发光学报, 2013, 34 (3): 268, 网络出版: 2013-04-07  

萘甲酸功能化的聚苯乙烯与Eu(Ⅲ)离子所形成的高分子-稀土配合物的荧光发射特性

Florescence Emission Character of Polymer-Rare Earth Ion Complex Formed by Naphthoic Acid-functionalized Polystyrene and Eu(Ⅲ)
作者单位
中北大学 化学工程系, 山西 太原030051
摘要
通过大分子反应将萘甲酸(NA)键合在聚苯乙烯(PS)侧链, 制得萘甲酸功能化的聚苯乙烯PSNA。 以PSNA为大分子配基, 以邻菲罗啉(Phen)为小分子配体, 与Eu(Ⅲ)离子配位, 分别制备了高分子-稀土二元发光配合物PS-(NA)3-Eu(Ⅲ)与高分子-稀土三元发光配合物PS-(NA)3-Eu(Ⅲ)-Phen。 采用红外光谱(FTIR)和紫外吸收光(UV)谱对配合物进行了表征, 深入研究了配合物的化学结构与发光性能的关系, 并应用Antenna效应理论, 从微观机理上进行了深入分析。 制备了配合物的固体薄膜, 考察了固体薄膜的荧光发射性能。 研究结果表明, 大分子配基PSNA与Eu(Ⅲ)离子所形成的二元或三元高分子-稀土配合物, 均能发射出很强的Eu(Ⅲ)离子的特征荧光, 即键合在PSNA侧链的配基NA能有效地敏化Eu(Ⅲ)离子的荧光发射。 大分子侧链的萘甲酸配基比苯甲酸配基对Eu(Ⅲ)离子荧光发射具有更强的敏化作用。 第二配体的协同配位效应导致三元配合物的荧光发射强度高于二元配合物。
Abstract
Naphthoic acid (NA) ligand was bonded on the side chains of polystyrene (PS) via a polymer reaction, obtaining naphthoic acid-functionalized polystyrene PSNA. The luminous secondary polymer-rare earth complex PS-(NA)3-Eu(Ⅲ) and the ternary complexe PS-(NA)3-Eu(Ⅲ)-Phen were prepared by the coordination of Eu(Ⅲ) ion, respectively, by using PSNA as a macromolecular ligand and small molecular phenanthroline (Phen) as the second ligand. The chemical structures of these complexes were characterized by FTIR and UV absorption spectra, and their florescence emission characters were examined, and especially, the relationship between their florescence emission properties and chemical structures was investigated in depth, and the corresponding microcosmic mechanism was described with Antenna effect theory. The experimental results show that the secondary and ternary complexes formed by the coordination of PSNA and Eu(Ⅲ) ion can emit the strong characteristic fluorescence of Eu(Ⅲ) ion, implying that the NA ligand bonded on the side chains of PSNA can effectively sensitized the fluorescence emission of Eu(Ⅲ) ion. The NA ligand bonded on the side chains of PSNA has stronger sensibilization than benzoic acid (BA) ligand. The florescence emission intensity of the ternary complex is stronger than that of the secondary complex due to the synergism coordination effect of the first and second ligands.

赵兴龙, 高保娇, 丁浩. 萘甲酸功能化的聚苯乙烯与Eu(Ⅲ)离子所形成的高分子-稀土配合物的荧光发射特性[J]. 发光学报, 2013, 34(3): 268. ZHAO Xing-long, GAO Bao-jiao, DING Hao. Florescence Emission Character of Polymer-Rare Earth Ion Complex Formed by Naphthoic Acid-functionalized Polystyrene and Eu(Ⅲ)[J]. Chinese Journal of Luminescence, 2013, 34(3): 268.

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