A Series Of Coordination Polymers Constructed By Carboxylate Ligands And N-donor Ligands: Luminescence Tuning And Sensing And Photocatalytic Performance

Based on the diversity and designability of structure,metal-organic coordination polymers exhibit potential application in the fields of gas storage and separation,ferroelectric,non-linear optics,heterogeneous catalysis and luminescence and so on.In this thesis,20 compounds were designed and constructed used H₄btca and Htpbpc?H₄btca = biphenyl-2,3,3',5'-tetracarboxylic acid,Htpbpc = 4'-[4,2';6',4"]terpyridin-4'-yl-biphenyl-4-carboxylic acid?combining with different metal ions via hydrothermal or solvothermal conditions;phen and H₂bdc?phen = 1,10-phenanthroline,H₂bdc = terephthalic acid?were introduced during some processes of the synthesis.According to the structural features of these compounds,the luminescence tuning,luminescence sensing and photocatalysis properties were investigated,respectively.The main contents are summarized as follows:Firstly,a series of Ln-MOFs?1-13?were successfully synthesized using H₄btca ligand,phen ligand and LnCl3·6H₂O via hydrothermal method.Based on the bright red and green luminescence of complexes 6 and 8,series of hetero-metallic compounds,namely[EuxTb1-x?Hbtca??phen?]?0 ? x ? 1??14-17?,were constructed by the co-doping method with different metal co-doping ratio.Through change the excitation wavelength and the co-doping ratio of Eu3+/Tb3+,tuned luminescence and white-light emission could be realized easily.Secondly,through solvothermal method,a 1D Complex 18,namely[Eu2?tpbpc?4·CO3·4H₂O]·DMF·solvent?18?,was successfully constructed.The luminescent investigations confirm that the red light of Complex 18 possess excellent water-stability and pH-stability and it is the first example of MOF-based fluorescent probe,with high selectivity,high sensitivity and low detection limit,targeting to Cr3+,CrO42-and Cr2O72-ions in aqueous solution.Furthermore,the simple fluorescent-based test paper were successfully prepared and provided a reliable and visual detection of Cr?III?and Cr?VI?ions in daily applications.Thirdly,a sequence of 3D compounds,[M?tpbpc?2·]·solvent?19-22?,were synthesized by Htpbpc ligand and transition metal.Herein,MOF 19 could be regarded as a ratiometric luminescence sensor for Hg²⁺ ion in the region of 10-6-10-3 M.Besides,it can quantitatively sensing of Cr?VI?ions in the aqueous solution with high selectivity,low detection limit,short response time and reusability.Finally,a 2D Co-MOF with the formula {Co?tpbpc??bdc?0.5·H₂0]·solvent},have been successfully synthesized under solvothermal conditions.Furthermore,a series of 2D isomorphous Co²⁺/Zn²⁺ metal-doped metal-organic frameworks have been constructed through co-doping Zn²⁺ ions in the MOF.Interestingly,when Co²⁺ ions are gradually replaced by Zn²⁺ ions in the isostructural MOFs as a catalyst,the ability of degradation for methyl orange?MO?have improved gradually.This work can offer a controllable regulation of photocatalytic properties by changing metal ions in isostructural metal-doped MOFs.