| In recent years, with the development of social science and technology, the demands of various functional materials is more and more widely, as the research object of coordination chemistry coordination polymer also gradually attention by researchers in material science disciplines. Coordination polymer is not only the diversity of the structure, and in optical, magnetic, electrical, ferroelectric, dielectric, gas adsorption separation, light (electric) catalytic and biological materials and many other areas show the good performance so make it increasingly attracting the materials science workers’ attention and research. As a result of the Coordination Polymers’ synthesis process is influenced by many factors, their structural is diversity and difficult to predict, so many of their excellent properties has not been discovered.So more and more researchers by choosing appropriate organic ligands, metal ions and controlling reaction conditions to design experiments reasonable, aimd to synthesis new coordination polymer and t study its nature in all aspects, in order to achieve the purpose of use.The study of coordination polymer base on tetrazole is more active in recent years. Mainly due to the tetrazole is a kind of important five-member heterocyclic and with more nitrogen rich electronic conjugated system, so it has the properties that can give electronic and accept electronic meanwhile and four nitrogen atoms ligand with metal ions to form a variety of coordination model, Easy to synthesis novel structure of Coordination Polymers. So increasing the attention of coordination chemistry and material science workers, which is the research emphasis of this paper.Herein,we mainly used tetrazole(3-pyridine tetrazolium,4-pyridine tetrazolium, of benzene m, benzene tetrazolium, the fluorine benzene tetrazolium, etc.) as the first organic bridging ligands, aromatic carboxylic acid (terephthalic acid, all three formate benzene, benzene tetracarboxylic acid, the fluorine, chlorine, bromine, iodine, benzoic acid, etc.) for the auxiliary organic bridging ligands, transition metal (zinc, Cd, Ag, Cu, etc.) for the center with a metal atoms, using in situ synthesis technology, successfully synthesize 18 novel coordination polymer was not reported in the literature by simply hydrothermal method or solvent hot method. Explores the different ligands and auxiliary ligand and metal ions at different reaction conditions (raw material proportioning, pH value of solution, reaction temperature and time, different solvents etc.) the influence to the synthesis and structure of these coordination polymer. And using infrared spectrum, element analysis, thermogravimetric analysis, single crystal diffraction (XRD) characterization methods, analyzed their crystal structure, also studied their photoluminescence properties and mechanism of the band of their theoretical calculation, and dielectric properties of ferroelectric behavior research. The mainly content of this thesis is as follows:1) The synthetize of Zn(Ⅱ) mental coordination polymers{Zn[4-Fluorobenzonitetrazole)]2}n (2a)、{Zn[4-Fluorobenzonitetrazole)]2}n (2b) based on 5-Phenyl-1H-tetrazole and 4-Fluorobenzoic tetrazole. Using 4-Fluorobenzonitrile as raw material, with zinc salt as Lewis acid catalyst,by hydrothermal in situ [2+3] cycloaddition, Under different reaction temperature two novel chiral CPs were orbtained. CP2a and 2b are polymorphism, CP2a is Tetragonal Crystal system and I-42d Space group,but CP2b is Cubic Crystal system and F-43m Space group. Each Zn centre is four coordination in a similar Slightly distorted tetrahedron. The ligands of CP1 uesμ2-bridg link mode,It features a interpenetrating diamond framework. We mainly study the fluorescence emission, ferroelectric, dielectric, and the nature of the catalytic degradation of dye, And the band gap and density of state(DOS) the theoretical calculation. Ferroelectric indicates that the complexes with ferroelectric behavior, and dielectric constant is very stability with the change of frequency, temperature and bias voltage. It’s potential application as low k dielectric materials are important.2) Compounds {[Cd2(4-ptz)(SO4)(OH)(H2O)2](H2O)}n (3a)、{[Cd2(4-ptz)(SO4)(OH) (H2O)]}n (3b) and [Cd(4-ptz)2(H2O)4](H2O)2 (3c) were synthesis by reacting 4-Cyanopyridine with Sodium azide by in situ hydrothermal synthesis with cadmium sulfate as catalyst,under different pH. [Cu3(C6H4N5)-(CN)2]n(3e) and [Ag2(C6H4N4)(N3)]n(3d) were synthesis with copper cyanide and silver nitrate as catalyst. We also use 4-Nitrobenzoic acid、3-Nitrobenzoic acid as auxiliary carboxylic acid ligands, wo gain the coordination compounds (3f)、(3g). The structure of coordination compounds 3a,3b and 3c was mainly affected by solvent pH, the CPs(3e) and (3d) show that different metal ions also leads to different structure of the product. And the auxiliary carboxylic acid ligands affect the structure of the CPs (3f)、(3g).3) Zn(Ⅱ)/Cd(Ⅱ) metal CPs based on 5-(3-Pyridy1)-1H-tetrazole. Using 3-Cyanopyridine as Organic cyanogen. Via the hydrothermal method, five complexes with two-dimensional structure were synthesized [Cd(3-pttz)(4-Clba)]n(4a)、[Cd(3-pttz)(4-Brba)]n (4b)、 [Cd(3-pttz)(4-Iba)]n (4c)、[Zn(3-pttz)(4-Clba)]n(4d) and [Zn(3-pttz)(4-Brba)]n (4e), and they are isologues. The DOS calculate by theory demonstrate that fluorescence of CP4a、4b、4e come from π-π* electron transition interligand. In order to study the influence of auxiliary carboxylic acid ligands on structure, we use 1,3,5-Trimesic Acid、4-Methylbenzoic acid, 3,5-Dinitrobenzoic acid、4-Nitrobenzoic acid、3-Nitrobenzoic acid as auxiliary carboxylic acid ligands,five CPs were gained (4f)、(4g)、(4h)、(4i)、(4j).4) The Cd(II)metal CPs based on 1,4-H2BDT. Using 1,4-Benzenedicarbonitrile as precuesor, oxalic acid and 1,4-dicarboxybenzene as second ligand, two novel coordination polymers containing Cd(II) have been synthesized via in situ hydrothermal technology. Compounds 5a and 5bhave the same link organic ligand 1,4-Bis(cyano)benzene, but different auxiliary carboxylic acid ligand leads to different coordination model, form two very difference three-dimensional molecular structure.The (1,4-H2BDT) bonds with Cd and Na ions in μ3 coordination models to form three-dimensional pore channel structure in compound 5a and bonds with Cd and Mn ions in μ2- coordination models to form three-dimensional structure in compound 5b. The porosity of complexes 5a can reach 39% by theoretical calculation, it has the potential application as the gas absorption material. |
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