The Synthesis,Structure And Properties Of Complexes Based On Sulfhydryl Nitrogen Heterocyclic Ligands

For the synthesis of coordination compounds,the targeted synthesis of specific structural and functional complexes remains a complex challenge for researchers.Since mercapto nitrogen heterocyclic ligands generally have two coordination atoms of N and S,the coordination modes are diversified,and in recent years,complexes synthesized with various metal ions have various structures,in biological activity,catalysis,medicine,and adsorption.,fluorescence and other fields have shown a unique application prospects.In this paper,the fluorenyl nitrogen heterocyclic ligand 1-?4-hydroxyphenyl?-5-mercaptotetrazole?HOPMTZ?and 2-mercapto-5-methyl-1,3,4-thiadiazole?Hmthd?are used.Nine fluorescent complexes were synthesized under solvothermal conditions in copper,silver,zinc and manganese.The structure and properties were tested and characterized.The details are as follows:1.Using 1-?4-hydroxyphenyl?-5-mercaptotetrazole?HOPMTZ?as the organic ligand and Cu?I?and Ag?I?as the coordination center metal,synthesized by solvothermal method.Two complexes:{[Cu?OPMTZ?]·H₂O}_n?1?and[Ag?OPMTZ?]_n?2?.Due to the strong coordination of ethylenediamine and copper,the amount of ethylenediamine added is appropriate.Both complexes 1 and 2 are 2D layered structures.2.Using 2-mercapto-5-methyl-1,3,4-thiadiazole?Hmthd?as organic ligand,seven complexes were synthesized under the conditions of changing reaction solvent,temperature and pH:[Cu₄I?DMT?₃]_n?3?,[Cu₃?mthd?₂Br]_n?4?,[Ag₂?mthd?₂]_n?5?,[Ag₂?mthd?I]n?6?,[Cu?mthd?₂Cl]_n?7?,[Zn₄?OH?₆?SO₄?·3H₂O]_n?8?and[?H₃O?₂Mn₂?SO₄?₃]_n?9?.The complexes were tested for infrared,solid fluorescence,thermogravimetry and PXRD.In complex 3,acetonitrile forms a 2,5-dimethyl-1,3,4 triazole ligand in situ under the catalysis of copper?I?.Although Hmthd does not participate in the reaction,it cultures the crystal.Played an important role.The complex 3 is constructed by a Cu₄I secondary structural unit and an organic ligand to form a three-dimensional left-handed spiral channel structure.The fluorescence spectrum of complex 3 shows that different excitation wavelengths can change the luminescence properties of the compound,emitting blue-violet light between excitation wavelengths of 280-320 nm,and emitting yellow light at 330-410 nm.The complexes 4,5,and 6 are all two-dimensional layered structures.The solid fluorescent properties of the complex 5 and the complex 6 were measured and found to be yellow fluorescent under the irradiation of an ultraviolet lamp.Complex 7 has a zero dimensional structure.Complex 8 and complex 9 are inorganic salt compounds,complex 8 is a two-dimensional layered structure,sulfate is suspended on a two-dimensional layer;complex 9 is a three-dimensional inorganic manganese sulfate skeleton,and protonated water molecules are filled in the skeleton.