Preparation And Researching On Photoluminescence Proterty Of Benzioc Acid Derivative-functionalized Polysulfone-Eu(Ⅲ)Ion Complexes

Bonding type polymer-rare earth complexes luminescence materials is shaped by polymerization of functional monomers or rare earth-organic luminescence complexes bonded to the polymer side chain, which is a class of high-performance luminescence materials, not only retains the excellent photoluminescence proterty of rare earth-organic complexes, still possesses good mechanical properties and easy processing and molding characteristics of polymers,but also makes the luminescence materials internal were homogeneous characteristics. Although such luminescence materials has been reported still relatively small,but it has potential applications, needed to vigorous expansion.In this paper, Benzoic acid derivative which concurrently has dual function of sensibilization and coordination was bonded to the chains of chloromethylated polysulfone (CMPSF) via a polymer nucleophilic substitution reaction. Preparing macromolecular ligands which can sensitizes luminescence of rare earth ions mightily,obtaining a high-performance bonding type polymer-rare earth complexes luminescent materials accordingly, studying their fluorescence emission properties.In this study, firstly,wo will use Friedel-Crafts alkylation reaction, based on1,4-dichloro-methoxy butane as chloromethylation reagent to prepare chloromethylated polysulfone(CMPSF).Secondly the nucleophilic substitution reaction between the chloromethyl group of chloromethylated polysulfone (CMPSF) and phenolic hydroxyl group of3-nitro-4-hydroxy benzoic acid (NHBA) was conducted, and the nitro-benzoic acid (NBA) ligand was bonded on the side chains of polysulfone (PSF),obtaining nitrobenzoic acid functionalized polysulfone NBA-PSF. In this work, the functionalization reaction of PSF was mainly investigated, and the effects of the main factors on the substitution reaction between CMPSF and NHBA were examined to optimize the reaction conditions.The chemical structure of NBA-PSF was characterized by FTIR and lH-NMR spectra.In this paper, nitrobenzoic acid(NHBA) and formylbenzoic acid(FHBA) were bonded on the side chains of polysulfone (PSF) in a similar manner, obtaining two benzoic acid derivative-functionalized polysulfone, PSF-NBA and PSF-FBA.Obviously, PSF-NBA and PSF-HBA are all the ligand-macromolecule aromatic acid containing electron-withdrawing substituents groups. The two macromolecular ligands were allowed to be coordinated with Eu(III) ion, and the binary complexes PSF-(NBA)3-Eu(III) and PSF-(FBA)3-Eu(III) were prepared.At the same time, ternary complexes were prepared with small molecular phenanthroline (Phen) as the second ligand.The photo physical behaviors of these complexes were examined, and the effects of the two electron-withdrawing substituent groups, nitro group and formyl group, on the luminescence property of these complexes were mainly investigated. The experimental results indicate that the two electron-withdrawing substituent groups affect the luminescence property of the complexes of benzoic acid-functionalized polysulfone and Eu(III) ion greatly.They make the excitation energy of ligand BA to be dissipated through an intraligand charge transfer (ILCT),and lead to the triplet state energy of ligand BA to be declined.As a result, the matching degree between the lowest triplet level of ligand BA and resonance energy level of Eu(III) ion is enhanced markedly, and ligand BA produces a stronger sensitization for the florescence emission of Eu(III) ion, resulting in the strong florescence emission of the complexes.However, on the other hand, the fluorescence quenching action of nitro group for the fluorescence of the complexes still will occur, resulting in the decreasing of the luminescence property of the complexes with increasing complex concentration.In this paper, nitrobenzoic acid(HMOBA) and formylbenzoic acid(DHBA) were bonded on the side chains of polysulfone (PSF) respectively in a similar manner, obtaining two benzoic acid derivative-functionalized polysulfone, PSF-MOBA and PSF-HBA. Obviously, PSF-MOBA and PSF-HBA are all the ligand-macromolecule aromatic acid containing electron-donating substituents groups.The two macromolecular ligands were allowed to be coordinated with Eu(III)ion, and the binary complexes PSF-(MOBA)3-Eu(III) and PSF-(HBA)3-Eu(III) were prepared. At the same time, ternary complexes were prepared with small molecule phenanthroline (Phen) as the second ligand. The photo physical behaviors of these complexes were examined,and the effects of the two electron-donating substituent groups,Methoxy group and hydroxy group, on the luminescence property of these complexes were mainly investigated.The experimental results indicate that the two electron-donating substituent groups affect the luminescence property of the complexes of benzoic acid-functionalized polysulfone and Eu(III)ion greatly. They can decrease the excitation energy of ligand BA through p-π conjugation effect, and so lead to the triplet state energy of ligand BA to be declined. As a result, the matching degree between the lowest triplet level of ligand BA and resonance energy level of Eu(III) ion is enhanced markedly, and ligand BA produces a stronger sensitization for the florescence emission of Eu(III)ion, resulting in that the florescence emission intensities of the binary complexes of PSF-(MOBA)3-Eu(III) and PSF-(HBA)3-Eu(III) are much higher than that of the binary complex of PSF-(BA)3-Eu(III).The florescence emissions of the ternary complexes and solid films of the complexes also exhibit a similar trend.