1. State Key Laboratory of Polymer Physics and Chemistry, Joint Laboratory of Polymer Science and Materials, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China 2. State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China 3. Key Lab of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012, China 4. Graduate School of Chinese Academy of Sciences, Beijing 100039, China
Abstract：In order to investigate the relationship between the aggregation structure and fluorescence properties of composites of rare earth fluorescent complexes and polymers, the fluorescent complexes of Eu(TTA)3·2H2O and Eu(TTA)3·(TPPO)2 were synthesized by the reaction of TTA(2-thenoyltrifluoroacetone), TPPO(triphenylphosphine oxide) and EuCl3, and their composites with polyvinylpyrrolidone (PVP K30) were prepared. The fluorescence spectroscopy, FTIR spectroscopy and TEM were used to characterize these composites. Fluorescence spectroscopy results indicated that the fluorescence intensity of the PVP/Eu(TTA)3·2H2O composites is obviously improved compared with that of the Eu(TTA)3·2H2O complexes. For the composites with the molar ratio of the complexes to the repeat unit of PVP being 1∶35, the intensity of 612nm emission peak of the composites is 5.5 times for PVP/Eu(TTA)3·2H2O and 0.3 times for PVP/Eu(TTA)3·(TPPO)2 higher than that of the corresponding pure rare earth fluorescent complexes. And the emission intensity ratio of 612 to 590 nm peak is 14.7 in PVP/Eu(TTA)3·2H2O composite, larger than that of Eu(TTA)3·2H2O complexes. These results suggested that the luminescent properties of the europium fluorescent complexes were obviously enhanced in the presence of PVP matrix and there are interactions between the fluorescence complexes and PVP molecules. In the presence of PVPK30, the FTIR spectra of the Eu(TTA)3·2H2O complexes were obviously influenced as well. Based on the curve-fitting results of IR spectra of PVP/Eu(TTA)3·2H2O composites with the molar ratio of repeat unit of PVP to Eu(TTA)3·2H2O being 7∶1 and 2∶1, multiple absorption peaks of νCO are observed. The IR spectral variations indicated that there are coordination interactions between Eu3+ ions and the carbonyl groups of PVP, and multiple coordination fashion exists. TEM results showed that there are microphase separation structures in PVP/Eu(TTA)3·2H2O and PVP/Eu(TTA)3·(TPPO)2 composites. The microphase separation phenomenon in composite of PVP/Eu(TTA)3·(TPPO)2 is more obvious than that of the PVP/Eu(TTA)3·2H2O. And the Europium complexes are in amorphous state, which further proved the interactions between PVP molecules and the rare earth fluorescence complexes Eu(TTA)3·2H2O and Eu(TTA)3·(TPPO)2.
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