The Structures And Properties Of Coordination Compounds Based On The Pyridimine And Terazole Sulfhydryl N-heteroatom Ligand

In recent years,complexes constructed from pyrimidine,tetrazole sulfhydryl N-heteroaton with metal ions of IB and IIB have attracted more and more chemists to research,not only the novel structures,but also the broad application prospects in fluorescence,catalysis,adsorption,biologicalactivityandetc.Inthispaper,wechoose1-methyl-1H-tetrazole-5-thiol?HMMTZ?,1-phenyltetrazole-5-thiol?HPMTZ?and 2-pyrimid-inethiol?Hpymt?as organic ligands with group IB transition metals ions Zn and Cd of IB,group IIB transition metals ions Cu and Ag were used as coordination centers to form nine complexes by solvothermal reaction and solvent evaporation method at temperature.These complexes were characterized by infrared and X-ray single crystal diffraction.X-ray powder diffraction,elemental analysis and other characterization methods to determine and analyze their structure and purity.Then the thermal stability of the nine complexes was studied by thermogravimetry?TG?.The results showed that the stability of the nine complexes was good.In addition,some of the complexes were studied for their fluorescence properties and photocatalytic degradation of organic dyes.The main contents of this paper are as follows:1.Five new compounds with novel structures based on 1-methyl-1H-tetrazole-5-thiol?HMMTZ?ligand and metal ions of Zn?II?,Cd?II?,Cu?I?and Cu?II?were successfully synthesized:a mononuclear structure[?Zn₄O??MMTZ?₆]·EtOH?1?with Zn₄O building unit;a1D chain structure[Zn?MMTZ?₂]_n?2?with an eight-membered ring Zn₂?MMTZ?₂ building unit;a 2D network structure[Cu?MMTZ?]_n?3?with six-membered ring Cu?MMTZ?₄ building unit;a mononuclear structure Cu?en?₂?MMTZ?₂?4?;a 1D chain structure[Cd?MMTZ?₂Cl₂]_n?5?with 1D chain of[Cd₂Cl₂]_n.1,2,5 were synthesized by solvent evaporation method at temperature and 3 and 4 are synthesized by the solvothermal method.At the same time,the reaction conditions revealed that the small molecule halogen-anion ligand Cl^-and ethylenediamine played an important role in the formation of the structure,and they both participated in the coordination with metal centers of 4 and 5.In addition,the solid-state fluorescence analysis of complexes 1-3 were performed,it was found that the fluorescence intensity of 1 and 3 was weak,while complex 2 emitted a strong yellow-green fluorescence under the irradiation of UV lamp and the solvent,cation liquid fluorescence were performed,it was found that it can selectively detect the aniline organic small molecules,Cu²⁺and Fe³⁺.2.Two new compounds with novel structures based on 1-phenyltetrazole-5-thiol?HPMTZ?ligand and metal ions of Ag?I?,Cu?I?were successfully synthesized:a 1D chain structure of silver-chloro complex[Ag₈?PMTZ?₈KCl]_n?6?with thirty-six-membered ring[Ag₁₂C₈S₈N₈KCl₄]building unit;a 2D layered structure of copper iodine complexes[Cu₂?PMTZ?I]_n?7?with an eight-membered ring[Cu₂?PMTZ?₂]building unit and a diamond-shaped Cu₂I₂ unit.6 and 7 were synthesized by the solvethermal method.At the same time,the reaction conditions revealed that the three mixed solvents DMF,CH₃CN,CH₃OH and ethylenediamine were crucial for obtaining crystalline silver halides and copper halide complexes,and the Cl^-and I^-were also participated in the coordination with metal centers,while K⁺played a cationic template role.Moreover,we use the photocatalytic mothod for the degradation of methyl orange?MO?,rhodamine B?Rh B?and methylene blue?MB?by silver-chloro complex 6 under UV light irradiation,it was found that the effect was not obvious.3.Two new compounds with novel structures based on 2-pyrimidinethiol?Hpymt?ligand and metal ions of Ag?I?were successfully synthesized:a 1D chain struture[Ag?mpymt?]_n?9?with Ag₆S₆ structural unit,a 2D layer structure of silver iodide complex[Ag₃?pymt?₂I]_n?10?with 1D Z-Z-shaped[AgI]_n chain and 1D wavy[AgS]_n chain.At the same time,the reaction conditions revealed that the mixed solvents DMF,CH₃CN,CH₃OH,en,and I^-were also crucial for the formation of the structure,and when the solvent methanol was replaced by glycol,the resulting crystal form will be a little better.In addition,the solid-state fluorescence analysis of complexes 9 and 10 were performed,it was found that they have a strong fluorescence intensity.Under the irradiation of ultraviolet light,obvious yellow fluorescence was obversed.