| It is of great significance to explore isopolymolybdate-based metal organic complexes with novel structures.In this paper,a hydrothermal/solvothermal synthesis method is used,with three novel flexible bis-imidazole bis-amide ligands and one semi-rigid bis-pyrazole bis-amide ligand as organic ligands,fourteen isopolymolybdate-based metal organic complexes were constructed by changing metal ions,solvent ratios and polyoxometalates:[（Co2（L1）2（H2O）3）2(γ-Mo8O28)（MoO3）2]·6H2O（1）,[（Ni2（L1）2（H2O）3）2(γ-Mo8O28)（MoO3）2]·6H2O（2）,[ZnL1(Mo3O10)]·H2O（3）,[（L1）(γ-Mo8O26)0.5]·2H2O（4）,[CoL1（MoO4）]·H2O（5）,[Co2（L2）2（H2O）4](β-Mo8O26)·4DMA·6H2O（6）,[Cd(C8N4H13O)2（H2O）2(β-Mo8O26)]·4H2O（7）,[Ni（L3）0.5（H2O）(β-Mo8O26)0.5]·3H2O（8）,[Co（L4）0.5(Mo3O10)（H2O）2]·2H2O（9）,[Ni（L4）0.5(Mo3O10)（H2O）2]·2H2O（10）,[Zn（L4）（H2O）3][γ-Mo8O26]0.5（11）,[Cd（L4）1.5(θ-Mo8O26)0.5]·2H2O（12）,[Co2（L4）2（MoO4）2]·H2O（13）,[Zn2（L4）2（MoO4）2]·H2O（14）.Complexes 1 and 2 are isostructural two-dimensional structures in which isopolymolybdates are induced into a new type of[(γ-Mo8O28)（MoO3）2]8–anion cluster,and such structure affects its performance.While complexes 3,9 and 10 all contain one-dimensional[Mo3O10]n2n–inorganic chains,the[Mo3O10]n2n–isopolymolybdate chains induced by construction are rarely reported.Complex 4 is a two-dimensional supramolecular structure,and metal ions do not participate in coordination during the synthesis process.Isopolymolybdates are induced as[MoO4]2–anions in complexes 5,13 and 14,which are the first reported isopolymolybdate-based metal organic complexes based on pyrazole-amide ligands having such a structure.The[β-Mo8O26]4–anions are induced in complexes 6,7 and 8.The complex 11 has a one-dimensional infinite chain{γ-Mo8O26}n connected by an angle sharing mode.The isopolymolybdate anion in complex 12 is induced as[θ-Mo8O26]4–anions.The length of the spacers between the imidazol-amide groups in the organic ligands,the metal ions,the ratio of the solvent and the polyoxometalate raw materials show a key role in inducing the isopolymolybdate anionic isomers and constructing the target complexes.In addition,the fluorescence sensing,electrocatalytic and photocatalytic degradation properties of the complexes were studied,and the reaction mechanism was investigated in detail. |
