Construction And Sensing Applications Of Luminescent Coordination Polymers Based On Polycarboxylic Acid Ligands

Coordination Polymers?CPs?have attracted great attention for chemists due to their structural and functional diversities.The luminescent coordination polymers can recognize various objects based on the interaction between the host and the guest,which has potential applications in luminescent sensing for anions,cations,small organic molecules,explosives,and biomarkers.In this thesis,coordination polymers based on transition/lanthanide metal ions with different dimensionalities were designed and synthesized with the mixed ligands strategy.Their applications as luminescent sensors in sensing ions and small organic molecules were studied.1.Threewater-stableCPs,{[Cd₂?bptc??2,2'-bipy?₂?H₂O?₂]}_n?1?,{[Cd₂?bptc??phen?₂]·4H₂O}_n?2?,and{[Cd₂?bptc??4,4'-bipy??H₂O?₂]·4H₂O}_n?3?,were synthesizedundersolvothermalconditionsbyusing3,3',5,5'-biphenyltetracarboxylic acid?H₄bptc?as the main ligand and various N-donor ligands as auxiliary ligands?2,2'-bipy=2,2'-bipyridine;1,10-phen=1,10-phenanthroline;4,4'-bipy=4,4'-bipyridine?.CPs 1-3 show structural diversity from 1D ladder chain,2D layer to 3D framework,respectively.Luminescent studies reveal that CPs 1-3 are promising luminescent sensors that can detect ferric ions and chromate/dichromate ions with highly selectivity and sensitivity.CP 1 with 1D structure showed the best performance freeing from the interference of other ions present in aqueous medium.2.Two CPs containing d¹⁰ metal ions,{[Cd₂?FDA??trz?DMA]}_n?4?and{?CH₃?₂NH₂[Zn_2.5?FDA?₂?trz?₂]·2DMA}_n?5?,wereobtainedwith2,5-furandicarboxylic acid?H₂FDA?as the main ligand and 1,2,4-triazole?Htrz?as the auxiliary ligand.The results of acid-base stability analysis and luminescent properties show that CP 4 has good pH stability and can selectively recognize1-hydroxy-2-butanone?a metabolite of chloroprene?through luminescent quenching effect in a simulated urine environment.3.Two 3D isomorphic lanthanide CPs,{?CH₃?₂NH₂[Ln₂?FDA?₃?HCOO?]}_n?Ln=Eu?6?,Gd?7??,were obtained with 2,5-furandicarboxylic acid?H₂FDA?.The luminescent intensities of ethanol suspensions of CP 6 were almost unchanged when toluene was added,but the addition of benzaldehyde made the luminescent intensities quench significantly.Moreover,the luminescent intensities of suspension changes with the volume ratio change of toluene/benzaldehyde mixture.