Peng Chunyun, Zhang Hongjie, Yu Jiangbo, Meng Qingguo, Fu Lianshe, Li Huanrong, Sun Lining, Guo Xianmin
Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022, People's Republic of China.
J Phys Chem B. 2005 Aug 18;109(32):15278-87. doi: 10.1021/jp051984n.
A novel mesoporous SBA-15 type of hybrid material (phen-SBA-15) covalently bonded with 1,10-phenanthroline (phen) ligand was synthesized by co-condensation of tetraethoxysilane (TEOS) and the chelate ligand 5-[N,N-bis-3-(triethoxysilyl)propyl]ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as a template. The preservation of the chelate ligand structure during the hydrothermal synthesis and the surfactant extraction process was confirmed by Fourier transform infrared (FTIR) and (29)Si MAS NMR spectroscopies. SBA-15 consisting of the highly luminescent ternary complex Eu(TTA)(3)phen (TTA = 2-thenoyltrifluoroacetone) covalently bonded to a silica-based network, which was designated as Eu(TTA)(3)phen-SBA-15, was obtained by introducing the Eu(TTA)(3).2H(2)O complex into the hybrid materials via a ligand exchange reaction. XRD, TEM, and N(2) adsorption measurements were employed to characterize the mesostructure of Eu(TTA)(3)phen-SBA-15. For comparison, SBA-15 doped with Eu(TTA)(3).2H(2)O and Eu(TTA)(3)phen complexes and SBA-15 covalently bonded with a binary europium complex with phen ligand were also synthesized, and were named SBA-15/Eu(TTA)(3), SBA-15/Eu(TTA)(3)phen, and Eu-phen-SBA-15, respectively. The detailed luminescence studies on all the materials showed that, compared with the doping sample SBA-15/Eu(TTA)(3)phen and binary europium complex functionalized sample Eu-phen-SBA-15, the Eu(TTA)(3)phen-SBA-15 mesoporous hybrid material exhibited higher luminescence intensity and emission quantum efficiency. Thermogravimetric analysis on Eu(TTA)(3)phen-SBA-15 demonstrated that the thermal stability of the lanthanide complex was evidently improved as it was covalently bonded to the mesoporous SBA-15 matrix.
通过在作为模板的Pluronic P123表面活性剂存在下，使四乙氧基硅烷（TEOS）与螯合配体5-[N,N-双-3-(三乙氧基甲硅烷基)丙基]脲基-1,10-菲咯啉（phen-Si）共缩合，合成了一种与1,10-菲咯啉（phen）配体共价键合的新型介孔SBA-15型杂化材料（phen-SBA-15）。通过傅里叶变换红外光谱（FTIR）和（29）Si MAS NMR光谱证实了在水热合成和表面活性剂萃取过程中螯合配体结构得以保留。通过配体交换反应将Eu(TTA)₃·2H₂O配合物引入杂化材料中，得到了由共价键合到二氧化硅基网络上的高发光三元配合物Eu(TTA)₃phen（TTA = 2-噻吩甲酰三氟丙酮）组成的SBA-15，将其命名为Eu(TTA)₃phen-SBA-15。采用XRD、TEM和N₂吸附测量对Eu(TTA)₃phen-SBA-15的介观结构进行了表征。为作比较，还合成了掺杂Eu(TTA)₃·2H₂O和Eu(TTA)₃phen配合物的SBA-15以及与含phen配体的二元铕配合物共价键合的SBA-15，分别命名为SBA-15/Eu(TTA)₃、SBA-15/Eu(TTA)₃phen和Eu-phen-SBA-15。对所有材料的详细发光研究表明，与掺杂样品SBA-15/Eu(TTA)₃phen和二元铕配合物功能化样品Eu-phen-SBA-15相比，Eu(TTA)₃phen-SBA-15介孔杂化材料表现出更高的发光强度和发射量子效率。对Eu(TTA)₃phen-SBA-15的热重分析表明，镧系配合物与介孔SBA-15基质共价键合后，其热稳定性明显提高。
