2O}n (3) and {[Cu(4,4'-Azo)(phen)(H2O)]·0.5DMA}n (4) have been reported. Complex 1, 2, 3 belong to triclinic crystal system with space group P-1. In 1, the coordination geometry of Co(Ⅱ) center a six-coordinated distorted octahedron. 1 is a 1D chain complex connected by bridging 4,4'-azobenzoic dicarboxylate; In 2, the coordination geometry for the five-coordinated center Zn (Ⅱ) is a distorted square pyramid. Similar to 1, 2 is a zigzag chains of Zn bridged by 4,4'-azobenzoic dicarboxylate. The coordination geometry for the four-coordinated center Cu(Ⅱ) is a distorted square in complex 3, which also is a 1D chain connected by bridging 4,4'-azobenzoic dicarboxylate. Complex 4 belongs to monoclinic crystal system with space group P2(1)/n. The coordination geometry for the five-coordinated center Cu(Ⅱ) is a distorted square pyramid. The structure of complex 4 consists of zigzag chains of copper(II) connected by 4,4'-azobenzoic dicarboxylate ligands. The TGA and IR of four coordination polymers are well agree with the crystal structures.In chapter 3, three 2D coordination polymers [RE(3'3-Azo)1.5(phen)]n (RE=Y(5),Sm(6),Er(7))have been synthesized. X-ray single crystal diffraction analysis indicated that they possess very similar structural features. All three complexes belong to monoclinic crystal system with P2(1)/n space group. The coordination geometry for the eight-coordinated RE(Ⅲ) center is a trigonal dodecahedron and surrounded by six O and two N atoms from four 3,3'-ADB and one 1,10-phen ligands, respectively. 3,3'-ADB have two coordination modes,chelate (a) and bridge (b).They have very similar TG curves,still stable when the temperature near 400℃。In chapter 4, two 3D pillar-like coordination polymers [Ba(4,4'-Azo)]n (8) and [Mn(4,4'-Azo)(H2O)2]n (9) have been synthesized. Complex 8 belongs to orthorhombic crystal system with space group Pbca. The coordination geometry for the eight-coordinated Ba(Ⅱ) center is a distorted square antiprism and coordinated by eight oxygens from seven 4,4'-ADB. Ba(II) atoms are bridged by the 4,4'-azobenzoic dicarboxylate anions to form inorganic plymeric layers as honeycomb. 4,4'-ADB plays a role of organic pillar, which exhibited an unusual eight dentate binding fashion (f) to link the BaO layer into 3D pillar-like structures. Complex 9 belongs to monoclinic crystal system with space group P2(1)/c. The coordination geometry for the six-coordinated Mn(Ⅱ) center is a distorted octahedron and surrounded by six oxygens from four 4,4'-ADB ligands and two H2O. Mn(II) are bridged by the 4,4'-azobenzoic dicarboxylate anions to form inorganic plymeric layers. 4,4'-ADB plays a role of organic pillar, which exhibited anti-anti bidentate bridge binding fashion (e) to link the MnO layer into 3D pillar-like structures. The TGA and IR of two coordination polymers are well agree with the crystal structures.In chapter 5, four 1D coordination polymers[Ni(IHQS)(4,4'-bpy)0.5(H2O)2]n (10), [Cu(IHQS)(4,4'-bpy)0.5(H2O)]n (11), {[Mn(IHQS)(H2O)2]·2H2O}n (13), [Cd(HQS)(phen)]n (14) and a dinuclear complex [Cu(IHQS)(bpe)0.5(H2O)2]n (12) have been synthesized. Complex 10, 12 belong to monoclinic crystal system with space group P2(1)/n. In 10, the coordination geometry for the six-coordinated Ni(Ⅱ) center is a distorted octahedron. Ni(Ⅱ) is coordinated by two IHQS to form a dinuclear unit. 10 is a 1D infinite chain connected by bridging 4,4'-bpy. The coordination geometry for the five-coordinated center Cu(Ⅱ) is a distorted square pyramid in complex 12, two Cu(Ⅱ) were bridged by bpe to form a dinuclear unit. Complex 11, 13, 14 belong to triclinic crystal system with space group P-1. In 11, the coordination geometry for the five-coordinated Cu(Ⅱ) center is a distorted square pyramid, in which the Cu(Ⅱ) was linked by IHQS to form a infinite chain, and further generated a 1D ladder bichain structure by bridging 4,4'-bpy. The coordination geometry for the six-coordinated center Mn(Ⅱ) is a distorted octahedron in complex 13, every two IHQS adopt bridged (i) to link two Mn(Ⅱ) to form a infinite line of cage; the coordination geometry for the six-coordinated center Cd(Ⅱ) is close to a distorted octahedron in complex 14. The Cd(Ⅱ) is coordinated by two ox from two IHQS to form a dinuclear unit(j), and further formed a 1D infinite chain by bridging the unit with inverted IHQS.The TGA and IR of five coordination polymers are well agree with the crystal structures. Compound 14 emits intensive fluorescence at 488nm upon radiation UV light in solid sate at room temperature.