Design,Synthesis And Fluorescent Recognition Properties Of Triazine Derivatives And Their Organometallic Functional Materials

A chemical fluorescence sensor uses a specific interaction between a measured substance and a fluorescent molecule or material to induce an increase or decrease in fluorescence intensity,or is the emission of fluorescence wavelength changes to achieve the detection of the material and signal transmission.Chemical fluorescence sensors are a new means of analytical testing for Analytical Chemistry.It has the advantages of high sensitivity,convenience,good selectivity,real-time on-line detection,short response time,high accuracy and so on,in particular,it has found concrete applications in the fields of life sciences,materials science,environmental science,Energy Sciences,nanosciences and Information Sciences.At the same time,it also shows a wide range of applications,such as industrial production,chemical technology,biological science,clinical medicine,catalytic science,Environmental Monitoring,factory automation control and Scientific Research,and many other aspects.The general idea of this research is to design and synthesize several triazine derivatives and their organometallic compounds.The structure and composition of compounds were characterized by FT-IR,Vario EL,¹H NMR,¹³C NMR,powder polycrystalline diffraction(PXRD),thermogravimetric analysis(TGA),scanning electron microscopy(SEM)and x-ray photoelectron spectroscopy(XPS).The fluorescence properties of the compounds were studied by fluorescence and ultraviolet Spectra.The recognition properties of transition metal cations(including rare earth cations),anions and organic solvents by fluorescent materials were investigated,and the mechanism of multi-response fluorescent recognition materials was studied,it provide a useful reference for the synthesis of multi-response fluorescent recognition materials and the recognition of ionic molecules.The thesis is divided into four parts.In the first part,a 2,2',2'-[(1,3,5)-triazine-2,4,6-triamine group]tribenzoic acid fluorescence sensor(L)was designed and synthesized.The recognition of metal cation and organic solvent by the sensor was studied.The results showed that Zr⁴⁺and Al³⁺had strong fluorescence enhancement effect on the fluorescent material,while Fe³⁺and acetone had typical fluorescence quenching effect on the fluorescent material.The influence mechanism of fluorescence enhancement and quenching was analyzed by ultraviolet spectrum.The application of the sensor to detect Fe³⁺in human urine and drinking water was also studied.In the second part,a new zirconium-based organometallic framework fluorescence sensor(Zr-L)was designed and synthesized from 2,2',2"-[(1,3,5)-triazine-2,4,6-triimino]tribenzoic acid(L)and Zr ONO₃·2H₂O.The structure of Zr-L is stable in boiling water and different p H value solution,but the fluorescence intensity of Zr-L shows a parabola distribution of opening up in different p H value solution.In recognition of metal ions,anions and organic solvents,it was found that the fluorescence quenching effect of Fe³⁺,Cr₂O₇^2-,acetone,CCl₄ and xylene.Compared with the MOF reported in the literature,this material has the characteristics of low dosage(0.001 mg/m L)and multiple recognition,but the quenching of fluorescence is unfavorable to the further development of the synthesis and application of the new fluorescent material.At the same time,the application of the sensor to the determination of Fe³⁺in different water samples and the determination of CCl₄ and xylene in organic solvents were studied.In the third part,a new aluminum-based metal-organic framework fluorescence sensor(Al-L)was designed and synthesized from 2,2',2"-[(1,3,5)-triazine-2,4,6-triamine group]tribenzoic acid(L)and Al NO₃·9H₂O.The structure of Al-L was highly stable in boiling water and different p H solutions,but its fluorescence intensity also showed certain changes in different p H solutions.In the recognition of metal ions,anions and organic solvents,it was found that this fluorescent material showed strong fluorescence enhancement effect on Fe³⁺,Sr²⁺and SiO₃^2-ions,especially when the concentration of SiO₃^2-ions was 10^-8 M,which could enhance the fluorescence intensity of this fluorescent material,with high selectivity and sensitivity.It was found that toluene had strong fluorescence quenching effect on the fluorescent material.At the same time,the fluorescence enhancement of Fe³⁺,Sr²⁺and SiO₃^2-ions on the fluorescence sensor laid a foundation for further expanding the new fluorescence sensor.The application of Fe³⁺detection in different water samples and vegetables was also studied.The fourth part,designs,synthesizes 1,1'-(6-chloro-1,3,5-triazine-2,4-diyl)bis(1H-benzo[d][1,2,3]triazole)fluorescence sensor(Q).Compared with the first part,the sensor does not contain-COOH,but is rich in nitrogen atoms.The synthesized material has no fluorescence characteristic,but the synthesized Ligand Q has strong fluorescence characteristic and has the property of lumped luminescence.In the recognition of metal Ions,anions and organic solvents,it is found that ligand Q exhibits the typical fluorescence quenching effect on Fe³⁺,Cr₂O₇^2-and nitrobenzene.whereas Ligand Q exhibits strong fluorescence enhancement effect on toluene and xylene.At the same time,the detection of Fe³⁺in different water samples and vegetables,as well as the detection of toluene and xylene in oil were studied.In this paper,two new triazine derivatives,one containing-COOH and one without-COOH,have been synthesized from synthetic chemical fluorescence sensors.The fluorescence properties of these two kinds of chemical fluorescence sensors have been analyzed.Taking Fe³⁺ion as an example,Ksv(L)>Ksv(Q),LOD(L)>LOD(Q),triazine derivative(L)containing carboxylic group showed significantly better selectivity to Fe³⁺ion than triazine derivative(Q)without carboxylic group.The main reason is that-COOH in Ligand L can easily coordinate with Fe³⁺ions to form metal complexes without fluorescence.Furthermore,two kinds of metal organic complexes(Zr-L and Al-L)fluorescent sensors were developed by using chemical sensors(l)containing-COOH.The Zr-L continued the fluorescence characteristics of Ligand L and exhibited strong fluorescence quenching effects on the identified ions(Fe³⁺and Cr₂O₇^2-)and molecules(acetone,CCl₄ and xylene).Different from Ligand L,the Al-L can recognize Fe³⁺,Sr²⁺and SiO₃^2-ions by fluorescence enhancement and toluene by fluorescence quenching.From the analysis of ions and moleculars recognition effect,the structure of triazine derivatives can be regulated not only for detection of Fe³⁺,Cr₂O₇^2-,acetone,toluene and nitrobenzene by fluorescence quenching,but also for the detection of Fe³⁺,Sr²⁺,SiO₃^2-,toluene and xylene by fluorescence enhancement.Furthermore,the types of ion and molecular detection are enriched in the current ion and molecular fluorescence recognition,such as chemical sensor for Sr²⁺,SiO₃^2-,CCl₄,toluene and xylene.For Fe³⁺,from the Lod analysis,LOD(Zr-L)>LOD(L)>LOD(Al-L)>LOD(Q).The results show that among the four kinds of fluorescent materials,the zirconium based organic complex(Zr-L)formed by ligand L and Zr4 ions has the strongest ability to detect Fe3 ions,but the traditional fluorescence quenching is still used to detect Fe³⁺ions.