| As an oxygen-containing multidentate organic ligand,hydroxycarboxylic acid can interact with metal ions to obtain a multi-nuclear,multi-dimensional structured functional coordination polymer.This kind of material not only has a diversity of structures,but also has a wide range of application.It also indicates new directions for the design and synthesis of new energy materials and catalytic materials.2-hydroxybenzenetricarboxylic acid?2-OH4btc?was used as a precursor ligand to precisely synthesize dinuclear complexes in this paper.Zinc and manganese complexes were hydrothermal synthesized by adding different metal ions,adjusting the system's counter anion,reaction ratio,pH and system cooling rate,etc.,14 kinds of coordination polymerization based on 2-hydroxybenzenetricarboxylic acid were synthesized in this paper,which have not been reported yet.The complexes based on zinc and manganese were characterized by EA,IR,XRD,CV,TG and CCD.Single crystal diffraction was used to confirm their crystal structures.The photoluminescenc-e,electrochemical,photocatalytic water oxidation,cyanosilylation were also studied.The organization of chapters is given as follows:1.The first chapter is the introduction part,the metal-organic complexes,the method of how to synthesize them,the research progress of hydroxyl-containing benzene carboxylic acid ligands,as well as the functional application of them are introduced systematic here.In particular,we focus on the research progress of photocatalytic water oxidation and cyanosilylation.2.Zn was usd as the metal center,seven novel zinc coordination polymers constructed from 2-OH4btc,namely,[Zn?H2Obtc??H2O?3]?1??[Zn4?Obtc?2?bpye??H2-O?4]·H2O?2??[Zn?H2Obtc??bpy??H2O?]·H2O?3??[Zn2?Obtc??bpy?0.5]?4??[Zn4?Obtc?2-?bpyE??H2O?4]·H2O?5??[Zn4?Obtc?2?phen??H2O?2]?6?and Zn2?Obtc??H2O?2]·H2O?7?,have been synthesized with hydrothermal methods.Among them,?2?and?5?are isomorphic,the coordination environment,the coordination number and structural configuration of metal centers are the same.Complex?1?-?7?have strong fluorescence properties at room temperature.Compared with the maximum emission peak position of the ligand,the maximum emission wavelength of?1?-?3?shows a blue shift to varying degrees.The maximum emission wavelength of?4?-?7?have a different degree of red shift.The?2?complex was used as a kind of fluorescence sensor to detect metal ions in aqueous solution.The percentage of annihilation caused by Fe3+was over 90%,and the quenching effect was best.In the non-solvent heterogeneously catalyzed cyanide cyanide reaction,complexes?1?-?7?showed good activity,has good catalytic selectivity for benzaldehyde.The corresponding catalytic yields were?3?>?5?>?2?>?7?>?6?>?4?>?1?,in which the catalytic efficiency of the complex?3?is as high as 99.1%,and has good recycling performance.3.Mn was used as the metal center,seven novel manganese coordination polymers constructed from 2-OH4btc,namely,[Mn?H2Obtc??H2O?3]?8??[Mn2?Obtec??bpy??H2O?4]·2H2O?9??[Mn2?H2Obtc?2?phen?2?H2O?2]?10??[Mn2?Obtc?-?phen?2?H2O?]·H2O?11??[Mn3?Obtec?2?bpyE?2?H2O?2]·H2O?12??[Mn2?Obtc??bpy?-?H2O?3]·2H2O?13?and[Mn4?Obtc?2?bpye?2?H2O?5]·7H2O?14?,have been synthesized with hydrothermal methods,Among them,?1?and?8?are isomorphic.The dinuclear manganese complex?9?has electrochemical activity in the scanning potential range of 0-1.6Vs,and simultaneously studies the?9?water-catalyzed photolysis properties.The results show that the dinuclear manganese complex?9?has a certain photocatalytic water oxidation activity.4.Summarizing the full text and looking forward to the follow-up work:The[2+2]binuclear unit can be formed by 2-hydroxyisophthalic acid and this compound.A hole structure complex with dual-nuclear active centers can be prepared by using relevant coordination group of frame construction and control the experimental conditions.This kind of complex"wrapped"photosensitizer to achieve efficient photocatalytic water oxidation heterogeneous catalytic purposes. |
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