Preparation And Researching On Fluorescence Emission Character Of Photoluminescence Functionalized Naphthoic Acid Functionalized Polysulfone Rare Earth Ion Complexes

Bonding type polymer-rare earth complexes luminescence materials possesses theexcellent photoluminescence and easy processing characteristics of polymers, and goodmechanical properties, still can make the luminescent material internal showshomogeneous characteristics. It attracts more attention as rare earth complexes ofphotoluminescence materials. Polymer-metal complexes is a investigative hotspot inluminescence materials. Its application prospect is very broad, especially in the field ofelectroluminescent, can be used as a light-emitting layer material, the preparation ofelectroluminescent devices, In this paper, Small molecule ligands naphthoic acid wasbonded to the chains of polysulfone （PSF） via a polymer nucleophilic substitutionreaction. and its fluorescence properties and thermostability were mainly investigated.Based on1,4-dichloro methoxy butane which is used as chloromethylation reagent,we will get chloromethylation polysulfone （CMPSF） through Friedel-Crafts alkylationreaction. Then we use chloromethylation polysulfone （CMPSF） as the starting materialand we will improve the functionalization of chloromethylation polysulfone （CMPSF）through the nucleophilic substitution reaction which brings about bonding6-hydroxy-2-naphthoic acid （HNA） ligands modified polysulfone PSFNA. UsingFourier transform infrared spectroscopy （FTIR） and nuclear magnetic resonancehydrogen spectrum （¹H-NMR）, we get the characterization on the structure. We mainlystudy the influence of main factors on the nucleophilic substitution reaction, and theexperiment shows that under the action of absorb acid agent, the reaction temperatureand polarity of the solvent has great influence on nucleophilic reaction. What is more,the results also show that HNA nucleophilic reagent concentration had no effect on the reaction, indicating that this is a typical unimolecular nucleophilic substitution reactioni.e. SN1. and the suitable reaction conditions are as follows: temperature of70℃, withdimethyl sulfoxide as solvent, In this conditions, the NA bonding quantity of modifiedpolysulfone were1.28mmol/g.The coordination reaction between PSFNA and Eu³⁺and Tb⁺³ion was allowed tocarry out, preparing the polymer-rare earth complex, PSF-（NA）₃-Eu（Ⅲ） andPSF-（NA）₃-Tb（Ⅲ）. PSF-（NA）₃-Eu（Ⅲ） possesses the characteristic fluorescenceemission spectrum of Eu³⁺ion. More significantly, the macromolecular ligand PSFNAcan strongly sensitize the fluorescence-emission of Eu³⁺ion. The NA ligand bonded onthe side chains of PSFNA has no sensibilization for the fluorescence emission of Tb（Ⅲ）ion, in contrast, a energy back transfer from the excited state5D3of Tb（Ⅲ） ion to thetriplet state T1of the NA ligand will occur. The ternary complexesPSF-（NA）₃-Eu（Ⅲ）-（Phen）1and PSF-（NA）₃-Eu（Ⅲ）-（Bipy）1, were prepared by thecoordination of Eu（Ⅲ） ion, respectively, with PSFNA as a macromolecular ligand andsmall molecular phenanthroline （Phen） and2,2′-bipyridine （Bipy） as the second ligand.The chemical structures of these complexes were characterized by FTIR and UVabsorption spectra, and their florescence emission characters were examined, andespecially, the relationship between their florescence emission properties and chemicalstructures was investigated in depth. and the corresponding experimental results wereexplained from the view of micro-mechanism with Antenna effect theory. Theexperimental results show that all of the secondary and ternary complexes formed bythe coordination of PSFNA and Eu（Ⅲ） ion can emit the strong characteristicfluorescence of Eu（Ⅲ） ion, suggesting that the NA ligand bonded on the side chains ofPSFNA can effectively sensitized the fluorescence emission of Eu（Ⅲ） ion.The apparently saturated coordination number of the binary complexPSF-NA-Eu（Ⅲ） is10, and it is PSF-（NA）5-Eu（Ⅲ） which is with apparent saturationligand structure. The ternary complex PSF-（NA）5-Eu（Ⅲ）-（Phen）1, which is preparedby adding Phen to the solution of PSF-（NA）5-Eu（Ⅲ） for the complementary coordination, not only possesses the strongest fluorescence emission but also hasexcellent thermal stability.