Syntheses,Structures And Properties Of Co/Cu/Zn/Cd Coordination Polymers Based On Flexible Bis(Pyridyl-tetrazole)as Main Ligands And Organic Carboxylates As Co-ligands

In this thesis,we use four kinds of different flexible[1,4-bis（5-（3-pyridyl）tetrazolyl）propane（3-bptzp）,1,4-bis（5-（4-pyridyl）tetrazolyl）propane（4-bptzp）,1,4-bis（5-（3-pyridyl）tetrazolyl）hexane（3-bptzh）,and 1,4-bis（5-（4-pyridyl）tetrazolyl）hexane（4-bptzh）] as main ligands,and use different aromatic dicarboxylic acids [1,3-benzenedicarboxylic acid（1,3-H₂BDC）,1,4-benzenedicarboxylic acid（1,4-H₂BDC）,4,4′,4″-benzene-1,3,5-triyl-tribenzoic acid（1,3,5-H₃BTB）] as auxiliary ligands,and use Co（Ⅱ）/Cu（Ⅱ）/Zn（Ⅱ）/Cd（Ⅱ）as metal ions under hydrothermal/solvothermal conditions.Fifteen new complexes have been obtained and characterized by single-crystal X-ray diffraction,infrared spectrum（IR）,and powder X-ray diffraction（PXRD）.The fluorescent properties,electrochemical behaviors,and dye adsorption properties of some polymers have been studied.1.Purposefully synthesized under hydrothermal/solvothermal conditions3-bptzp/4-bptzp as main ligands,and 1,3-H₂BDC/1,4-H₂ BDC for auxiliary ligands,ten new complexes have been synthesized.The influences of center metal（Ⅱ）ions and solvent ratio on the structures of the title compounds were investigated.[Cu（4-bptzp）（1,3-BDC）]（1）[Cu₂（4-bptzp）₂（1,3-BDC）Cl₂]（2）[Co（4-bptzp）（1,3-BDC）]（3）[Zn（4-bptzp）（1,3-BDC）]（4）[Cd（4-bptzp）（1,3-BDC）]（5）[Co（3-bptzp）（1,3-BDC）]（6）[Zn（3-bptzp）（1,3-BDC）]（7）[Cd（3-bptzp）（1,3-BDC）]（8）[Co（3-bptzp）（1,4-BDC）（1,4-H₂BDC）_0.5]（9）[Cu（3-bptzp）（1,4-BDC）]（10）Complexes 1,3,4,5,6,7,8 exhibit similar 1D ladder-like chains constructed from 1D [M（1,3-BDC）]_n chain and M₂（4-bptzp）₂ rings（M=Cu,Co,Zn,Cd）.Complex 2 is also 1D chain structure,which contains 1D [Cu₂（1,3-BDC）Cl₂]_n linear chain and Cu₂（4-bptzp）₂ rings.The structures of complexes 9 and 10 are 2D layered network.In complex 9,the 2D layered network is formed by 1,4-BDC anions and neutral 1,4-H₂ BDC ligands,whilst the 3-bptzp ligands bridge the adjacent two Co（Ⅱ）atoms to form a [Co₂（3-bptzp）₂] ring.In complex 10,adjacent Cu（Ⅱ）atoms are bridged by 1,4-BDC anions to form a 1D [Cu（1,4-BDC）]_n chain,then adjacent1 D [Cu（1,4-BDC）]_n chains are further linked together by the 3-bptzp ligands to generate a 2D layered network.The dye adsorption properties of complexes 1-10,electrochemical behaviors of complexes 1,2,6,9,10 and fluorescence properties of complexes 4,5,7,8 have been studied.2.Five new Co（Ⅱ）/Cu（Ⅱ）/Zn（Ⅱ）coordination complexes based on3-bptzh/4-bptzh ligands and different nitro-substituted carboxylates（1,3-H₂ BDC and 1,3,5-H₃BTB）,were synthesized under hydrothermal/solvothermal conditions.The influences of metal（Ⅱ）ions and N-donor ligands on the structures of the title complexes were discussed.[Zn（3-bptzh）（1,3-BDC）]（11）[Zn（4-bptzh）（1,3-BDC）]（12）[Co₆（4-bptzh）₃（1,3,5-BTB）₆（H₂O）₂]（13）[Cu₄（4-bptzh）₂（1,3,5-BTB）₄]·Me CN（14）Complex 11 is a 2D wave layered structure,complex 12 is a 2D network containing a helical chain.The 3-bptzh and 4-bptzh ligands both connect adjacent1 D [Zn₂（1,3-BDC）₂]_n chains in a μ₂-bridging mode.Among them,the 3-bptzh ligand serves as a linear connector,and the 4-bptzh ligand serves as a U-shaped connector,resulting in different final structures of the complexes 11 and 12.The results show that the difference of the site of the pyridine tetrazolium ligand affects the structure of the complexes.In complex 13,1,3,5-BTB anion adopts the monodentate-bidentate-chelate linkage mode to connect Co（Ⅱ）ions to form a honeycombed two-dimensional bilayer [Co₆（1,3,5-BTB）₆]_n macrocyclic structure.The two-dimensional network is connected in a μ2-bridging mode by 4-bptzh ligands into a three-dimensional framework.In compound 14,all 1,3,5-BTB anions adopt double（double-tooth）linking mode,connecting four Cu（Ⅱ）ions to form a four-dimensional two-dimensional layer [Cu₄（1,3,5-BTB）₄]_n structure.There is a left/right double helix chain structure in this two-dimensional network.The two-dimensional network is connected in a μ₂-bridging mode by 4-bptzh ligands into a three-dimensional framework.The results show that the central metal is an important factor that affects the structure of CPs.In addition,we also studied the dye adsorption properties of complexes 11-14,the fluorescence properties of complexes 11-12 and the magnetic properties of complexes 13.