Synthesis Of 1,2,4-pyridyl Triazole Derivatatives And Structure And Properties Of Their Copper Complexes

The study on synthesis, crystal structures and property researches of the complexes of N-containing polydentate ligands has attracted considerable attentions during the past few years for their potentional application in polymeric materials,catalytic materials,biological materials, optical materials and so on. Therefore, it is an important study to design and synthesis of new multi-triazole ligands and self-assembles into complexes which have novel structure and unique properties with metal ions.This paper designed and synthesized four new multi-triazole ligand, four new polymeric were synthesized in this paper by the reaction of the copper inor with 3-(pyridine-2-yl)-1,2,4-triazole under hydrothermal condition.By X-ray collect diffraction data and use SHELXL-97 program solved the crystal structure. The fluorescence properties and thermal stability of part of the complexes were determined. The main results are as follows:1.3-(pyridine-2-yl)-1,2,4-triazole were synthesized by multi-step reaction of 2-cyanopyri-dine(Hpt). Four new triazole derivatives:4,4'-bis{[3-(2-pyridyl)-1,2,4-triazol-1-yl]-methyl}biph-eny,3-(2-pyridyl)-1-(2-methyl pyridine)-1,2,4-triazol,3-(2-pyridyl)-1-(3-methyl pyridine)-1,2,4-triazol,3-(2-pyridyl)-1-(4-methyl pyridine)-1,2, 4-triazol were synthesized and characterized by IR,1H-NMR,13C-NMR.2. Four Cu(Ⅰ), Cu(Ⅱ) complexes were synthesized with hydrothermal synthesis reactor,ofwhich, one is trinuclear coordination polymers [Cu3Hpt3]n with pore structure and three are heterocyclic carboxylic acid complexes [Cu2(Hpt)2(CH3COO)2 (H2O)2]·H2O, [Cu2(Hpt)2(CO3)2(H2O)2]·H2O, [Cu(Hpt)(3,5-DMBA)]n·3. The different type structures of the four complexes have been characterized by X-ray single diffraction. Complexe [Cu3Hpt3]n belong to the monoclinic system,space group:P2(1)/n, In the crystal structure,the central copper ion is coordinated with four atoms,and they form distorted tetrahedron geometry. Complexes [Cu2(Hpt)2(CH3COO)2 (H2O)2]·H2O, [Cu2(Hpt)2(CO3)2(H2O)2]·H2O, [Cu-(Hpt)(3,5-DMBA)]n belong to the triclinic system, space group:P2(1)/n.The three of the complexs form distorted aqua.4. The fluorescence properties and thermal stability of part of the complexes were determined. Thus the luminescent spectra of complex [Cu3Hpt3]n as well as free Hpt were investigated in solid state at room temperature.Experiments show that complex [Cu3Hpt3]n exhibits an intense broad photoluminescence with maximum emission at 414 nm upon excitation at 360 nm, which is a little red-shift than the fi-ee ligand Hpt under the same conditions. Therefore the emission observed in [Cu3Hpt3]n is attributed to theπ-π* intraligand photoluminescence due to its resemblance to that of HL ligand.TGA results of three complexes show that:with increasing temperatu-re, the complexes solvent molecules first, then the complexes were thermal decompo-sition gradually in the higher temperature.