Syntheses, Structures, Electrochemical And Magnatic Properties Of Functional Complexes Based On Triazole And Bis-triazole-bis-amide Ligands

In this thesis,4-amino-1,2,4-triazole （atrz）, bis-triazole-bis-amide ligandsN,N′-di（4H-1,2,4-triazole）cyclohexane-1,4-dicarboxamide （dtcd）,N,N′-di（4H-1,2,4-triazole）butanamide （dtb） and N,N′-di（4H-1,2,4-triazole）hexanamide（dth） have been used as the main ligands and various aromatic polycarboxylic acidshave been selected as the auxiliary ligands to react with transition metal Cu^Ⅱionsunder hydrothermal conditions. Seventeen new complexes have been synthesized andcharacterized by elemental analyses, IR, TG and single-crystal X-ray diffraction. Theelectrochemical, fluorescent and magnetic properties of the title complexes have beenstudied.1. Seven complexes have been hydrothermally synthesized with atrz as mainligand, and different aromatic polycarboxylic acids as auxiliary ligands, reacting withCu^Ⅱions to obtain7complexes. The electrochemical, fluorescent and magneticproperties of some complexes have been explored.[Cu₄（μ3-OH）₂（atrz）₂（DNBA）₆]（1）[Cu₃（μ2-OH）₂（atrz）₂（NPH）₂·（H₂O）₂]·H₂O （2）[Cu₅（atrz）₂（1,3,5-BTC）4·（H₂O）₂]（3）[Cu₄（μ3-OH）₂（atrz）₂（1,3-BDC）₃]·2H₂O （4）[Cu₄（μ3-OH）₂（atrz）₂（SIP）₂]·4H₂O （5）[Cu₄（μ3-OH）₂（atrz）₂（1,2,4-BTC）₂·（H₂O）₂]·3H₂O （6）[Cu₂（μ3-OH）（atrz）（1,2,4-BTC）·（H₂O）]·H₂O （7）In complexes17, the Cu^Ⅱions and atrz ligand were used as center actoms and mainligand, respectively. All the atrz ligands of complexes17adopted bridging bidentatemode （μ-N1, N2-atrz）. In complexes17, the only difference is auxiliary ligands aromaticpolycarboxylic acids, which are divided into single-carboxyl, double-carboxyl and three-carboxyl, and they have a variety of coordination modes, finally forming into0D,1D,2D and3D different structures. Complex1formed into a0D structure with atetranuclear CuⅡ4cluster. Complex2showed a–CuOCu–1D chain. Complex3constructed a2D sheet with two different second building units. Complexes47aresimilar to complex1with the analogical tetranuclear CuⅡ4clusters. Nevertheless,aromatic polycarboxylic acids from complexes47have multiple carboxyls, which areused as linkers building3D frameworks.2. Ten complexes based on CuⅡions have been hydrothermally conduce toforming synthesized with bis-triazole-bis-amide dtcd, dtb and dth as the mainligands and various aromatic polycarboxylic acids as the auxiliary ligands. Theelectrochemical, fluorescent and magnetic properties of some complexes have beeninvestigated.[Cu（dtcd）（DNBA）₂]（8）[Cu（dtcd）（DNBA）₂]（9）[Cu（dtcd）（DNBA）₂]（10）[Cu（dtcd）₂（1,3-HBDC）₂]·2H₂O （11）[Cu（dtcd）（1,3,5-H2BTC）₂]·2H₂O （12）[Cu₄（μ3-OH）₂（dtcd）₂（SIP）₂]·4H₂O （13）[Cu₄（μ3-OH）₂（dtb）（DNBA）₆（H₂O）₂]·2H₂O （14）[Cu（dtb）（DNBA）₂]（15）[Cu₂（dth）（NPH）₂]·2H₂O （16）[Cu（dth）（NIPH）₂]（17）Complexes810were synthesized in one-pot reaction, in which dtcd and DNBAligands were selected as the main ligands and auxiliary ligands, respectively.Complexes14and15were also synthesized in one-pot reaction, in which dtb andDNBA ligands were selected as the main ligands and auxiliary ligands, respectively.They were all influenced by pH of medium and presented a certain regularity. Incomplex8, DNBA ligand adopted a monodentate coordination mode to generate a1Dlinear chain. For complex9, DNBA ligand exhibited a chelate/monodentate-bridgingcoordination mode showing the unique double chains. Different from8and9,10 exhibited a2D network. Polymer14showed a1D Cu^Ⅱ4cluster-based chain linked bythe dtb ligands, whereas polymer15exhibited a1D Cu^Ⅱchain connected by the dtbligands. In complexes1113, dtcd ligand was selected as the main ligands. Complex11showed a discrete uninuclear structure. Complex12afforded a1D chain. Complex13formed into a2D sheet with tetranuclear Cu^Ⅱ4clusters. For complexes16and17,dtcd ligand was used as the main ligands. Complex16was a3D coordination polymerwith a R-Po412.63topology. Complex17generated a3D network structure with a424·64topology. They were all influenced by aromatic carboxylic acid ligands andmolar ratio of reactants.