The Synthesis And Properties Of Transition Metals And N-containing Hybrid Organic Ligands Based Coordination Polymers

In this thesis,5-[4-?1H-Imidazol-1-yl?phenyl]-1H-tetrazole?HL?ligand and three different carboxylate ligands?H₂pbda,H₃btc,H₂ip?have been selected as the ligands to obtain three new coordination compounds based on Cu^IIions.The organic ligand1-?tetrazo-5-yl?-4-?triazo-1-yl?benzene?Httbz?has been selected as the main ligands,and three different carboxylate ligands?H₂pbda and H₃btc?have been used as the auxiliary ligands to react with different transition metals,obtaining three new coordination compounds.Six new complexes have been synthesized and characterized by single-crystal X-ray diffraction,IR,elemental analyses and X-ray powder diffraction?XRPD?patterns.In addition,the TG,fluorescent properties,electrochemical behaviors and catalytic oxidation activities of some complexes have been studied.1?Using the 5-[4-?1H-Imidazol-1-yl?phenyl]-1H-tetrazole?HL?ligand and three different carboxylate ligands,a series of coordination compounds based on Cu^IIions have been synthesized under hydrothermal conditions and structurally characterized.We study on the roles of different reaction conditions,the coordination modes and the different substituent groups of the ligands for structures of complexes.[Cu?L??pbda?_0.5?H₂O?]?1?[Cu₂?L??H₂btc?₂?OH?]?2?[Cu₅?L?₄?ip?₂?OH?₂?H₂O?₂]·2H₂O?3?Complex 1 represents“weave”-type 2D layers consisting of wave-like 1D chains and1D straight chains,which are further connected by hydrogen bonds to form a 3D supramolecular structure.Complex 2 exhibits a uninodal?4?-connected 2D layer with a point symbol of{4⁴·6²},in which the L ligand can be described as?₅-bridge and the H₂btc^-ions display multiple kinds of coordination modes to connect Cu?II?ions into 1D“H”-type Cu-H₂btc chains.In complex 3,2D Cu-L layers with two kinds of grids and 1D“stair”-type Cu-ip chains link each other to construct a 3D{4¹²·6³}framework,which contains the pentanuclear subunits.Deprotonated degree and coordination modes of carboxylate ligands may consequentially influence the coordination patterns of main ligands and the final structures of complexes 1–3.Furthermore,electrochemical behaviors and electrocatalytic activities of the title complexes have been analyzed at room temperature,suggesting practical applications in areas of electrocatalytic reduction toward nitrite and hydrogen dioxide in aqueous solutions,respectively.2?Using the main ligand 1-?tetrazo-5-yl?-4-?triazo-1-yl?benzene?Httbz?and different aromatic carboxylate ligands,three coordination compounds based on different transition metal ions have been hydrothermally synthesized and structurally characterized.Study on the roles of metal ions and the coordination modes of ligands for sructures of complexes.[Cu₂?ttbz??H₂btc?₂?OH?]_n?4?[Mn?ttbz?₂?H₂O?₂]_n?5?[Cu?ttbz?₂?H₂O?₂]_n?6?Complex 4 exhibits a?3,5,5,5?-connected 2D layer with a Schl?fli symbol of{3·4²}{3·4⁴·5²·6³}{3²·4⁴·5²·6²}{3²·4⁴·5³·6},in which the ttbz ligand can be described as?₅-bridge and the H₂btc^-ions display multiple kinds of coordination modes:monodentate and bidentate,linking Cu?II?ions into 1 D“H”-type Cu-H₂btc chains.The ttbz ligand in complex 4 and complex 5 represents the bridging coordination mode,connecting two Cu?II?/Mn?II?ions to the infinite 1D zigzag chains,respectively,which are further connected by two different types of hydrogen bonds to form a 3D supramolecular.Furthermore,catalytic oxidation activities toward organic dyes as well as electrochemical behaviors and electrocatalytic activities of the title complexes have been investigated at room temperature in aqueous solutions,indicating these complexes may be applicable to color removal in a textile wastewater stream and practical applications in areas of electrocatalytic reduction toward nitrite,respectively.