Syntheses,Structures And Properties Of Coordination Polymers Based On Azoles Carboxylic Acid Ligands

In recent years, polymeric coordination frameworks attracted great interest for great potential of being applied to adsorption, magnetism, luminescence, catalysis,ion-exchange. In this article, we designed and synthesized two ligands:1-（pyridin-4-ylmethyl）-1H-1,2,4-triazole-3-carboxylate lithium（ppmtc Li）,1-（pyridin-2-ylmethyl）-1H-1,2,4-triazole-3-carboxylate lithium（pomtc Li）. This paper contains two parts as follows:1.Thirteen polymers have been synthesized by the self-assembly of Cd（II） ions and ppmtc Li ligand, {[Cd（ppmtc）2]·（CH3OH）·2H₂O}n（1）, {Cd1.5（ppmtc）2（NO3）]·H₂O}n（2）, [Cd2（ppmtc）2（SO4）（H₂O）]n·1.25H₂O}n（3）,{[Cd3（ppmtc）3]·（HSO4）（SO4）·（H₂O）]·（CH3OH）}n（4）, [Cd（ppmtc）（NO2）（CH3OH）]n（5）, {[Cd2（ppmtc）3（NO2）]（CH3OH）·2H₂O}n（6）, [Cd（ppmtc）（SCN）]n（7）,[Cd2（ppmtc）2（SCN）2]n（8）, [Cd3（ppmtc）4（SCN）2]n（9）, {[Cd1.5（ppmtc）2（N3）]·H₂O}n（10）, {[Cd（ppmtc）2（Cl）2（H₂O）2]·4H₂O}n（11）, {[Cd（ppmtc）（Br）（H₂O）]·CH3OH}n（12）,{Cd（ppmtc）（I）（H₂O）]·CH3OH}n（13）. In previous literature, the studies of complexes concluding metal salts and neutral ligands and coordinated anion are more, but it is rare that anion coordinated complex containing anionic organic ligand. In our a series of polymers, anions containing NO3-, SO42-, NO2-, SCN-, N3-, Cl-, Br-, I- all participate in coordination, which is quite rare in the reported literature, and it is significant for the study of the coordination of the ligands, the choice of the ligands, and anion coordination mode in anion coordination chemistry.2.Six coordination polymers have been synthesized by the self-assembly of Pb（II）ions and ppmtc Li ligand, [Pb（ppmtc）（Ac）]n（14）, {[Pb（ppmtc）2·（H₂O）2]·H₂O}n（15）,[Pb（ppmtc）（μ2-Cl）]n（16）, [Pb（ppmtc）（I）（H₂O）]n（17）,[Pb3（ppmtc）3（H₂O）3]·（H₂O）·2（CH3OH）]（18）, [Pb（ppmtc）Br]n（19）, four Co coordination complexes: {[Co（ppmtc）2]·2H₂O}（20）, {[Co（ppmtc）2]·H₂O}n（21）,{[Co（ppmtc）2]·2H₂O}n（22） have been obtained. Two Zn coordination complexes:[Zn（ppmtc）2]·2H₂O}n（23） and {[Zn（ppmtc）2]·0.5H₂O}n（24）. One coordination complexes {[Ni（ppmtc）2]·2H₂O}n（25） based on Ni. We also synthesized a magnetic polymer [Cu2（ima）（SO4）（H₂O）（OH）]n（26） with Hima ligand based on Cu（II）. Their molecular structures were obtained by means of elemental analysis, IR spectra and single-crystal X-ray diffraction. And according to the relationship between the reaction conditions and the reaction products, the influence of metal ions, template,temperature and solvent on the structure of the complex was analyzed.3. According to the coordination of anion and metal, we analyzed the coordination ability and coordination mode of anions. Part of complexes were aslo characterized by fluorescence, thermal stability and their purities were verified by X-ray powder diffraction.