The Synthesis,Structure And Proton Conductivity Of Transitiometal Complexes Based On Carboxylic Acid Ligands

Transition metal complexes based on the carboxylic acid ligands occupy a very important position in coordination chemistry,and they have been widely used in gas storage,sensors,magnetic materials,gas adsorption and separation,etc.However,the study of these complexes in proton conduction is rarely reported.In this paper,by chosing H₃PDC（3,5-pyrazoledicarboxylicacid）,formate 5-Aipa（5-Aminoisophthalic acid）and 5-Hipa（5-Hydroxyisophthalic acid）as ligands,nine coordination polymers have been obtained.Their magnetic properties and proton conduction behavior are also studied.The main contents of this paper are as follows:1.Three transition metal coordination polymers have been designed and synthesized by solvothermal method based on H3PDC ligand.[Ni（OH）（HPDC）（H2O）]n（1）,[Mn（HPDC）（H₂O）₂]_n（2）,and[Cu₂（HPDC）₂（H₂O）₂]₃·9H₂O·2CH₃CN（3）.The structural analyses show that complexes 1 and 2 are one-dimensional chain structures.The adjacent chains are connected with each other via the hydrogen bonds to form a two-dimensional network structure.All the complexes are characterized by element analysis and thermogravimetric analysis.The magnetic properties of complexes 1 and 2 indicate that weak antiferromagnetic interaction exists in complex 1 and strong antiferromagnetic interaction exists in complex 2.All the three complexes have good proton conducticity behaviors.2.Three transition metal coordination polymer were designed and synthesized by solvothermalmethodwithdifferentkindsofamidessolvents.[Zn₂（HCOO）₄（H₂O）·]_n·5nH₂O（4）,[Co（HCOO）₂（4,4’-Bipy）]_n（5）,（CH₃NH₃）[Co（HCOO）₃]_n（6）.The structural analyses show that complexes 4-6 are three-dimensional structures with large pores.All the complexes were characterized by elements and thermogravimetric analysis.Proton conduction properties measurement indicates that complexes 4 and 6 have the largest conductivity with 1.42×10^-2 and 7.27×10^-3 S/cm,respectively.3.Based on 5-Aipa and 5-Hipa ligands,three transition metal complexes,[Zn（5-Aipa）（H₂O）]_n（7）,[Mn（5-Aipa）（H₂O）]_n·2nH₂O（8）,[Zn（2,2’-Bipy）（5-Hipa）]_n（9）have been obtained by solvothermal method.Complexes 7 and 8 are two-dimensional network structures and complex 9 is two-dimensional structure formed byπ…πstacking interaction between adjacent chains.Complexes 7 and 8 were characterized by elements and thermogravimetric analysis.The highest proton conductivity of complex 8 is 1.76×10^-3S/cm.