Zhang Dandan, Gao Baojiao, Li Yanbin
Department of Chemical Engineering, North University of China, Taiyuan, People's Republic of China.
Luminescence. 2017 Aug;32(5):855-865. doi: 10.1002/bio.3264. Epub 2017 Jan 24.
Using molecular design and polymer reactions, two types of bidentate Schiff base ligands, salicylaldehyde-aniline (SAN) and salicylaldehyde-cyclohexylamine (SCA), were synchronously synthesized and bonded onto the side chain of polysulfone (PSF), giving two bidentate Schiff base ligand-functionalized PSFs, PSF-SAN and PSF-SCA, referred to as macromolecular ligands. Following coordination reactions between the macromolecular ligands and Eu(III) and Tb(III) ions (the reaction occurred between the bonded ligands SAN or SCA and the lanthanide ion), two series of luminescent polymer-rare earth complexes, PSF-SAN-Eu(III) and PSF-SCA-Tb(III), were obtained. The two macromolecular ligands were fully characterized by Fourier transform infrared (FTIR), H NMR and UV absorption spectroscopy, and the prepared complexes were also characterized by FTIR, UV absorption spectroscopy and thermo-gravity analysis. On this basis, the photoluminescence properties of these complexes and the relationships between their structure and luminescence were investigated in depth. The results show that the bonded bidentate Schiff base ligands, SAN and SCA, can effectively sensitize the fluorescence emission of Eu(III) and Tb(III) ions, respectively. PSF-SAN-Eu(III) series complexes, namely the binary complex PSF-(SAN) -Eu(III) and the ternary complex PSF-(SAN) -Eu(III)-(Phen) (Phen is the small-molecule ligand 1,10-phenanthroline), produce strong red luminescence, suggesting that the triplet state energy level of SAN is lower and well matched with the resonant energy level of the Eu(III) ion. By contrast, PSF-SAN-Eu(III) series complexes, namely the binary complex PSF-(SCA) -Tb(III) and the ternary complex PSF-(SCA) -Tb(III)-(Phen) , display strong green luminescence, suggesting that the triplet state energy level of SCA is higher and is well matched with the resonant energy level of Tb(III).
通过分子设计和聚合物反应,同步合成了两种双齿席夫碱配体,即水杨醛 - 苯胺(SAN)和水杨醛 - 环己胺(SCA),并将它们键合到聚砜(PSF)的侧链上,得到了两种双齿席夫碱配体功能化的聚砜,即PSF - SAN和PSF - SCA,称为大分子配体。在大分子配体与Eu(III)和Tb(III)离子之间发生配位反应(反应发生在键合的配体SAN或SCA与镧系离子之间)后,得到了两个系列的发光聚合物 - 稀土配合物,即PSF - SAN - Eu(III)和PSF - SCA - Tb(III)。通过傅里叶变换红外光谱(FTIR)、核磁共振氢谱(¹H NMR)和紫外吸收光谱对这两种大分子配体进行了全面表征,同时通过FTIR、紫外吸收光谱和热重分析对制备的配合物进行了表征。在此基础上,深入研究了这些配合物的光致发光性能及其结构与发光之间的关系。结果表明,键合的双齿席夫碱配体SAN和SCA能够分别有效地敏化Eu(III)和Tb(III)离子的荧光发射。PSF - SAN - Eu(III)系列配合物,即二元配合物PSF - (SAN) - Eu(III)和三元配合物PSF - (SAN) - Eu(III) - (Phen)(Phen为小分子配体1,10 - 菲啰啉)产生强烈的红色发光,这表明SAN的三重态能级较低,与Eu(III)离子的共振能级匹配良好。相比之下,PSF - SCA - Tb(III)系列配合物,即二元配合物PSF - (SCA) - Tb(III)和三元配合物PSF - (SCA) - Tb(III) - (Phen),呈现出强烈的绿色发光,这表明SCA的三重态能级较高,与Tb(III)的共振能级匹配良好。