芳羧酸功能化的聚砜与Tb(III)形成的高分子-稀土配合物的结构与荧光发射性能

通过大分子反应将苯甲酸(BA)键合在聚砜(PSF)侧链,制得芳羧酸功能化的聚砜(PSFBA).以PSFBA为大分子配基,以邻菲啰啉(Phen)为小分子配体,与Tb(Ⅲ)配位,分别制备了二元配合物PSFBA-Tb(Ⅲ)与三元配合物PSFBA-Tb(Ⅲ)-Phen,采用傅里叶变换红外(FTIR)光谱和紫外(UV)吸收光谱对配合物进行了表征,深入研究了配合物(溶液与薄膜)的荧光发射性能及热稳定性与结构的关系.研究结果表明,以PSFBA为大分子配基所形成的高分子-稀土配合物,均能发射出很强的Tb(Ⅲ)特征荧光,即键合在PSFBA侧链的配基BA能有效地敏化Tb(Ⅲ)的荧光发射.二元配合物PSFBA-Tb(Ⅲ)的表观饱和配位数为10,即当二元配合物具有PSF-(BA)5-Tb(Ⅲ)的结构时,BA对Tb(Ⅲ)的配位表观上达到饱和,此时二元配合物具有最强的荧光发射.按n(Phen):n(Tb(Ⅲ))=1的比例将Phen加入二元配合物PSF-(BA)5-Tb(Ⅲ)溶液中进行补充配位,所制备的三元配合物PSF-(BA)5-Tb(Ⅲ)-(Phen)1与惯用比例的三元配合物PSF-(BA)1-Tb(Ⅲ)-(Phen)3或PSF-(BA)1-Tb(Ⅲ)-(Phen)2相比,不仅荧光发射强度高,而且热稳定性能好,是一种高性能的场致发光材料.

Structure and Florescence Emission Properties of a Polymer-Rare Earth Complex Composed of Aryl Carboxylic Acid-Functionalized Polysulfone and Tb(Ⅲ)

Benzoic acid (BA) was bonded to the side chains of polysulfone (PSF) via a polymer reaction,giving aryl carboxylic acid-functionalized polysulfone (PSFBA).The binary complex PSFBA-Tb(Ⅲ) and ternary complex PSFBA-Tb(Ⅲ)-phenanthroline (Phen) were prepared by the coordination of Tb(Ⅲ) to PSFBA using PSFBA as a macromolecular ligand and Phen as a smaller ligand.The chemical structures of the complexes were characterized by Fourier transform infrared (FTIR) and UV absorption spectroscopies.The relationships between the structure and properties,including the fluorescence emission properties,of the complexes in solution and films were investigated,as well as their thermal stability.All of the polymer-rare earth complexes containing PSFBA exhibited very strong characteristic fluorescence emission from Tb(Ⅲ),namely,BA bonded to the side chains of PSFBA can effectively sensitize Tb(Ⅲ).The apparent saturated coordination number of PSFBA-Tb(Ⅲ) is 10,which implies that the coordination of BA to Tb(Ⅲ) reaches saturation and maximum fluorescence is achieved for the complex PSF-(BA)5-Tb(Ⅲ).The ternary complex PSF-(BA)5-Tb(Ⅲ)-(Phen)1,which is prepared by adding Phen to a solution of PSF-(BA)5-Tb(Ⅲ),possesses the strongest fluorescence emission and excellent thermal stability compared with ternary complexes PSF-(BA)1-Tb(Ⅲ)-(Phen)3 and PSF-(BA)1-Tb(Ⅲ)-(Phen)2,which were prepared using the conventional ratios of reagents.