| Coordination polymers?CPs?are novel hybrid crystalline materials formed by the coordination of inorganic metal centers and organic functional linkers through coordination bonds.Coordination polymers have a highly ordered structure and tunable functional characteristics,which make its show broad application prospects in many fields such as drug delivery,enzyme immobilization,gas storage,separation and catalysis.During the construction of the coordination polymer,the choice of metal central ions and organic linkers played a decisive role in the formation of the final structure and its functional properties.Carboxylic acid-based ligands have a variety of coordination modes and can be used with transition metal ions and alkaline earth metal ions to synthesize coordination polymers with excellent performance.In this dissertation,six three-dimensional complexes were synthesized by symmetric rigid ligands 3,5-bis?2,4-dicarboxyphenyl?nitrobenzene?H4L?,transition metal ions and alkaline earth metal ions under hydrothermal conditions,and the structure determination and basic characterization of the six complexes were performed.Based on the different structures of the complexes,we conducted detailed studies on their gas adsorption,CO2conversion,dye adsorption,and magnetic properties.The full text is divided into three chapters:Chapter 1:The coordination polymers are summarized,and its synthesis,classification and application are briefly introduced.The research progress of zeolite-like porous coordination polymer is summarized.Chapter 2:A zeolitic Zn4O-cluster-based porous coordination polymer{[Zn4?O??L?2]·4DMF·6H2O}n?1?has been hydrothermally synthesized by ligands H4L and Zn???ions,and its structure can be simplified as Sodalite?SOD?topology network.Based on complex 1,we introduced Co???ions to synthesize Zn/Co bimetal doped coordination polymer{[Znx?Co?4-x?O??L?2]·4DMF·6H2O}n?2?,and the gas adsorption properties of complexes 1 and 2 were tested,1 and 2 exhibits a high CO2/CH4adsorption selectivity,and the CO2and CH4adsorption capacity of complex 2 at room temperature was much greater than 1.At the same time,the high-density metal sites in 1and excellent capability of capturing CO2at ambient temperature,which enables it to catalyzing CO2and epoxides to synthesize cyclic carbonates under mild reaction conditions?70°C,1atm?.In addition,complex 1 also exhibits good adsorption capacity for methyl green?MG?dyes.Chapter 3.Four three-dimensional complexes[Ba2?L??H2O?2]n?3?,[Sr2?L??H2O?2]n?4?,{[Ca?H2L?]·2H2O}n?5?,{[Co2?L??H2O?3]·DMA}n?6?was constructed using alkaline earth metal ions?Ba???,Sr???,Ca????and transition metal ion?Co????and ligand H4L.Among them,complexes 3 and 4 are isomorphic,complex 3 has a good CO2adsorption capacity at normal temperature.At the same time,a large number of open metal sites are obtained in 3after removing the coordinated water molecules,which can catalyze CO2cycloaddition reaction under mild reaction conditions,and shows high catalytic activity and excellent cycle stability.In addition,the magnetic performance studies show that antiferromagnetic interactions exist between Co???ions in complex 6. |
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