| In this dissertation,we used four double bond-containing pyridine ligands,(E,E-2,5-dimethoxy-1,4-bis-[2-pyridin-vinyl]-benzene)(L1),(E,E-2,5-dibutoxy-1,4-bis-[2-pyridin-vinyl]-benzene)(L2),(E,E-2,5-dioctyloxy-1,4-bis-[2-pyridin-vinyl]-benzene)(L3),tris[p-(4-pyridylvinyl)phenyl]amine(L4),as main organic ligands to react with 4,4'-dicarboxybiphenyl sulfone,4,4'-oxybis(benzoic acid),4,4'-biphenyldicarboxylic acid,4,4'-(pyrimidine-4,6-diyl)dibenzoic acid and different transition metal ions and successfully constructed twelve coordination polymers under hydrothermal and heating conditions.Their syntheses,crystal structures and physical properties were investigated and discussed in detail.This dissertation includes the following two parts:1.Solvothermal reactions of(E,E-2,5-dimethoxy-1,4-bis-[2-pyridin-vinyl]-benzene)(L1),(E,E-2,5-dibutoxy-1,4-bis-[2-pyridin-vinyl]-benzene)(L2),(E,E-2,5-dioctyloxy-1,4-bis-[2-pyridin-vinyl]-benzene)(L3)with 4,4'-dicarboxybiphenyl sulfone,4,4'-oxybis(benzoic acid),4,4'-biphenyldicarboxylic acid,in the presence of different transition metal ions yielded eleven coordination polymers,namely,{[Cd(L 1)(bpdc)]·DMA·3 H2O}n(1),{[Cd2(L1)2(bpdc)2]·2DMA·2H2O}n(2),{[Cd2(L1)2(bpdc)2]·2DMA}n(3),{[Cu(L1)(bpdc)]·Ll}n(4),{[Co(L1)(bpdc)]·DMF·2H2O}n(5),{[Zn(L1)0.5(bpdc)]·DMA·H2O}n(6),{[Co(L1)0.5(sdb)]·2DMF}n(7),{[Co2(L1)(sdb)2]·3DMF·3H2O}n(8),{[Co(L1)(oba)]·DMF·3H2O}n(9),{[Co(L2)0.5(sdb)]·1.5H2O}n(10),[Co(L3)0.5(sdb)]n(11).Compounds 1 and 2 are achieved by adjusting the solvent ratio of the solvothermal reaction.They are isostructuralism and display 3D frameworks with {412.63}-pcu topologies.But compound 1 is 2-fold interpenetrating and compound 2 is 3-fold interpenetrating.Compound 2 is the first case that contains two isomer ligands which are"trans,trans,trans-" and "trans,trans,cis-".We got compound 2 by irradiation compound 3 using 365 nm UV light with single crystal to single crystal transformation.They are isostructural,but the carboxylic acid coordination model changes from one pattern in compound 2 to two different kinds of patterns in compound 3,the shape of tunnels in 2D layer change from square to parallelogram,the dihedral angles between the benzene rings of carboxylic acid ligand also take place obvious change.Compound 4 exhibits a 2D sheet structure with {44.62}-sql topology framework.In the channel of compound 4 contains free ligand L1.Compound 5 is isostructuralism with compound 2,it shows a 3D network with{412.63}-pcu topology,which only contains the "trans,trans,trans-" ligand.Compound 6 possesses a 4-fold interpenetrating 3D framework with 6-connected {412.63}-pcu topology.Compounds 1,2,4,5,6 are composed of the same organic ligands and different metal irons such as Cd(II),Cu(II),Zn(II),Co(II).Different radius and varies electronic configuration of these four kinds of metal ions leading to differences in coordination modes of metal and organic ligands.With different compounds,dihedral angle of two benznen rings in the same co-ligands are different,especially in compound 2 which has two different kinds of dihedral angles.Two different compounds 7 and 8 were co-crystallized in a one-pot reaction,they possess{44.62}-sql topology,compound 7 exhibits non-interpenetrating and compound 8 exhibits interpenetrating.Compound 9 possesses a non-interpenetrating{44.610.8}-mab topology.Compound 10 and 11 are isostructuralism which are crossover sql topology structure.Compounds 5,7,9 are composed of the same L1 ligand and Co(?)center but different carboxylic acid ligands,their porosity are 9.9%,40.8%,39.9%,respectively.Compounds 7,10,11 are composed of the same H2sdb ligand and Co(?)center but different pyridine ligands which are obtained by increasing of the branched chain group based on L1 ligand.With the increasing of the branched chain group,the porosity of the three kinds of compounds decreases.we investigate their adsorption property,compound 7 shows good properties of hydrogen sorption and selective adsorption of carbon dioxide and methane compared with compounds 8,10,11.2.Solvothermal reactions of double bond-containing Y-type pyridine ligand tris[p-(4-pyridylvinyl)phenyl]amine with rigidity carboxylate ligands,namely 4,4'-(pyrimidine-4,6-diyl)dibenzoic acid as co-ligands in the presence of transition metal salt Cd(NO3)2·4H2O yielded compound 12,namely,{[Cd(Ll)(pdba)]·H2O}n(12).Compound 12 shows a 2D network with {42.67.8}{42.6}-3,5L2 topology structure.It is a type of temperature sensitive material which shows different color and fluorescence intensity under different temperatures.From room temperature to 350? at 25? for a temperature intervals,compounds 12a-12m were obtained.We compare the structures of these compounds,under the condition of heating,groups of ligand L4 shift,bond length and bond angle composed by coordination atoms and metal ions were changed.With the rise of temperature,the content of triphenylamine radical cation in compound 12 gradually increased.These changes influenced the color and fluorescence intensity of coordination polymers.Thermal stabilities and variable-temperature powder X-diffraction for compound 12 have been examined.Furthermore,the UV-vis absorption spectra of compounds 12a-12m were investigated. |
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