Syntheses,Structures And Properties Of Coordination Ploymers Based On The Dicarboxylic、Tricarboxylic Acid Ligand

In the past 20 to 30 years,remarkable progress has been made in the research of the metal organic coordination polymer（CPs）,therefore,it has become an important research frontier and a new type of research field.In this work,fourteen new CPs have been successfully synthesized via the utilization of two and carboxylate ligands and N-donor ligands with transition metal salts.These results include the following issues:1.Seven new metal-organic frameworks（MOFs）were achieved by reactions of corresponding metal salts with mixed organic acid of 4,4-（phenylazanediyl）dibenzoic acid（H₂L）and different nitrogen ligands.Namely,[Co₂L₂（bif）₂]·4DMF（1）、[Cd（L）]n（2）、[Cd（L）（bif）]（3）、[Zn（L）（bimb）_0.5]（4）、[Ni₂（L）₂（bimb）₂·（H₂O）₂]·5H₂O（5）、[Ni（L）（bif）·（H₂O）₂]·L（6）、[Ni（L）（bif）]·4H₂O（7）.These crystals were clearly characterized by elemental analysis,IR spectra,X-ray powder diffraction（PXRD）.The crystal structures showed that compound 1 displayed a two dimensional layer,compound 2 showed a one dimensional chain,compounds 3、6 showed a three dimensional framework connected byπ-πbonds,compound 4 showed a three dimensional framework,compound 5 revealed a two dimensional network structure with two different helix chains,compound 7 exhibited a three dimensional framework by hydrogen bonds.In addition,we also further studied properties of compounds and found 1、6 and 7 have electrochemically active substances with good electrochemical reversibility,compound 3 can selectively adsord sodium fluorescein dyestuff.2.Seven new metal-organic frameworks（MOFs）were achieved by reactions of correspondingmetalsaltswithmixedorganicacidof3,5-bi（4-carboxy-phenoxy）benzoic acid（H₃L）and different nitrogen ligands.Namely,[Zn（HL）（tpim）]·H₂O（8）、[Co（HL）（tpim）]（9）、[Ni（HL）（bpmp）（H₂O）]·2H₂O（10）、[Ni（HL）（bibpa）_0.5]·2H₂O（11）、[Cu₂（HL）₂（bibp）₂]·2DMF（12）、[Zn₄（HL）₂（H₂L）₂（bpmp）]·5H₂O（13）、[Cd（L）（bibp）_0.5]（14）.These crystals were clearly characterized,compound 8 displayed a two dimensional layer,compound 9 also exhibited a two dimensional layer,which had a zero-dimensional ring structure link Co（II）ion by N-containing ligand tpim,compounds 10、11 and 13 showed a two dimensional layer,compounds 12 and 14 are exhibited a three dimensional framework.The results show that compounds 8 and 14 have good luminescence properties and good stability in aqueous solution,can be used as fluorescence probes for sensing Fe³⁺ions,compounds 9、10 and 11 have electrochemically active substances with good electrochemical reversibility,compound 12 can efficiently adsorb methyl orange（MO） solution under natural light.