Luminescent Sensor Of Coordination Complexes Constructured By Lanthanide-Oxygen Clusters

Because of the unique 4f electron of lanthanide ions,lanthanide coordination complex that based on lanthanide-oxygen cluster has a wide application in the fields of photoluminescence,fluorescent probe and so on.In this thesis,a series of coordination complexes based on lanthanide-oxygen cluster were synthesized by room temperature volatilization and solvothermal method.The crystal data were obtained by SCXRD and their precise structures were determined,and further characterized by PXRD,FT-IR,TGA and ICP.Luminescence properties of the lanthanide complexes constructed by Tb³⁺/Eu³⁺-oxygen cluster were analyzed in detail,and their performance as luminescent sensors was studied in detail.The main contents of this paper include the following three parts:（1）pH-controlled assembly Ln-Ba nano-clusters and luminescent sensing devices for for acetylacetone and anilineThis chapter uses 7-chloro-1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxoquinoline-3-carboxylic acid as the ligand,and four series of trinuclear,tetranuclear,heptanuclear and octanuclear Ln-Ba clusters,{[Dy₂Ba(C₁₃H₈ClFNO₃)₈·4H₂O]·C₃H₇NO·3H₂O}（1a,[Dy₂Ba]）,[Tb₂Ba₂(C₁₃H₈ClFNO₃)₈·7H₂O]（1b,[Tb₂Ba₂]）,{[Ln₄Ba₃(C₁₃H₈ClFNO₃)₁₆·2NO₃·6H₂O]·5H₂O}(Ln³⁺=Tb³⁺,1c;Eu³⁺,1d;[Ln₄Ba₃])and{[Tb₄Ba₄(C₁₃H₈ClFN-O₃)₁₆·（C₃H₄NO）₂·2NO₃·10H₂O]·3H₂O}（1e,[Tb₄Ba₄]）were synthesized by controlling the pH of the reactant solutions.The work features the first example of lanthanide cluster that the number of nucleus changes regularly with the pH.Moreover,detailed investigation reveals nano-cluster 3a represents a highly selective and sensitive sensor towards acac and aniline.Interestingly,theory analysis reveals that 3a is possible to be fabricated into devices,thus,easy to use sensing devices of test paper,agarose gel,and films on CaCO₃,polyfoam,coin,mask and wall that based on 3a are fabricated by facile methods,and they show a remarkable ability to sense acac and aniline vapors with visibility to the naked eyes.This is the first work on multiple real-time and visual sensing devices based on the lanthanide nano-cluster.（2）Lanthanide metal-organic frameworks based on lanthanide-oxygen cluster as luminescent sensor for tolueneTwo series of lanthanide metal-organic frameworks based on lanthanide-oxygen cluster by solvothermal method,based on the ligands of methylmalonic acid（MMA）and 1,10-phenanthroline（phen）,were successfully synthesized in this chapter.Where[Ln（MMA）（Ac）₂·H₂O]_n（Ln=Eu（2a）,Gd（2b）,Tb（2c））are synthesized by Ln（NO₃）₃ and MMA,[Ln（MMA）（Ac）（phen）]_n（Ln=Eu（2d）,Tb（2e））are obtained with Ln（NO₃）₃,MMA and phen.The five new compounds were structurally determined by single-crystal X-ray diffraction,FT-IR,PXRD,TGA and luminescence.Furthermore,the sensing property reveals that 2a is a luminescent sensor for toxic solvent of toluene.（3）One-pot synthesis of complexes containing lanthanide-oxygen cluster and disulfide bondsThis chapter use 2-mercaptonicotinic acid as ligand and reacts with lanthanide metalsalts.Threesinglecrystalstructuresof{[Ln（C₆H₄NO₂S）₂(C₁₂H₄N₂O₄S₂)₂·8H₂O]·C₁₀H₈N₂·3H₂O}_n(Ln³⁺=La³⁺（3a）,Sm³⁺（3b）)and{[Tb₂(C₁₂H₄N₂O₄S₂)₂]·C₁₂H₄N₂O₄S₂}_n（3c）are obtained by one-pot method at room temperature.Both inorganic synthesis and organic reactions were happened in the one-pot synthesis,（1）coordination of carboxyl oxygen of ligand with lanthanide metal to form lanthanide-oxygen cluster complexes;（2）oxidation of2-mercaptonicotinic acid ligand through thiol group,form disulfide bond.