| Metal-organic complexes are ordered supramolecular assemblies,which are composed of molecular building blocks via coordination bonds.By means of the coordination driven self-assembly,target functional complexes can be achieved from a simple reactant.In this thesis,a new imidazole-modified resorcin[4]arene ligand（TIC4R）was used to assemble metal-organic complexes with remarkable structures and functionalities under solvothermal conditions.Their crystal structures were determined by single crystal X-ray diffraction.These complexes were characterized by elemental analysis,infrared spectra（IR）,powder X-ray diffraction（PXRD）,thermogravimetric analysis（TGA）and other techniques.The relationships between structures and properties of the complexes were also studied.First,considering the structural characters of the assembled dimers,we tried to improve the dispersion and stability of the resulting Pd nanoparticles（NPs）through their interactions with the uncoordinated Lewis base（-NH2）of the auxiliary ligand.The catalytic performances of the Pd-based catalyst for the hydrogenation of nitroaromatics were explored.Second,a series of complexes with the related structures were synthesized by changing the components of the reactants,and their catalytic behaviors for Knoevenagel condensation reactions were conducted.Third,three porous cationic metal-organic frameworks（MOFs）with hexameric TIC4R nanocapsules were rationally synthesized,and their ability to remove ReO4-/Tc O4-from aqueous solutions was studied.1.Using TIC4R as building block,metal-organic supramolecular complexes with specific structures and functions were assembled via synthetic strategy for regulating the auxiliary ligands.A series of tunable supramolecular dimers were precisely synthesized under solvothermal conditions by adjusting 1,4-benzenedicarboxylic acid analogs with different lengths or functional groups,namely,[Zn4（TIC4R）2·（L1）2·（OH）2]·2HCOO·4DMF（1）,[Zn4（TIC4R）2·（L2）2·（OH）2]·2HCOO·4DMF（2）,[Zn4（TIC4R）2·（L3）2·（OH）2]·2HCOO·3H2O（3）,[Zn4（TIC4R）2·（L4）2·（OH）2]·2HCOO·H2O（4）,[Zn4（TIC4R）2·（L5）2·（OH）2]·2HCOO（5）,[Zn4（TIC4R）2·（L6）2·（OH）2]·2HCOO·6DMF（6）,[Zn4（TIC4R）2·（L7）2·（OH）2]·2HCOO·4DMF·8H2O（7）and[Zn4（TIC4R）2·（L8）2·（OH）2]·2HCOO·6DMF·4H2O（8）（H2L1=terephthalic acid,H2L2=2-aminoterephthalic acid,H2L3=2,6-naphthalenedicarboxylic acid,H2L4=4,4’-biphenyldicarboxylic acid,H2L5=2,2’-bipyridine-5,5’-dicarboxylic acid,H2L6=4,4’-stilbenedicarboxylic acid,H2L7=azobenzene-4,4’-dicarboxylic acid,H2L8=p-terphenyl-4,4’-dicarboxylic acid and DMF=N,N-dimethylformamide）.In compounds 1-8,a pair of dicarboxylic acid auxiliary ligands linked two TIC4R via Zn（II）ions to yield novel metal-organic supramolecular dimers.Taking 2 as a representative,their chemical and thermal stabilities were studied.In view of the uncoordinated amine groups in the dimer of 2,the composite material Pd@2 with loaded Pd nanoparticles was synthesized.The hydrogenation of nitroarenes was studied in aqueous solution with the Pd@2 catalyst at room temperature.The result demonstrated that the Pd@2 catalyst featured high catalytic performance and great selectivity.2.Under solvothermal conditions,three structurally related complexes were synthesized by adding three different organic acids to modulate the composition of the reactants,namely,[Zn（TIC4R）（HCOO）]·HCOO·0.5DMF·1.5H2O（9）[Zn（TIC4R）（CN）]·HCOO·DMF·2.5H2O（10）and[Zn（TIC4R）（H2O）]·2HCOO·2H2O（11）.The cavitands of TIC4R in compound 9 are arranged in a face-to-face manner to afford a double-layered structure with rectangle windows,while 10 and 11 displayed monolayered structures.Compared to 9,the layers of 10and 11 were slided along the a-axis with different offsets,which also led to different pore sizes of 10 and 11.Considering the Lewis acid Zn（II）sites,9-11 as heterogeneous catalysts for the Knoevenagel condensation reactions were investigated.At the same time,the effect of different pore sizes on the catalysis was explored.The result indicated that their catalytic behaviors were influenced by their different channel sizes.3.Three cationic metal-organic framework,with hexameric resorcin[4]arene nanocapsules were rationally prepared under solvothermal conditions by assembly of TIC4R with metal ions,namely,[Zn（TIC4R）]·0.33HCOO·1.67NO3·4DMF·12H2O（12）,[Cd（TIC4R）]·0.33HCOO·1.67NO3·5DMF·12H2O（13）and[Co（TIC4R）]·0.33HCOO·1.67NO3·5DMF·12.5H2O（14）.Single crystal X-ray diffraction indicated that isostructural 12-14 retain the intrinsic cavity of resorcin[4]arene and form nanocapsules with large internal space.Taking 12 as an example,its stability of the MOFs at different p H values was explored.Considering the cationic characteristics of the frameworks,their performances for capturing Tc O4-/ReO4-from aqueous solutions were evaluated.Remarkably,the cation frameworks exhibited rapid exchange kinetics,good adsorption capacity and high selectivity during the capture of ReO4-.The results indicated that 12 still maintained high removal percentage of ReO4-after three cycles. |
PDF Full Text Request