| Metal-Organic Frameworks materials both have the rigidity of inorganic materials and the flexibility of organic materials.They can be used widely in biosensing,catalytic adsorption,fluorescence recognition and antibacterial fields due to the rich functional coordinate sites and post-modification treatment features.However,the functional properties of Metal-Organic Frameworks materials depend on their structure and composition.So it will affect the final structure of the complex directly when we choose different metal ions and functional organic ligands.Therefore,we used the solvent volatilization method,ultrasonic method and hydrothermal method to synthesize 47 target metal complexes of azole.The X-ray,thermogravimetric,fluorescence,FTIR and elemental analysis studies revealed the crystal structure,luminescence,thermal stability and elemental composition of these complexes.The main contents of the paper include the following four parts:（1）We used 2-methylbenzimidazole（mbzm）as a neutral ligand together with metal ion Zn and organic carboxylic acid to obtain twelve complexes with different structures by self-assembly.Structure analysis showed that complexes[Zn（mbzm）2（nap）2]（5）,[Zn（mbzm）2（bbza）2]（6）and[Zn（mbzm）2（mpba）2]（7）were two-dimensional double-layer structure.Except for the complexes[Zn（mbzm）2（nap）2]（5）,[Zn（mbzm）2（bbza）2]（6）and[Zn（mbzm）2（mpba）2]（7）,other complexes exhibit 3-D network structures.We analyzed the crystal structure and thermal stability of twelve new complexes.We also tested the fluorescent of complexes[Zn（mbzm）2（mpba）2]（7）and[Zn（mbzm）2（cnba）2]·Me OH（10）.The result showed good thermal stability and luminescence performance.（2）We designed and synthesized the semi-flexible ligand,1,4-bis（（2-methyl-1H-imidazole-1-yl）methyl）benzene（bimb）.We chose carboxylic acid ligands with different functional groups and the metal ion Zn to synthesize twelve metal-organic framework compounds with different spatial structures by self-assembly.Structure analysis showed that all complexes have Zn with four coordination capacities and N group on bidentate bimb.Complexes Zn（bimb）（cpa）2（14）,Zn（bimb）（dcpa）2（15）,Zn（bimb）（dpa）2（16）,[Zn（bimb）（cnba）2]·CH3OH（20）,[Zn（bimb）（mpba）2]（22）and[Zn（bimb）（ppba）2]（23）showed one-dimensional chains of Z model.Complexes[Zn（bimb）（cnba）2]·CH3OH（20）and[Zn（bimb）（bdmba）2]·Et OH（21）showed microporous structure,so they showed good adsorption performance in organic dye adsorption test.Complexes[Zn（bimb）（dcba）2]·Et OH（18）and[Zn（bimb）（mpba）2]（22）showed strong fluorescence emission peaks,and we also analyzed their luminescence mechanism.（3）We used double azole ligand,1,5-bis（1-yl-2-methylbenzimidazole）-3-oxopentan（obmim）and the metal salts of Zn（Ⅱ）/Cd（Ⅱ）and different carboxylic acid ligands to obtain twelve new complexes by self-assembly.Complexes Zn（obmim）（mpba）2·Et OH（25）,[Cd（obmim）（dcba）2]（33）,[Zn（obmim）（msal）2]（35）and[Zn（obmim）（tpa）2]（36）were mononuclear.The others were binuclear.The CH2of obmim ligands had shown the CH2-A bond（A is S,O,π,C,Cl and CH）in all complexes,and the CH3of obmim ligands had shown CH3-πstacking in complexes Zn（obmim）（mpba）2·Et OH（25）,[Cd（obmim）（cnba）2]2（27）,[Cd（obmim）（dcpa）2]2（32）and[Zn（obmim）（tpa）2]（36）.One-dimensional chains were connected into two-dimensional slices,or two-dimensional slices were constructed into three-dimensional net structure by CH2-A non-covalent bonding or CH3-πstacking in each complex.For each complex,we performed thermogravimetric analysis.For complexes[Cd（obmim）（ccnia）2]2（29）and[Zn（obmim）0.5（dcpa）2]2（31）,we investigated the adsorption properties.For complexes[Zn（obmim）0.5（dcpa）2]2（31）and[Cd（obmim）（dcpa）2]2（32）,we investigated the luminescence properties.（4）We used 3,3’,5,5’-tetramethyl-4,4’-bipyrazole as neutral ligand,together with transition metal（Zn/Cd）and carboxyl anion to synthesize eleven mixed complexes under ultrasonic and hydrothermal conditions.For all complexes,we analyzed their crystalstructureandthermalstability.Forcomplexes[Cd2（H2Bpz）3（hpa）2]2·2（THF）0.5·4Me OH·4H2O（40）and[Cd（H2Bpz）2（cnba）2]（45）,we discussed the fluorescence properties.In this thesis,we used three methods to construct and synthesize 47 dual ligand mixed complexes by adjusting reaction conditions and ligand composition.We analyzed the crystal structure of these complexes and explored the adsorption and luminescence properties of some complexes.So we not only enriched the structures of the complexes,but also provided some experimental experience for exploring the properties of the complexes.Therefore,the studies of the luminescence properties and mechanism of these complexes along with the adsorption performance of organic dyes have a potential application prospect in molecular fluorescence and adsorption. |
