Synthesis,Structures And Properties Of Zinc Coordination Polymers Based On Triazol-Carboxylate Ligands

As a new kind of multifunctional crystalline materials,coordination polymers have attracted extensive attention from chemists and material scientists due to their wide application prospects in many research fields such as gas storage/separation,heterogeneous catalysis,magnetic,fluorescence-based sensing,and so on.In this thesis,seven novel zinc coordination polymers were synthesized under hydrothermal/solvothermal conditions by using different Zn?II?salts with triazole ligand 3,5-dimethyl-1,2,4-triazole?Hdmtz?,bifunctional triazole-carboxylate ligands4-?1H-1,2,4-triazol-1-yl?benzoic acid?4-Htba?and 3-?4H-1,2,4-triazol-4-yl?benzoic acid?3-Htba?.The specific contents are as follows:1.A novel 3D zinc coordination polymer formulated as{[Zn₄?dmtz?₃?OH?₃?HCOO?]?NO₃?}_n?1?was synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction analysis,elemental analyses,and IR spectroscopy.Compound 1 show a?3,4,5?-connected 3D cation framework constructed by?₃-bridging dmtz with hydroxyl and formate anions as the auxiliary ligands.In addition,the photocatalytic properties of compound 1 have been investigated and it exhibits selective photocatalytic degradation for methyl orange?MO?under UV light.2.A luminescent zinc porous coordination polymer with uncoordinated triazolate N-donors,namely[Zn?4-tba?₂]·?DMA??2??DMA=N,N-Dimethylacetamide?,was synthesized by using a triazolate-carboxylate bifunctional ligand 4-Htba.Single-crystal X-ray diffraction analyses showed that compound 2was connected by 4-tba ligands to form a three-dimensional porous structure with dia topology,and the activated 2a also shows selective adsorption of CO₂ over N₂.Moreover,compound 2 shows significant luminescence quenching of nitrobenzene and Fe³⁺,which can be used for sensing nitrobenzene and Fe³⁺.3.A series of Zn?II?coordination polymers,namely[Zn?3-tba?₂]·H₂O?3?,[Zn?3-tba?₂]·NMF?4?,[Zn?3-tba?₂]·0.5DMF?5?,[Zn?3-tba?₂]·DMA·H₂O?6?,and[Zn?3-tba?₂]·2NMP?7??NMF=N-methylformamide,DMF=N,N-dimethyl-formamide,NMP=1-methyl-2-pyrrolidone?,were synthesized under hydrothermal/solvothermal conditions by using a V-shaped,bifunctional triazole-carboxylate ligand 3-Htba.Single-crystal X-ray diffraction analysis showed that the znic ion of compounds 3-7 adopts tetrahedral coordination geometry.Compounds 3-5 were two-dimensional layer structure,Compounds 3 and 5 were?4,4?lattice topology network structure,Compound 4 was single-nodal four-connected 4L7 topology network structure and point symbol was 6⁶.Compounds 6 and 7 were one-dimensional chain structure,and compound 7 was ladder chain.Meanwhile,the solid stete photoluminescence study indicates that compounds 3-7 have ligand-based fluorescence emission at room temperature.