The Synthesis, Structure And Properties Of The Metal-organic Coordination Complexes With Aromatic-1,2,4-triazolates

This dissertation is working for exploring the optimum synthesis condition ofdifferent aromatic-1,2,4-triazolates and its metallic coordination polymers on the basisof different aromatic cyanide and ammonia or amine by the method of in situhydro/solvo-thermal synthesis， and investigated the mechanism of relevant in situreactions. Also, a series of coordination polymers with aromatic-1,2,4-triazolates anddifferent anion ligands have been assembled, and we have systematically investigatedthe influence of auxiliary ionic ligands on the structure and properties ofaromatic-1,2,4-triazolates coordination polymers, as well as, the structure-activityrelationship between the structure and performance has been discussed in this paper.The main contents are summarized as follows:1. The3,3′-Hbpt (3,3′-Hbpt=3,5-bis(4-pyridyl)-1H-1,2,4-triazole),4,4′-Hbpt(4,4′-Hbpt=3,5-bis(4-pyridyl)-1H-1,2,4-triazole) ligands were successfully in suitsynthesized by using3-cyanopyridine or4-cyanopyridine and hydroxylaminehydrochloride or hydroxylamine sulfate under hydrothermal conditions without anymetal ions catalyst, and we have studied the effect of pH, temperature, solvent andmetal salts on the synthesis of aromatic-1,2,4-triazolates. The crystal structure of4,4′-Hbpt ligand have been determined by single-crystal X-ray diffraction analyses, andfurther characterized by elemental analyses, powder X-ray diffraction (PXRD), infraredspectra (IR), nuclear magnetic resonance (NMR) and fluorescence property.2. Two novel zinc halide complexes with4,4′-Hbpt ligand, namely[Zn(4,4′-Hbpt)Cl2]n(1) and [Zn(4,4′-Hbpt)Br2]n(2) have been in suit synthesized byusing4-cyanopyridine and hydroxylamine under the condition of zinc halide acidicaqueous solution. Single crystal X-ray diffraction analysis reveals that complexes1exhibiting a1-D helical chain structure, while complexes2revealing a1-D zigzagachiral chain structure. Their elemental analyses, PXRD, IR, TG analyses andfluorescence properties have been characterized. In addition to, we have tried toinvestigated the antibacterial performance of the aqueous solution of the two complexesand the4,4′-Hbpt ligand, as well as the influence of the chloride, bromide ionic ligands on the structure and properties of coordination polymers was compared and analyzed.3. Four aromatic-1,2,4-triazolates complexes, namely [Cu3(4,4′-Hbpt)2(CN)3]n(3),[Cu2(4,4′-Hbpt)(SCN)2]n(4),[Cd(4,4′-Hbpt)(SCN)2]n(5) and[Cu(4,4′-Hbpt)(CH3CN)2PF6]n(6) have been synthesized under different conditions.Their crystal structures have been determined by single-crystal X-ray diffractionanalyses, and further characterized by elemental analyses, PXRD, IR, TG analyses andfluorescence properties. Complexes3shows a3D nanoporous framework containinglarge elliptical channels, complexes4and5also exhibit3D nanoporous frameworkswith similar pore size. The three complexes have similar thermal stablility andfluorescence properties, all display violet emission band around410nm and begin todecompose at the range of230-250°C for their similar crystal structure. Therefore, therelationship between the similar structure and similar properties has been discussed，which hope to provide a reference for the design and synthesis of multifunctionalmaterials with specific structural on purposes. Complexes6exhibits a1-D linear chainstructure, which is not stable without the protect of concentrate.