Preparation And Researching On Fluorescence Emission Character Of Photoluminescence Functionalized Polysulfone-Metal Ion Complex

Bonding type polymer-metal complexes is a electroluminescent materials which notonly has high luminous intensity and high thermal stability, but also has goodmechanical properties and processed film easily. Preparation of polymer-metalcomplexes luminescent materials make sense for the development of new type ofphotoelectric material. In this paper, small molecul organic ligands was bonded to theside chains of Polysulfone （PSF） via a polymer reaction. two species of highperformance luminescence materials polymer-metal complexes were prepared, and itsfluorescence properties were mainly investigated. It provide a new idea for polymeric ofthe metal complexes.Polysulfone （PSF） was functionalization-modified with 4-（chloromethyl） benzoicacid （CMBA） as reagent via Friedel-Crafts alkylation action, and benzoic acid （BA）_ligand was bonded to the side chains of PSF, obtaining the functional macromoleculeBAPSF. The chemical structure of BAPSF was characterized by Fourier TransformInfrared spectroscopy （FTIR） and ¹H-NMR spectra. In this work, The effects of the mainfactors on the Friedel-Crafts alkylation action were examined,the reaction mechanismwas discussed, and the reaction conditions were optimized. The experimental resultsshow that the Friedel-Crafts alkylation reaction between CMBA and PSF can proceedsuccessfully, and the suitable reaction conditions are as follows: a temperature of 70℃,with N, N-dimethylacetylamide （DMAC） as solvent, and using SnCl₄as Lewis catalyst,and In this conditions, the BA bonding quantity of modified Polysulfone were 2.45mmol/g. The binary complexes PSFBA-Tb（III） and PSFBA-Eu（III） were prepared by thecoordination of Tb（III） and Eu（III） ion with modified Polysulfone PSFBA. The chemicalstructures of the complexes were characterized by Fourier Transform Infraredspectroscopy（FTIR） and UV absorption spectra. In this work, the fluorescence emissionproperties of the solution and the film for the complexes was mainly investigated. Theexperimental results show that the BA ligands bonded on the side chains of PSFBA notonly with double teeth chelating coordination effect, but also can produce significantAntenna effect. The solution and the film of binary complex PSFBA-Tb（III） possess thestrong characteristic fluorescence emissions spectra of Tb（III） ion, and the binarycomplex PSFBA-Eu（III） possess the characteristic fluorescence emissions spectra ofEu（III） ion, and the sensitization effect to Tb（III） ions of BA ligands was stronger than toEu（III） ions, or the triple state energy level （T1） of ligands BA matches well with theresonance level of Tb （III） than with Eu （III）.The binary complex with more ligands PSF-（BA）n-Tb（III） was prepared by thecoordination of Tb（III） ion and PSFBA, and two kinds of the ternary complexPSF-（BA）n-Tb（III）-Phen, PSF-（BA）1-Tb（III）-（Phen）2and PSF-（BA）1-Tb（III）-（Phen）3were prepared by the coordination of Tb（III） ion and PSFBA using PSFBA as amacromolecular ligand and phenanthroline（Phen） as a smaller ligand. The chemicalstructures of the complexes were characterized by Fourier Transform Infraredspectroscopy（FTIR） , UV absorption spectra and Thermo-Gravimetric Analysis （TG）. Inthis work, the relationship between the structure and properties including thefluorescence emission properties of the solutions and the films and the thermal stabilityfor the complexes were mainly investigated. The experimental results show that theapparent saturated coordination number of the binary complex PSF-（BA）n-Tb（III） is 10,which implies that the coordination of BA to Tb（III） reaches saturation and right now thebinary complex has a maximum fluorescence as the binary complex has the structure ofPSF-（BA）5-Tb（III）. The ternary complex PSF-（BA）5-Tb（III）-（Phen）1, which is preparedby adding Phen to a solution of PSF-（BA）5-Tb（III）, possesses the strongest fluorescence emission and excellent thermal stability compared with ternary complexesPSF-（BA）₁-Tb（III）-（Phen）₃ and PSF-（BA）₁-Tb（III）-（Phen）₂, which are prepared using theconventional ratios of reagents.5-chloromethyl-8-hydroxyquinoline （CHQ） was first prepared through the reactionHQ and chloromethylation reagent 1,4-bichloromethoxy-butane （BCMB）. Polysulfone（PSF） was functionalization-modified with CHQ as reagent via Friedel-Crafts alkylationaction, obtaining the modified polysulfone HQ-PSF. The chemical structures of HQ-PSFwas characterized by Fourier Transform Infrared spectroscopy （FTIR） and1H-NMRspectra. Polymer-metal complex Mq_n-PSF were prepared by the coordination ofmetal（Al³+,Cu²+,Zn²+） and HQ-PSF using HQ-PSF as a macromolecular ligand and HQas a smaller ligand. The chemical structures of the complexes were characterized byFTIR and UV spectra. In this work, the fluorescence emission properties of the solutionsand the films for the complexes were mainly investigated. The experimental results showthat the Friedel-Crafts alkylation reaction between PSF and CHQ can proceedsuccessfully. The solution and the films of Polymer-metal complex Mq_n-PSF possessesthe the strong characteristic fluorescence emissions spectra, and fluorescence spectrumof films were stronger and red shift than solution, In comparison with the fluorescenceintensity of films and solution, the size order was Znq₂–PSF>Alq₃-PSF>Cuq₂-PSF.