The Synthesis,structures And Properties Of Cu, Ag Coordination Compounds Based On The Sulfhydryl N-heteroatom Ligand

Copper and silver compounds have attracted great attention on many scientific researchers due to their intriguing structures and photophysical behavior.The sulfhydryl N-heteroatom ligands is also widely used in the synthesis of compounds,because of they have two kinds of coordinating atoms: N and S atoms and easy to coordinate with Cu and Ag ions.In this paper,twelve complexes with distinct performance were synthesized based on 1-phenyl-5-mercaptotetrazole（HPMTZ）,2-mercapto-4-methylpyrimidine（Hmpymt）,2-mercaptopyrimidine（Hpymt）,3-mercapto-1,2,4-triaz（HtrzSH）and Cu,Ag ions under solvothermal conditions.The structure and properties of the complexes were characterized by single crystal X-ray diffraction,infrared spectroscopy,thermogravimetric analysis,XRD and fluorescence.The details are as follows:1.Four compounds based on HPMTZ ligand and Cu（I）,Ag（I）ions were successfully synthesized under solvothermal method,namely: [Ag（PMTZ）]_n（1）,[Ag₈（PMTZ）8KCl]_n（2）,[Ag₂（PMTZ）I]_n（3）,[Cu2（PMTZ）I]_n（4）.Compound 1 exhibits 1D chain structure because the HPMTZ ligand is directly linked to the Ag（I）ion.In compound 2,the HPMTZ ligand and Cl anion are linked Ag（I）and K（I）ions to form a 1D framework and via C-H···π bonding and π-π stacking interactions form a 3D supramolecular structure.Compounds 3 and 4 have similar 2D framework which are connected by [M（PMTZ）]_n layer and [MI]_n layer.Fluorescence analysis revealed that the emissions of compounds 1-4 are similar to HPMTA ligand,due to the π*→π and π*→n transition within the ligand.2.Four compounds with Cu₆S₆ cluster based on Hmpymt ligand and Hpymt ligand and Cu（I）ions were synthesized under solvothermal method,namely: [Cu3（mpymt）3]2（5）,{（Cu4Br4）[Cu6（mpymt）6]}n（6）,{[（Cu6I6）[Cu6（mpymt）6]}n（7）,[Cu3（pymt）3]2（8）.Compounds 5 and 8 are interconnected by Cu atoms and S atoms to form a compound with Cu₆S₆ structure.Compound 6 displays an interesting 3D framework constructed from Cu₆S₆ and Cu4Br4 clusters simultaneously.Compound 7 displays an infinite 1D framework constructed from Cu₆S₆ and Cu6I6 Cu（I）clusters.The reaction conditions reveal that the ethylenediamine and CH3 CN play an important role in the preparation of compounds 5-8.The solid-state luminescent properties of compounds 5-8 were investigated,it was found that they had strong fluorescence and red fluorescence emission was observed under UV light,which could be detected organic small molecules and metal ions as fluorescent probes.We have investigated the fluorescent properties of compounds 5-7 in various solvent emulsions in detail,the results of which indicate that compounds 5-7 are all highly sensitive naked eye colorimetric sensors for NB,2-NT and Fe3+.3.Two compounds based on Hmpymt ligand and Ag（I）ions were synthesized under solvothermal method,namely: [Ag（mpymt）]_n（9）,[Ag4（mpymt）2Cl2]_n（10）.Both compounds 9 and 10 are formed by ligands and metal ions to form a 2D layered framework.We can also observed obvious yellow-green fluorescence emission under the UV light of compounds 9 and 10,which can also be used as organic small molecules or metal ions fluorescent probe.4.Two compounds based on HtrzSH ligand and HPMTZ ligand and Cu（Ⅱ）ions were synthesized under solvothermal method,namely: {[CuII3（μ3-O）（μ3-trz）3（OH）（H2O）6]}n（11）,[（CuIISO4）4（K2O4）]_n（12）.Compounds 11 were synthesized under solvothermal method,the HtrzSH ligand was desulfurized to form the Htrz ligand reacts with Cu（Ⅱ）ion to form the compound with 3D framework structure.Compounds 12 were also synthesized under solvothermal conditions,HPMTZ was desulfurized and the corresponding thiol was oxidized into SO42-,which connects Cu（Ⅱ）ion and K（I）ion formed with a 3D framework structure.