Synthesis And Catalysis?Luminescence Of Metal-Organic Framework Materials

As a new class of crystalline porous solid,metal-organic frameworks?MOFs?have rapidly developed into a research hotspot in the cross realm of energy,materials and bioscience,mainly because of their attractive advantages of novel topology,the macro-control,as well as post-synthetic medication and potential applications in traditional areas of gas storage and separation,catalysis,chiral separation,chemical sensors and fluorescence properties and emerging fields of drug delivery and biomedicine.Based on the principle of crystal engineering,we turned to the synthesis of new MOFs materials and characterize their structures in detail.Furthermore,their gas storage and seration,catalysis,molecular recognition and fluorescence properties were mainly investigated.The major research contents are as follows:1 Five functionalized porous coordination polymers 1–5 with highly ordered amide groups in the channels show notable interaction with guest molecules.Catalytic studies on catalysts with two different active organic functionalities?amide-,amino-,hydroxyl-,and so on?within the cavities revealed that these porous materials are heterogeneous,efficient and recycled catalysts for the Knoevenagel condensation reaction.Most importantly,compound 3 with two different functionalities decorating the porous wall displays an elegant example of cooperative catalysis and excellent size-selectivity towards the substrate.2 A Co-MOF1 with both a cage and channel structure coexistence has been obtained through utilizing Co²⁺ions and bifunctional organic ligand HCPT?4-?4-carboxyphenyl?-1,2,4-triazole?.The gas sorption studies under room temperature illustrate that Co-MOF1 shows the higher C₂H₂ adsorption,N₂ and CH₄are almost not be adsorbed.The catalytic activity of Co-MOF1 was examined in[2+2+2]cycloaddition reaction.3 A cationic cage-based porous lanthani-organic framework Tb-MOF1 has been successfully constructed by using the Tb³⁺ion and tricarboxylate ligand H₃BTB?1,3,5-Ttis?4-Carboxypheny?benzene?).Luminescent studies reveal that Tb-MOF1 exhibits an effective detection of small organic molecules,metal cations especially for Al³⁺.Although sever MOFs have been reported as luminescent detectors for Al³⁺,most of them are based on one characteristic emission.Tb-MOF1 exhibits high-sensitivity sensing of Al³⁺ion via tuning the energy transfer efficiency between two different emissions.4 Coordination of the Tb³⁺ion and the flexible dicarboxylate ligand H₂OBA?4,4'-Oxybisbenzoic acid?with different auxiliary ligands resulted in two Tb-MOFs.Tb-MOF2 is three-dimensional framework with three-fold interpenetrated which can be simplified an unreported 3,6-connected double node topology,the short vertex symbol{4²·6}₂{4⁸·6⁶·8}.Tb-MOF3 has the two-fold interpenetrating structure with one-dimensional microporous channel.The gas sorption studies show that Tb-MOF3could adsorb more C2H2 and CO2 than CH4 and N2 under the same conditions.The luminescent colors change from green,yellow to red based on regulating the proportion of Eu³⁺and Tb³⁺ions in mixed Eu/Tb-MOFs.Luminescent studies indicate that Tb-MOF3 shows high sensitivity fluorescence recognition of organic small molecule solvent of acetone and metal cation Cu²⁺.