Synthesis And Characterization Of Coordination Polymers Constructed By Flexible Carboxylic Acids And Heterocyclic Thione Ligands

In recent years,The coordination polymers constructed from the flexible carboxylateligands and sulfur ligands already become one of the fastest developing areas in chemistry and materials science.they have variety of potential properties in applications such as gas storage,nonlinear optics,nonlinear optical materials?NLOM?,Single-Molecule Magnets,catalysis,etc.In this work,we focus on two flexible N-multicarboxylate ligands N,N-bis?2'-carboxy?1,1'-biphenyl?-4-methylene?acetateamine?H₃BCDA?and N,N,N-tri?2'-carboxy?1,1'-biphenyl?-4-methylene?amine?H3TCMA?.Under a rational synthetic strategy to design and synthesize a series of compounds with fascinating structures and novel properties.Some complexes were characterized by X-ray single crystal diffraction,TGA,IR,and XRD.All of coordination polymers as follows:?1?[Cd₃?2-Mercaptopyrazine?₆]_n?2?[Ag₂?2-Mercaptopyrazine?₂]_n?3?[Cu₄?2-Mercaptopyrazine?₄]_n?4?{[Zn?HBCDA??H₂O?]·H₂O}n?5?[Cu₁₀?HBCDA?₄??3-O?₆?H₂O?10]?6?{[Eu?TCMA??H₂0??DMF?]·H₂O}n?7?{[Tb?TCMA??H₂0??DMF?]·H₂O}n?8?[Cu?HTCMA??2,2'-Bipyrazine?]_n?9?[Co₂?HTCMA?₂?H₂O?]_nComplex[Cd₃?2-Mercaptopyridine?₆]_n?1?is a two-dimensional structure in which the building blocks[Cd₃?2-Mercaptopyridine?₆]constructed by three Cd2+ions and six 2-Mercaptopyridine are interlinked through 4-position N atoms of pyrazine.Complex[Ag₂?2-Mercaptopyrazine?₂]_n?2?is a three-dimensional structure in which the building blocks[Ag₂?2-Mercaptopyrazine?₂]constructed by two Ag+ions and two 2-Mercaptopyridine are interlinked through 4-position N atoms of pyrazine.Complex[Cu₄?2-Mercaptopyrazine?₄]_n?3?is a two-dimensional structure in which the building blocks[Cu₄?2-Mercaptopyrazine?₄]constructed by four Cu+ ions and four 2-Mercaptopyridine are interlinked through 4-position N atoms of pyrazine.Complex{[Zn?HBCDA??H₂0?]·H₂O}n?4?is a one-dimensional structure in which the building blocks[Zn?HBCDA??H₂O?]constructed by one Zn2+ions,one HBCDA 2-and one H₂O interlinked through Carboxyl oxygen of ligand with ?1-?¹:?¹ and ?1 coordination modes.Complex[Cu₁₀?HBCDA?₄??3-O?₆?H₂O?10]Complex?5?is a Cluster complexe constructed by four HBCDA2-,ten H₂O,six O2-and ten Cu2+,the copper ion are bridged by ?3-O resulting in Cu₁₀ cluster which is stablilized by four ligandsComplex {[Eu?TCMA??H₂O??DMF?]H₂O}n?6?is a two-dimensional structure in which the building blocks[Eu?TCMA??H₂O??DMF?]constructed by one Eu3+ ions,one TCMA 3-,one H₂O and one DMF interlinked through Carboxyl oxygen of ligand with?2-?¹:?² and ?1-?¹:?¹ coordination modes.Complex {[Tb?TCMA??H₂0??DMF?]·H₂O}n?7?and Complex?6?are allomerism.Complex[Cu?HTCMA??2,2'-Bipyrazine?]_n?8?is a one-dimensional structure in which the building blocks[Cu?HTCMA??2,2'-Bipyrazine?]constructed by one Cu2+ions,one HTCMA2-,and one 2,2'-Bipyrazine interlinked through Carboxyl oxygen of ligand with ?1 coordination modes.Complex[Co₂?HTCMA?₂?H₂O?]_n?9?is a two-dimensional structure in which the building blocks[Co₂?HTCMA?₂?H₂O?]constructed by two Co₂+ ions,two HTCMA 2-,and one H₂O interlinked through Carboxyl oxygen of ligand with ?1-?¹:?¹??1 coordination modes.