Study On The Construction And Fluorescence Properties Of The Complexes Of Mercaptopyrimidine Ligands With Cu(?)

Metal organic framework,are formed by the coordinate assembly of organic ligands and central metal ions through coordination bonds.Recently,due to the unique structure and performance,the compound has attracted more and more attention.In the complex synthesis process,it plays a vital role for the ideal ligand to construct the structure of complex.The traditional organic ligands are N and O type ligands,so there are little studies on S-containing ligands.Herein,we present the synthesis of eleven new metal-organic framework with N,S ligands?such as 4-?3-pyridyl?-2-mercaptopyrimidine?HTTP-3?,4-?4-pyridyl?-2-mercaptopyr-imidine?HTTP-4?,4,6-dime-thyl-2-mercaptopyrimidine?Hmpymt?,2-mercapto-4-methylpyri-midines?Hdmpymt??and metal salts?CuCl,CuBr,CuI,CuCN,CuSCN?,and then the structure and performance were characterized through single crystal X-ray diffraction,elemental analysis,infrared spectroscopy,thermogravimetric analysis and PXRD.1.Four novel metal-organic framework[Cu?3-ppds?Br]_n?1?,[Cu?3-ppds?I]_n?2?,[Cu₂?3-ppds??CN?₂]_n?3?,[Cu₂?3-ppds??SCN?₄]_n?4??3-ppds=di?4-?pyridin-3-yl?pyrimidin-2-yl?disulfide?,was solvothermally synthesized by 4-?3-pyridyl?-2-mercaptopyrimidine and the metal salts?CuBr,CuI,CuCN,CuSCN?.The structure analysis,it was concluded that compounds 1,2,3 exbibits a two-dimensional layered structureand,the compound 4 exhibit a3D network structure,and they are isomorphic of complexes 1 and 2,the different construction also conclude that different halogens play a vital role in regulating the structure of the compound.In addition,it is worth noting that the 3-ppds is formed by the situ reaction of the ligand of HTTP-3.After measuring the performance,as a result,the compound 2,exhibits the best the fluorescence intensity,which compared with compound 1?3?4,So we explored furtherly the fluorescence performance of the compound 2.Finally we found that the compound 2 show outstanding selectivity towards NB,and its corresponding K_SV=7.59163×10⁴M^-1.2.The three compound[Cu₂?4-ppds??Cl?₂]_n?5?and[Cu₂?4-ppds??CN?₂]_n?6?and[Cu₂?4-ppds??CN?₂]_n?7??4-ppds=di?4-?pyridin-4-yl?pyrimidin-2-yl?disulfide?,were formed successfully which were construction from the ligand 4-?4-pyridyl?-2-mercaptopyrimidine and the metal salts?CuCL and CuCN?.their structural analysis revealed that the compound 6and 7 exhibit 3D network structures,and 8 exhibits a two-dimensional layered structure,in which the complex 6 and 7 have a isomorphic structure.Meanwhile the 4-ppds was synthesized by the situ raction of HTTP-4.3.The ligand 2-mercapto-4-methylpyrimidine is coordinated with the metal salts CuCN and CuSCN to synthesize two compound{[Cu₃?Hmpymt?₃]?CuCN?₂}_n?8?,{[Cu₃?Hmpymt?₃]?CuSCN?}_n?9?,the result show that the 3D network structure of the two compound is formed by Cu₆?Hmpymt?₆ main structural unit and CuX secondary structural unit through interpenetration after analyzing the structure.Moreover,the compound 8 and 9 show a excellent fluorescence performance.Compound 8 show luminescence emission peak at647nm when the characteristic excitation peaks at 420nm.Compound 9 show luminescence emission peak at 686nm when the characteristic excitation peaks at 430nm.The luminescene peaks emission of excitation and emission of the compound can be attributed to electron transfer and ligand-metal charge transfer.These all indicate that the complexes 8 and 9 have potential applications in luminescene sensors.4.The compound{[Cu₃?dmpymt?₃]?CuCN?₂}_n?10?and Cu₆S₆ byproduct{Cu?en?₂[Cu₂?SCN?₄]}_n?11?has been synehesized by 4,6-dimethyl-2-mercaptopyrimidine and metal salts?CuCN and CuSCN?.After analyzed structure,the result show that the compound10 have the same two structural units Cu₆?dmpymt?₆ and CuX as 8?9.And its 3D network structure are form by interpenetrated OF the two structural units.The performance is studied and show that the complex 10 is expected to be a potential material for fluorescence sensors.Analyzed structure of the compound 11,the result show that{Cu?en?₂[Cu₂?SCN?₄]}_n?11?exists in a two-dimensional layered structure.